-
-
Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
期刊内检索
期刊内热点文章
期刊内下载排行
-
1
Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
- 2
-
3
Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
-
4
Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
-
5
Superiority of poly(L-lactic acid) microspheres as dermal fillers
2026, 37(4): 110726
doi: 10.1016/j.cclet.2024.110726
摘要:
Rechargeable aqueous zinc-ion batteries (AZIBs) have received considerable attention in recent years because of their high safety, low cost, and environmental friendliness. The properties of cathode materials are vital for the further development of AZIBs. Graphene-based composite materials have emerged as promising cathode materials for AZIBs on account of their superior electrical conductivity and excellent electrochemical performance. Considering the rapidly progress of graphene-based composites, we comprehensively summarize the recent progress in the applications of graphene-based composites as the cathode in AZIBs. Furthermore, the relationships between their synthetic methods, nano- and microstructures, and electrochemical performance are systematically concluded and discussed. Finally, rational suggestions and prospects for the future development of graphene-based composites are also proposed.
Rechargeable aqueous zinc-ion batteries (AZIBs) have received considerable attention in recent years because of their high safety, low cost, and environmental friendliness. The properties of cathode materials are vital for the further development of AZIBs. Graphene-based composite materials have emerged as promising cathode materials for AZIBs on account of their superior electrical conductivity and excellent electrochemical performance. Considering the rapidly progress of graphene-based composites, we comprehensively summarize the recent progress in the applications of graphene-based composites as the cathode in AZIBs. Furthermore, the relationships between their synthetic methods, nano- and microstructures, and electrochemical performance are systematically concluded and discussed. Finally, rational suggestions and prospects for the future development of graphene-based composites are also proposed.
2026, 37(4): 110790
doi: 10.1016/j.cclet.2024.110790
摘要:
Alkali metal-ion batteries, such as lithium-ion and sodium-ion batteries, have been widely recognized by both academia and industry for their high energy density, long cycle life, low self-discharge rate, and environmental friendliness. Theoretical calculations are crucial in elucidating the energy storage mechanism of alkali metal-ion batteries and in designing the next generation of high-performance energy storage systems. This article reviews the application of theoretical calculations in alkali metal-ion batteries. These calculations are instrumental for experimental researchers in understanding the microscopic design of electrode materials, optimizing various interfaces and electrolyte structures, and clarifying ion and electron transport behaviors as well as electrochemical reaction mechanisms. Specifically, researchers typically calculate the reduction reactions, charge state changes, and structural changes of cathode materials to predict their electrochemical reactivity and optimize their performance and stability. Calculations and simulations of alkali metal batteries focus on ion transport dynamics within the electrolyte, including energy level distribution, solvation structure, and molecular dynamics simulations. Analyzing oxidation reactions, ion diffusion, and volume changes in various alkali metal-ion battery anode materials enables the screening and design of new anode materials with superior electrochemical properties. This review also discusses the challenges of applying theoretical calculations in alkali metal-ion batteries and provides an outlook for future research. Critical insights are offered for advancing research paradigms that integrate theoretical and experimental approaches in the development of energy storage electrode materials.
Alkali metal-ion batteries, such as lithium-ion and sodium-ion batteries, have been widely recognized by both academia and industry for their high energy density, long cycle life, low self-discharge rate, and environmental friendliness. Theoretical calculations are crucial in elucidating the energy storage mechanism of alkali metal-ion batteries and in designing the next generation of high-performance energy storage systems. This article reviews the application of theoretical calculations in alkali metal-ion batteries. These calculations are instrumental for experimental researchers in understanding the microscopic design of electrode materials, optimizing various interfaces and electrolyte structures, and clarifying ion and electron transport behaviors as well as electrochemical reaction mechanisms. Specifically, researchers typically calculate the reduction reactions, charge state changes, and structural changes of cathode materials to predict their electrochemical reactivity and optimize their performance and stability. Calculations and simulations of alkali metal batteries focus on ion transport dynamics within the electrolyte, including energy level distribution, solvation structure, and molecular dynamics simulations. Analyzing oxidation reactions, ion diffusion, and volume changes in various alkali metal-ion battery anode materials enables the screening and design of new anode materials with superior electrochemical properties. This review also discusses the challenges of applying theoretical calculations in alkali metal-ion batteries and provides an outlook for future research. Critical insights are offered for advancing research paradigms that integrate theoretical and experimental approaches in the development of energy storage electrode materials.
2026, 37(4): 110791
doi: 10.1016/j.cclet.2024.110791
摘要:
Chirality, a fundamental property of biological systems, is widely present at the molecular, cellular, and tissue levels. Current studies have shown that chiral inorganic nanomaterials, have good chiral optical activity as well as high enantioselectivity. When interacting with biological systems, the enantioselective behavior of chiral inorganic nanomaterials towards biomolecules can distinguish between different isomers of biomarkers, which, combined with the excellent optical activity of chiral inorganic nanomaterials, allows for the rapid and sensitive detection of biomarkers. Moreover, chiral inorganic nanomaterials exhibit stronger internalization and retention capabilities in cells, and by specifically targeting specific biomarkers can regulate cellular activity and catalyze related reactions, thereby achieving synergistic treatment of various diseases. In addition, chiral inorganic nanomaterials also have good biocompatibility and do not cause cell damage in living organisms. Moreover, chiral inorganic nanomaterials have programmable surfaces that can be tailored to suit specific biological functions. Due to the important role of chiral inorganic nanomaterials in the biomedical field, this paper summarizes and discusses the synthesis and biomedical applications of chiral inorganic nanomaterials. It further looks forward to its future development prospects to provide a reference for promoting relevant research on chiral inorganic nanomaterials in biomedical fields.
Chirality, a fundamental property of biological systems, is widely present at the molecular, cellular, and tissue levels. Current studies have shown that chiral inorganic nanomaterials, have good chiral optical activity as well as high enantioselectivity. When interacting with biological systems, the enantioselective behavior of chiral inorganic nanomaterials towards biomolecules can distinguish between different isomers of biomarkers, which, combined with the excellent optical activity of chiral inorganic nanomaterials, allows for the rapid and sensitive detection of biomarkers. Moreover, chiral inorganic nanomaterials exhibit stronger internalization and retention capabilities in cells, and by specifically targeting specific biomarkers can regulate cellular activity and catalyze related reactions, thereby achieving synergistic treatment of various diseases. In addition, chiral inorganic nanomaterials also have good biocompatibility and do not cause cell damage in living organisms. Moreover, chiral inorganic nanomaterials have programmable surfaces that can be tailored to suit specific biological functions. Due to the important role of chiral inorganic nanomaterials in the biomedical field, this paper summarizes and discusses the synthesis and biomedical applications of chiral inorganic nanomaterials. It further looks forward to its future development prospects to provide a reference for promoting relevant research on chiral inorganic nanomaterials in biomedical fields.
2026, 37(4): 110972
doi: 10.1016/j.cclet.2025.110972
摘要:
With the increasing demand for high-energy-density lithium ion batteries, it has become increasingly imperative to address the safety concerns associated with batteries. At present, the design of flame-retardant electrolytes has been widely studied. However, most strategies lack the discussion of battery-level safety, and have only conducted primary safety tests such as ignition. In this situation, it is necessary to analyze the intrinsic link between flame-retardant electrolytes and battery safety. This paper elucidates the role of flame-retardant electrolytes in the thermal runaway process of batteries and proposes a strategy to enhance the safety of batteries from the aspect of electrolytes. Then the thermal, electrochemical and interfacial stability characteristics of different flame-retardant electrolytes are analyzed in detail based on their structures, and the basic principles for the design of their solvent structures are pointed out to enhance electrochemical performance. Furthermore, a prospective summary of safety characterization at the material and battery level is presented, aiming to build a comprehensive battery safety characterization system. This review provides insights into the design of flame-retardant electrolytes for high safety batteries.
With the increasing demand for high-energy-density lithium ion batteries, it has become increasingly imperative to address the safety concerns associated with batteries. At present, the design of flame-retardant electrolytes has been widely studied. However, most strategies lack the discussion of battery-level safety, and have only conducted primary safety tests such as ignition. In this situation, it is necessary to analyze the intrinsic link between flame-retardant electrolytes and battery safety. This paper elucidates the role of flame-retardant electrolytes in the thermal runaway process of batteries and proposes a strategy to enhance the safety of batteries from the aspect of electrolytes. Then the thermal, electrochemical and interfacial stability characteristics of different flame-retardant electrolytes are analyzed in detail based on their structures, and the basic principles for the design of their solvent structures are pointed out to enhance electrochemical performance. Furthermore, a prospective summary of safety characterization at the material and battery level is presented, aiming to build a comprehensive battery safety characterization system. This review provides insights into the design of flame-retardant electrolytes for high safety batteries.
2026, 37(4): 111013
doi: 10.1016/j.cclet.2025.111013
摘要:
Traditional chemotherapeutic approaches lack selectivity and damage both cancerous and healthy cells. In contrast, cancer immunotherapy harnesses the host's immune system to selectively target and eradicate tumor cells, offering tremendous potential for the long-term suppression of tumor growth and preventing its recurrence. However, tumors often develop immune evasion by exploiting immune checkpoints, which regulate the immune system. Among these checkpoints, programmed death protein 1 (PD-1) and its ligand (PD-L1) have garnered significant interest because they play a key role in protecting the tumor cells from immune-mediated eradication. The approval of monoclonal antibodies (mAbs) that target PD-1/PD-L1 by the Food and Drug Administration (FDA) is a milestone in immunotherapy. Although mAbs have demonstrated remarkable success in treating skin melanomas, their efficacy against other solid tumors remains limited. There is a clear need to explore new approaches to enhance the efficacy of mAbs and find more effective checkpoint inhibitors. Metal-based drugs offer a new platform to address this challenge. This review highlights the recent progress in leveraging metal complexes as PD-1/PD-L1 inhibitors. We discussed metal-based agents used either alone or in combination with mAbs to boost the immune system. We also highlighted examples of metallodrugs encapsulated within the nanoparticles to augment the efficacy of immune checkpoint therapy. While research on metal-based complexes targeting PD-1/PD-L1 is still in its infancy, the examples presented here will serve as the basis for future discussions and efforts in this emerging field. We anticipate that ongoing research in targeting immune checkpoint blockade with innovative metal-based therapeutics will enhance the scope of treatment across a wide range of cancers.
Traditional chemotherapeutic approaches lack selectivity and damage both cancerous and healthy cells. In contrast, cancer immunotherapy harnesses the host's immune system to selectively target and eradicate tumor cells, offering tremendous potential for the long-term suppression of tumor growth and preventing its recurrence. However, tumors often develop immune evasion by exploiting immune checkpoints, which regulate the immune system. Among these checkpoints, programmed death protein 1 (PD-1) and its ligand (PD-L1) have garnered significant interest because they play a key role in protecting the tumor cells from immune-mediated eradication. The approval of monoclonal antibodies (mAbs) that target PD-1/PD-L1 by the Food and Drug Administration (FDA) is a milestone in immunotherapy. Although mAbs have demonstrated remarkable success in treating skin melanomas, their efficacy against other solid tumors remains limited. There is a clear need to explore new approaches to enhance the efficacy of mAbs and find more effective checkpoint inhibitors. Metal-based drugs offer a new platform to address this challenge. This review highlights the recent progress in leveraging metal complexes as PD-1/PD-L1 inhibitors. We discussed metal-based agents used either alone or in combination with mAbs to boost the immune system. We also highlighted examples of metallodrugs encapsulated within the nanoparticles to augment the efficacy of immune checkpoint therapy. While research on metal-based complexes targeting PD-1/PD-L1 is still in its infancy, the examples presented here will serve as the basis for future discussions and efforts in this emerging field. We anticipate that ongoing research in targeting immune checkpoint blockade with innovative metal-based therapeutics will enhance the scope of treatment across a wide range of cancers.
2026, 37(4): 111076
doi: 10.1016/j.cclet.2025.111076
摘要:
Understanding the mechanisms of virus infection is pivotal for the effective prevention and treatment of viral diseases. This review provides a comprehensive overview of the latest advancements in real-time monitoring of viral dynamics within established infection models. We begin by summarizing the recent progress in fluorescent probe and labeling techniques for real-time and in situ virus tracking. Next, we provide an in-depth analysis of the types and characteristics of virus infection models and discuss their respective advantages and limitations in virus tracking. Finally, we detail the recent progress in viral dynamics tracking across different infection models, illustrating how to use these models to monitor virus infection dynamics and discussing the meaningful biological information that can be acquired.
Understanding the mechanisms of virus infection is pivotal for the effective prevention and treatment of viral diseases. This review provides a comprehensive overview of the latest advancements in real-time monitoring of viral dynamics within established infection models. We begin by summarizing the recent progress in fluorescent probe and labeling techniques for real-time and in situ virus tracking. Next, we provide an in-depth analysis of the types and characteristics of virus infection models and discuss their respective advantages and limitations in virus tracking. Finally, we detail the recent progress in viral dynamics tracking across different infection models, illustrating how to use these models to monitor virus infection dynamics and discussing the meaningful biological information that can be acquired.
2026, 37(4): 111140
doi: 10.1016/j.cclet.2025.111140
摘要:
Bone-related diseases resulting from accidents, illnesses, and injuries have become increasingly common in recent years. Treating these conditions poses significant challenges, including prolonged recovery times, high costs, and unpredictable outcomes, which can lead to complications such as infections and reduced muscle strength. Although autologous bone transplantation is regarded as the "gold standard" for addressing bone diseases, its application is often limited by complications at the donor site and the risk of infection. This underscores the urgent need to explore alternatives to autogenous bone transplantation. In response, a range of biomaterials for bone repair have been developed, with metal-based biomaterials emerging as effective adjuncts that enhance and optimize the repair and regeneration of bone tissue. These materials can actively influence the bone repair process through mechanisms such as inductive osteogenesis, immunomodulation, and pro-angiogenesis. This review begins by highlighting the biological effects of metal-based biomaterials, followed by a comprehensive overview of their macro- and micro-scale classifications and applications for treating various bone diseases. Finally, the review addresses future directions and challenges associated with the use of metal-based biomaterials in bone repair, aiming to propose promising strategies for the treatment of bone-related diseases.
Bone-related diseases resulting from accidents, illnesses, and injuries have become increasingly common in recent years. Treating these conditions poses significant challenges, including prolonged recovery times, high costs, and unpredictable outcomes, which can lead to complications such as infections and reduced muscle strength. Although autologous bone transplantation is regarded as the "gold standard" for addressing bone diseases, its application is often limited by complications at the donor site and the risk of infection. This underscores the urgent need to explore alternatives to autogenous bone transplantation. In response, a range of biomaterials for bone repair have been developed, with metal-based biomaterials emerging as effective adjuncts that enhance and optimize the repair and regeneration of bone tissue. These materials can actively influence the bone repair process through mechanisms such as inductive osteogenesis, immunomodulation, and pro-angiogenesis. This review begins by highlighting the biological effects of metal-based biomaterials, followed by a comprehensive overview of their macro- and micro-scale classifications and applications for treating various bone diseases. Finally, the review addresses future directions and challenges associated with the use of metal-based biomaterials in bone repair, aiming to propose promising strategies for the treatment of bone-related diseases.
2026, 37(4): 111600
doi: 10.1016/j.cclet.2025.111600
摘要:
Iron-based nanoparticles (Fe-NPs) have wide environmental applications in various areas due to their excellent physicochemical properties, and these processes also increase their release into the water environment. However, the existing literature on environmental behavior fate (e.g., sorption and transformation) and potential ecotoxicity of Fe-NPs remains limited, which is vital for understanding the Fe-NPs environmental behavior and application as a multifunctional product. In this review, the green synthesis, characterization, and environmental application of Fe-NPs are summarized. We systematically examined the impacts of Fe-NPs physicochemical properties on its adsorption, transformation (e.g., aggregation dispersion, dissolution, oxidation), and biodegradation behavior in aqueous ecosystems. Moreover, we highlight the potential ecological toxicity of Fe-NPs to aquatic organisms. Upon exposure in water environments, Fe-NPs have potential ecological toxicity on aquatic organisms (e.g., microorganisms, plants, zooplankton, and fish). The common mechanisms of Fe-NPs ecotoxicity (e.g., bioaccumulation, oxidation stress, and DNA damage) at the cellular level are presented and the remaining unclear points on nano-toxic mechanisms (e.g., metabolic disturbance, genotoxicity) are discussed. Given the unresolved issues, the substantial gaps and the environmental risk assessment of Fe-NPs require further attention in the future. This paper will provide useful information for assessing the fate and potential ecological risks associated with Fe-NPs in aquatic environments.
Iron-based nanoparticles (Fe-NPs) have wide environmental applications in various areas due to their excellent physicochemical properties, and these processes also increase their release into the water environment. However, the existing literature on environmental behavior fate (e.g., sorption and transformation) and potential ecotoxicity of Fe-NPs remains limited, which is vital for understanding the Fe-NPs environmental behavior and application as a multifunctional product. In this review, the green synthesis, characterization, and environmental application of Fe-NPs are summarized. We systematically examined the impacts of Fe-NPs physicochemical properties on its adsorption, transformation (e.g., aggregation dispersion, dissolution, oxidation), and biodegradation behavior in aqueous ecosystems. Moreover, we highlight the potential ecological toxicity of Fe-NPs to aquatic organisms. Upon exposure in water environments, Fe-NPs have potential ecological toxicity on aquatic organisms (e.g., microorganisms, plants, zooplankton, and fish). The common mechanisms of Fe-NPs ecotoxicity (e.g., bioaccumulation, oxidation stress, and DNA damage) at the cellular level are presented and the remaining unclear points on nano-toxic mechanisms (e.g., metabolic disturbance, genotoxicity) are discussed. Given the unresolved issues, the substantial gaps and the environmental risk assessment of Fe-NPs require further attention in the future. This paper will provide useful information for assessing the fate and potential ecological risks associated with Fe-NPs in aquatic environments.
2026, 37(4): 111611
doi: 10.1016/j.cclet.2025.111611
摘要:
Conjugated microporous polymers (CMPs) are a class of materials characterized by their rigid π-conjugated network, adjustable microporous structures, and high mechanical strength. Due to these exceptional structural features, CMPs have demonstrated outstanding potential and performance in molecular separation, energy storage, sensors, optoelectronic devices, and catalysts. It has garnered significant attention. However, despite the considerable attention and work paid to synthesizing CMP, the challenges associated with processing it in powders are frequently disregarded. Thus, future advancements must focus on developing strategies to obtain CMPs as film form and how they performed when they are integrated in devices such as batteries, LEDs, supercapacitors, sensors, and solar cells. This paper provides a comprehensive and detailed review of the most recent advances in fabrication strategies and their applications for CMP films as well as the challenges.
Conjugated microporous polymers (CMPs) are a class of materials characterized by their rigid π-conjugated network, adjustable microporous structures, and high mechanical strength. Due to these exceptional structural features, CMPs have demonstrated outstanding potential and performance in molecular separation, energy storage, sensors, optoelectronic devices, and catalysts. It has garnered significant attention. However, despite the considerable attention and work paid to synthesizing CMP, the challenges associated with processing it in powders are frequently disregarded. Thus, future advancements must focus on developing strategies to obtain CMPs as film form and how they performed when they are integrated in devices such as batteries, LEDs, supercapacitors, sensors, and solar cells. This paper provides a comprehensive and detailed review of the most recent advances in fabrication strategies and their applications for CMP films as well as the challenges.
2026, 37(4): 111632
doi: 10.1016/j.cclet.2025.111632
摘要:
Most bioactive compounds (amino acids, sugars, peptides, proteins) and drugs are chiral. Although the enantiomers have similar physical and chemical properties, they may exhibit completely different physiological effects in terms of biological activity, toxicity, and pharmacological effects. Therefore, chiral recognition is particularly important in numerous fields. Surface-enhanced Raman scattering (SERS) spectroscopy, a promising nondestructive analytical technique with wide applications in biosensing, food safety, and environmental analysis, exhibits exceptional potential for chiral recognition. However, there remains a notable scarcity of comprehensive reviews focusing on SERS-based chiral recognition. This review introduced the development of SERS and summarized the classification of chiral enantiomers recognition by SERS spectroscopy in detail in the past 10 years, mainly including EM-dominated chiral substrates, chiral ligand-modified systems, charge transfer (CT)-based "chiral-label-free" approaches, and chiral molecularly imprinted strategies. In addition, the potential challenges and prospects in SERS spectroscopy for chiral recognition are proposed, which is expected to effectively guide future research.
Most bioactive compounds (amino acids, sugars, peptides, proteins) and drugs are chiral. Although the enantiomers have similar physical and chemical properties, they may exhibit completely different physiological effects in terms of biological activity, toxicity, and pharmacological effects. Therefore, chiral recognition is particularly important in numerous fields. Surface-enhanced Raman scattering (SERS) spectroscopy, a promising nondestructive analytical technique with wide applications in biosensing, food safety, and environmental analysis, exhibits exceptional potential for chiral recognition. However, there remains a notable scarcity of comprehensive reviews focusing on SERS-based chiral recognition. This review introduced the development of SERS and summarized the classification of chiral enantiomers recognition by SERS spectroscopy in detail in the past 10 years, mainly including EM-dominated chiral substrates, chiral ligand-modified systems, charge transfer (CT)-based "chiral-label-free" approaches, and chiral molecularly imprinted strategies. In addition, the potential challenges and prospects in SERS spectroscopy for chiral recognition are proposed, which is expected to effectively guide future research.
2026, 37(4): 111637
doi: 10.1016/j.cclet.2025.111637
摘要:
Electrocatalysis stands as a cornerstone in the pursuit of clean energy conversion and environmental sustainability, with single-atom catalysts (SACs) emerging as a transformative paradigm for enhancing electrocatalytic efficiency. In the architectural design of SACs, supports transcend conventional roles as mere supports, actively governing catalytic performance via robust metal-support interactions (SMSI). This review comprehensively analyses the key role of support engineering in modulating SACs performance. The study begins with a systematic assessment of currently popular SACs synthesis strategies, critically comparing their advantages and limitations. Through a hierarchical analysis, it reveals the impact of various support materials, such as carbon-based materials, metal oxides, MXenes, and metal-organic frameworks (MOFs), on the catalytic performance of SACs, with emphasis on their structural characteristics, electronic properties, and interaction mechanisms with active sites. The review further explores applications in energy conversion/storage and environmental remediation, while addressing current challenges and proposing future research directions for SACs development. By providing actionable insights, this work aims to guide the design of next-generation SACs and advance sustainable electrocatalysis.
Electrocatalysis stands as a cornerstone in the pursuit of clean energy conversion and environmental sustainability, with single-atom catalysts (SACs) emerging as a transformative paradigm for enhancing electrocatalytic efficiency. In the architectural design of SACs, supports transcend conventional roles as mere supports, actively governing catalytic performance via robust metal-support interactions (SMSI). This review comprehensively analyses the key role of support engineering in modulating SACs performance. The study begins with a systematic assessment of currently popular SACs synthesis strategies, critically comparing their advantages and limitations. Through a hierarchical analysis, it reveals the impact of various support materials, such as carbon-based materials, metal oxides, MXenes, and metal-organic frameworks (MOFs), on the catalytic performance of SACs, with emphasis on their structural characteristics, electronic properties, and interaction mechanisms with active sites. The review further explores applications in energy conversion/storage and environmental remediation, while addressing current challenges and proposing future research directions for SACs development. By providing actionable insights, this work aims to guide the design of next-generation SACs and advance sustainable electrocatalysis.
2026, 37(4): 111669
doi: 10.1016/j.cclet.2025.111669
摘要:
Sustainable and efficient solutions are essential to address increasingly critical environmental issues, particularly in the field of pollutant removal and resource recovery. The latest research has shown that pulsed electrochemistry significantly contributes to these goals by precisely altering the local reaction environment, accelerating the reaction kinetics and decreasing the overall energy requirements. However, knowledge gaps exist in dynamic evolution mechanism of electric double layer (EDL) in this technology, and challenges remain toward fully implementation of this promising technology. In this review, the fundamentals of pulsed electrochemistry and its connection to the theoretical models of EDL are comprehensively presented. The critical parameters (e.g., duty ratio, frequency and waveform) for boosting the performance of the system are systematically discussed and the typical electrochemical reactions that occur with pulsed electrochemistry are outlined. The proposed pulsed electrochemistry methodologies tailored for environmental applications are also reviewed in detail. Finally, future opportunities and challenges of this promising but fledgling field are discussed, with the expectation that this technology offers a route to transform conventional chemical industries into cleaner and more sustainable production.
Sustainable and efficient solutions are essential to address increasingly critical environmental issues, particularly in the field of pollutant removal and resource recovery. The latest research has shown that pulsed electrochemistry significantly contributes to these goals by precisely altering the local reaction environment, accelerating the reaction kinetics and decreasing the overall energy requirements. However, knowledge gaps exist in dynamic evolution mechanism of electric double layer (EDL) in this technology, and challenges remain toward fully implementation of this promising technology. In this review, the fundamentals of pulsed electrochemistry and its connection to the theoretical models of EDL are comprehensively presented. The critical parameters (e.g., duty ratio, frequency and waveform) for boosting the performance of the system are systematically discussed and the typical electrochemical reactions that occur with pulsed electrochemistry are outlined. The proposed pulsed electrochemistry methodologies tailored for environmental applications are also reviewed in detail. Finally, future opportunities and challenges of this promising but fledgling field are discussed, with the expectation that this technology offers a route to transform conventional chemical industries into cleaner and more sustainable production.
2026, 37(4): 111733
doi: 10.1016/j.cclet.2025.111733
摘要:
Iron-based metal oxide catalysts are widely used for selective catalytic reduction (SCR) of NOx with NH3 due to their excellent catalytic performance at medium and high temperatures, high nitrogen selectivity, robust resistance to sulfur dioxide poisoning, environmental sustainability and cost effectiveness. However, several challenges including sub-optimal low-temperature catalytic activity, narrow operating temperature range, poor resistance to alkali/alkaline earth metal poisoning, as well as insufficient thermal stability and H2O/SO2 resistance always hinder the further application of iron-based metal oxide catalysts, which is in urgent need of further improvement in practical applications. This review provides a comprehensive overview of the development, applications and challenges associated with different types of iron-based metal oxide catalysts and suggests corresponding modification strategies to address the as-mentioned issues. Iron oxide catalysts can promote low-temperature catalytic performance by adjusting crystal structures and exposing specific crystal faces; however, their thermal stability and resistance to SO2/H2O and alkali metals still have substantial room for improvement. Iron-based composite metal oxide catalysts can effectively increase the resistance to SO2/H2O by coupling multiple metals and modulating adjacent electronic sites. Iron-based acidic salt catalysts greatly enhance the resistance to alkali metal poisoning by enriching the surface acid sites and providing sacrificial sites. Supported iron-based metal oxide catalysts can significantly improve both catalytic performance and resistance by modulating reaction pathways and constructing core-shell structures. This review clarifies the important direction of further research on iron-based metal oxide catalysts, and provides scientific basis and design ideas for the development and application of high-efficiency low-temperature NOx reduction catalysts.
Iron-based metal oxide catalysts are widely used for selective catalytic reduction (SCR) of NOx with NH3 due to their excellent catalytic performance at medium and high temperatures, high nitrogen selectivity, robust resistance to sulfur dioxide poisoning, environmental sustainability and cost effectiveness. However, several challenges including sub-optimal low-temperature catalytic activity, narrow operating temperature range, poor resistance to alkali/alkaline earth metal poisoning, as well as insufficient thermal stability and H2O/SO2 resistance always hinder the further application of iron-based metal oxide catalysts, which is in urgent need of further improvement in practical applications. This review provides a comprehensive overview of the development, applications and challenges associated with different types of iron-based metal oxide catalysts and suggests corresponding modification strategies to address the as-mentioned issues. Iron oxide catalysts can promote low-temperature catalytic performance by adjusting crystal structures and exposing specific crystal faces; however, their thermal stability and resistance to SO2/H2O and alkali metals still have substantial room for improvement. Iron-based composite metal oxide catalysts can effectively increase the resistance to SO2/H2O by coupling multiple metals and modulating adjacent electronic sites. Iron-based acidic salt catalysts greatly enhance the resistance to alkali metal poisoning by enriching the surface acid sites and providing sacrificial sites. Supported iron-based metal oxide catalysts can significantly improve both catalytic performance and resistance by modulating reaction pathways and constructing core-shell structures. This review clarifies the important direction of further research on iron-based metal oxide catalysts, and provides scientific basis and design ideas for the development and application of high-efficiency low-temperature NOx reduction catalysts.
2026, 37(4): 111742
doi: 10.1016/j.cclet.2025.111742
摘要:
The Maillard reaction (non-enzymatic browning reaction) is a complex reaction between carbonyl compounds such as reducing sugars, aldehydes and ketones and compounds containing free amino groups such as amino acids, peptides and proteins. This reaction not only affects product sensory qualities, but may also generate harmful substances such as acrylamide, polycyclic aromatic hydrocarbons, and advanced glycation end-products. These substances pose various health risks to humans, including carcinogenicity, neurotoxicity and diabetes mellitus. Therefore, monitoring the Maillard reaction process and precisely controlling reaction conditions are crucial for understanding its mechanism, optimizing product quality and ensuring product safety. This review systematically summarizes recent advancements in Maillard reaction research, outlining its fundamental processes and key influencing conditions, laying a foundation for the study of the monitoring methods of Maillard reaction process. Additionally, this review takes a cross-industry perspective to explore the applications of Maillard reaction monitoring methods (spectroscopic methods, chromatography/chromatography-mass spectrometry, electrochemical methods and nuclear magnetic resonance and enzyme linked immunosorbent assay) in various fields, including food industry, tobacco processing, biopharmaceuticals, materials science and textile dyeing. Through cross-industry applications, the challenges of monitoring the Maillard reaction process are analyzed, including the diversity of reaction products, complexity of sample preparation, and real-time monitoring. Future prospects are proposed through the challenges, including the development of advanced nanomaterials and biosensors, and the integration of machine learning into predictive modeling of reaction kinetics for application in industrial processes. The review aiming to provide valuable references and guidance for industrial safety production and process condition optimization.
The Maillard reaction (non-enzymatic browning reaction) is a complex reaction between carbonyl compounds such as reducing sugars, aldehydes and ketones and compounds containing free amino groups such as amino acids, peptides and proteins. This reaction not only affects product sensory qualities, but may also generate harmful substances such as acrylamide, polycyclic aromatic hydrocarbons, and advanced glycation end-products. These substances pose various health risks to humans, including carcinogenicity, neurotoxicity and diabetes mellitus. Therefore, monitoring the Maillard reaction process and precisely controlling reaction conditions are crucial for understanding its mechanism, optimizing product quality and ensuring product safety. This review systematically summarizes recent advancements in Maillard reaction research, outlining its fundamental processes and key influencing conditions, laying a foundation for the study of the monitoring methods of Maillard reaction process. Additionally, this review takes a cross-industry perspective to explore the applications of Maillard reaction monitoring methods (spectroscopic methods, chromatography/chromatography-mass spectrometry, electrochemical methods and nuclear magnetic resonance and enzyme linked immunosorbent assay) in various fields, including food industry, tobacco processing, biopharmaceuticals, materials science and textile dyeing. Through cross-industry applications, the challenges of monitoring the Maillard reaction process are analyzed, including the diversity of reaction products, complexity of sample preparation, and real-time monitoring. Future prospects are proposed through the challenges, including the development of advanced nanomaterials and biosensors, and the integration of machine learning into predictive modeling of reaction kinetics for application in industrial processes. The review aiming to provide valuable references and guidance for industrial safety production and process condition optimization.
2026, 37(4): 111850
doi: 10.1016/j.cclet.2025.111850
摘要:
Zinc ion hybrid capacitors (ZIHCs) are emerging electrochemical energy storage devices with the dual characteristics of high energy density and high power density. However, the mismatch of capacity and electrode kinetics between porous carbon cathodes and zinc metal anodes limits the development of ZIHCs. Lignin has high carbon content, high aromaticity, and three-dimensional functional molecular structures, which is an ideal raw material for preparing high-performance porous carbon electrode materials with high carbon yield, conductive carbon network and enriched heteroatom dopants. Currently, the high-value utilization ratio of industrial lignin is lower than 10%. In this review, the typical preparation methodologies of lignin-derived porous carbons are summarized. The latest research advances for the lignin-derived porous carbon cathodes in ZIHCs are critically focused from the perspectives of pore regulation, surface modification, and morphology design. The core points and development directions that lignin-derived porous carbon cathodes are expected to achieve an original breakthrough in the future are proposed from three levels of techniques, mechanisms, and applications. This review fills the blank region in the applications of lignin-derived porous carbons for ZIHCs, aiming to provide valuable guidance for the high-value utilization process of lignin and the industrialization process of ZIHCs.
Zinc ion hybrid capacitors (ZIHCs) are emerging electrochemical energy storage devices with the dual characteristics of high energy density and high power density. However, the mismatch of capacity and electrode kinetics between porous carbon cathodes and zinc metal anodes limits the development of ZIHCs. Lignin has high carbon content, high aromaticity, and three-dimensional functional molecular structures, which is an ideal raw material for preparing high-performance porous carbon electrode materials with high carbon yield, conductive carbon network and enriched heteroatom dopants. Currently, the high-value utilization ratio of industrial lignin is lower than 10%. In this review, the typical preparation methodologies of lignin-derived porous carbons are summarized. The latest research advances for the lignin-derived porous carbon cathodes in ZIHCs are critically focused from the perspectives of pore regulation, surface modification, and morphology design. The core points and development directions that lignin-derived porous carbon cathodes are expected to achieve an original breakthrough in the future are proposed from three levels of techniques, mechanisms, and applications. This review fills the blank region in the applications of lignin-derived porous carbons for ZIHCs, aiming to provide valuable guidance for the high-value utilization process of lignin and the industrialization process of ZIHCs.
2026, 37(4): 111892
doi: 10.1016/j.cclet.2025.111892
摘要:
Enantioselective enamine catalysis has enriched asymmetric synthesis by enabling precise stereochemical control. While classically thermal/photochemical strategies have expanded reaction diversity, electrochemical enantiocontrol remains underexplored despite its potential for tunable redox manipulation. This review systematically evaluates electrochemical enantioselective enamine catalysis through polar/radical mediated chemical bond formation pathways, aiming to delineate current mechanistic paradigms and highlight electrochemistry's unique role on asymmetric enamine catalysis beyond thermodynamic and photochemical conditions. Future efforts including developing enhanced compatibility of chiral catalysts and intermediates with electrochemical systems, as well as exploiting transformative techniques for mechanistic elucidation could be promising to unlock more novel transformations and stereoselectivity models.
Enantioselective enamine catalysis has enriched asymmetric synthesis by enabling precise stereochemical control. While classically thermal/photochemical strategies have expanded reaction diversity, electrochemical enantiocontrol remains underexplored despite its potential for tunable redox manipulation. This review systematically evaluates electrochemical enantioselective enamine catalysis through polar/radical mediated chemical bond formation pathways, aiming to delineate current mechanistic paradigms and highlight electrochemistry's unique role on asymmetric enamine catalysis beyond thermodynamic and photochemical conditions. Future efforts including developing enhanced compatibility of chiral catalysts and intermediates with electrochemical systems, as well as exploiting transformative techniques for mechanistic elucidation could be promising to unlock more novel transformations and stereoselectivity models.
2026, 37(4): 111955
doi: 10.1016/j.cclet.2025.111955
摘要:
Traditional cancer therapies are limited by side effects and damage to healthy tissues, while modern targeted treatments face challenges such as drug resistance and restricted applicability across cancer types. Early diagnosis also remains difficult, as many methods lack the sensitivity and specificity needed to reliably detect small, early-stage tumors. This review explores hybrid nanomaterial-based delivery systems, such as lipid–gold nanoparticle composites combined with polymeric nanocarriers, to improve the precision and efficacy of gene therapy. Advances in nanotechnology are highlighted for their ability to augment gene-editing tools including RNA interference and clustered regularly interspaced short palindromic repeats/CRISPR-associated protein 9 (CRISPR/Cas9), supported by techniques like optical tweezers, plasmonics, fluorescence imaging, and metamaterials. Nanophotonics in particular offers ultra-sensitive molecular imaging and real-time biomarker detection, underscoring its value for early cancer diagnosis. Artificial intelligence further strengthens these approaches by optimizing nanocarrier design, predicting therapeutic outcomes, and guiding personalized treatment strategies. Machine learning and deep learning platforms enable efficient analysis of complex genomic and clinical datasets, improving predictive accuracy and therapeutic customization. The review also outlines molecular mechanisms of gene therapy, from editing to expression, and addresses barriers to clinical translation, such as data integration, model validation, and regulatory considerations. Combining nanotechnology, artificial intelligence (AI), and gene-editing advances holds promise for more effective, targeted, and minimally invasive cancer treatments. These integrated strategies support earlier detection, enhance therapeutic precision, and provide a framework for translating experimental breakthroughs into clinical applications that better align with the goals of personalized medicine.
Traditional cancer therapies are limited by side effects and damage to healthy tissues, while modern targeted treatments face challenges such as drug resistance and restricted applicability across cancer types. Early diagnosis also remains difficult, as many methods lack the sensitivity and specificity needed to reliably detect small, early-stage tumors. This review explores hybrid nanomaterial-based delivery systems, such as lipid–gold nanoparticle composites combined with polymeric nanocarriers, to improve the precision and efficacy of gene therapy. Advances in nanotechnology are highlighted for their ability to augment gene-editing tools including RNA interference and clustered regularly interspaced short palindromic repeats/CRISPR-associated protein 9 (CRISPR/Cas9), supported by techniques like optical tweezers, plasmonics, fluorescence imaging, and metamaterials. Nanophotonics in particular offers ultra-sensitive molecular imaging and real-time biomarker detection, underscoring its value for early cancer diagnosis. Artificial intelligence further strengthens these approaches by optimizing nanocarrier design, predicting therapeutic outcomes, and guiding personalized treatment strategies. Machine learning and deep learning platforms enable efficient analysis of complex genomic and clinical datasets, improving predictive accuracy and therapeutic customization. The review also outlines molecular mechanisms of gene therapy, from editing to expression, and addresses barriers to clinical translation, such as data integration, model validation, and regulatory considerations. Combining nanotechnology, artificial intelligence (AI), and gene-editing advances holds promise for more effective, targeted, and minimally invasive cancer treatments. These integrated strategies support earlier detection, enhance therapeutic precision, and provide a framework for translating experimental breakthroughs into clinical applications that better align with the goals of personalized medicine.
2026, 37(4): 112036
doi: 10.1016/j.cclet.2025.112036
摘要:
In contrast to conventional cancer treatment modalities, cancer immunotherapy has increasingly emerged as one of the most promising therapeutic approaches for cancer, owing to its capacity to elicit long-lasting immune memory and its favorable safety profile. However, the immunosuppressive tumor microenvironment (ITME) significantly hinders its progression. While tumor stromal cells play a crucial role in the formation of the ITME, they also offer several potential targets for interventions aimed at reshaping this suppressive milieu. In clinical practice, the modulating of tumor stromal cells overcomes resistance mechanisms, exhibits broader therapeutic potential, and allows for more manageable toxicity profiles. Owing to the capacity of nanodrug delivery systems (nano-DDS) to facilitate accurate targeting and integrate multiple functions, a growing number of researchers are employing nano-DDS in the immunotherapy modulated to tumor stromal cells. This review begins by elucidating the roles played by different tumor stromal cells in the formation of the ITME. Subsequently, we provide the nanodelivery strategies modulating distinct tumor stromal cells. Finally, we propose the current challenges and discuss potential future development directions in this field.
In contrast to conventional cancer treatment modalities, cancer immunotherapy has increasingly emerged as one of the most promising therapeutic approaches for cancer, owing to its capacity to elicit long-lasting immune memory and its favorable safety profile. However, the immunosuppressive tumor microenvironment (ITME) significantly hinders its progression. While tumor stromal cells play a crucial role in the formation of the ITME, they also offer several potential targets for interventions aimed at reshaping this suppressive milieu. In clinical practice, the modulating of tumor stromal cells overcomes resistance mechanisms, exhibits broader therapeutic potential, and allows for more manageable toxicity profiles. Owing to the capacity of nanodrug delivery systems (nano-DDS) to facilitate accurate targeting and integrate multiple functions, a growing number of researchers are employing nano-DDS in the immunotherapy modulated to tumor stromal cells. This review begins by elucidating the roles played by different tumor stromal cells in the formation of the ITME. Subsequently, we provide the nanodelivery strategies modulating distinct tumor stromal cells. Finally, we propose the current challenges and discuss potential future development directions in this field.
2026, 37(4): 112220
doi: 10.1016/j.cclet.2025.112220
摘要:
Inspired by the natural synthesis of biomolecules, the artificial production of therapeutic agents within cells has emerged as a powerful and versatile approach for disease treatment. Performing artificial chemical reactions within living cells to achieve various physiological goals remains both an intriguing and highly challenging endeavor. This review summarizes recent advancements and future trends in the field of chemical reactions inside living cells, organized by different reaction mechanisms. We also provide an in-depth discussion of their chemical designs, reaction mechanisms, and functional applications. Furthermore, we explore the underlying chemical principles of these reactions and discuss strategies for these materials to enhance their therapeutic efficacy. As researchers continue to expand the repertoire of intracellular synthesis techniques, it is anticipated that these advancements will provide valuable tools for probing biological systems and developing innovative therapeutic strategies.
Inspired by the natural synthesis of biomolecules, the artificial production of therapeutic agents within cells has emerged as a powerful and versatile approach for disease treatment. Performing artificial chemical reactions within living cells to achieve various physiological goals remains both an intriguing and highly challenging endeavor. This review summarizes recent advancements and future trends in the field of chemical reactions inside living cells, organized by different reaction mechanisms. We also provide an in-depth discussion of their chemical designs, reaction mechanisms, and functional applications. Furthermore, we explore the underlying chemical principles of these reactions and discuss strategies for these materials to enhance their therapeutic efficacy. As researchers continue to expand the repertoire of intracellular synthesis techniques, it is anticipated that these advancements will provide valuable tools for probing biological systems and developing innovative therapeutic strategies.
2026, 37(4): 110733
doi: 10.1016/j.cclet.2024.110733
摘要:
Modulating the exposed facets of metal-organic frameworks (MOFs) is an effective strategy to enhance the synergistic effects between adsorption and photocatalytic reduction of U(Ⅵ). Herein, we successfully synthesized four morphologically distinct types of NH2-MIL-125(Ti), offering insights into the impact of facet engineering on the combined adsorption and photoreduction of U(Ⅵ). An elevated exposure ratio of the {001} facet endows NH2-MIL-125(Ti) with a larger surface area, enhanced light absorption, and efficient separation of photogenerated charge carriers. Among the four photocatalysts (W, D, S and T), T with a high proportion of {001} facets, demonstrated outstanding adsorption-photocatalytic synergy, achieving over 97% of U(Ⅵ) within 20 min of visible light irradiation across a broad concentrations and pH range, without requiring a hole-trapping agent. The uranium extraction mechanism involves U(Ⅵ) coordination and chelation with active sites during adsorption, followed by reduction to U(Ⅳ) via photogenerated electrons during photocatalysis. This study highlights the use of facet engineering to enhance adsorption and photocatalytic efficiency in MOF-based photocatalysts.
Modulating the exposed facets of metal-organic frameworks (MOFs) is an effective strategy to enhance the synergistic effects between adsorption and photocatalytic reduction of U(Ⅵ). Herein, we successfully synthesized four morphologically distinct types of NH2-MIL-125(Ti), offering insights into the impact of facet engineering on the combined adsorption and photoreduction of U(Ⅵ). An elevated exposure ratio of the {001} facet endows NH2-MIL-125(Ti) with a larger surface area, enhanced light absorption, and efficient separation of photogenerated charge carriers. Among the four photocatalysts (W, D, S and T), T with a high proportion of {001} facets, demonstrated outstanding adsorption-photocatalytic synergy, achieving over 97% of U(Ⅵ) within 20 min of visible light irradiation across a broad concentrations and pH range, without requiring a hole-trapping agent. The uranium extraction mechanism involves U(Ⅵ) coordination and chelation with active sites during adsorption, followed by reduction to U(Ⅳ) via photogenerated electrons during photocatalysis. This study highlights the use of facet engineering to enhance adsorption and photocatalytic efficiency in MOF-based photocatalysts.
2026, 37(4): 110749
doi: 10.1016/j.cclet.2024.110749
摘要:
Water electrolysis for practical applications faces challenges such as slow kinetics of catalysts in oxygen evolution reaction (OER). These can be effectively improved by facilitating the migration of oxygen intermediates at the material's interface. In this work, we employed carbon dots to modify a heterophase Ir-based oxide catalyst (h-IrO2@CDs) to improve their acidic OER performance. Experimental and theoretical studies reveal that CDs enhances oxygen intermediate migration between rutile and 1T phases, enabling a synergistic oxidation pathway. The small amount addition of CDs reduces energy barriers in the rate-determining step and mitigates excessive oxidation, which significantly boost catalytic activity and stability of IrO2@CDs. The optimal h-IrO2@CDs-3 catalyst achieves a low overpotential (161 mV) for 10 mA/cm2 OER current and remains stable for > 762 h at 10 mA/cm2. The low cost and easy synthesis make CDs highly promising for enhancing overall performance in catalytic fields.
Water electrolysis for practical applications faces challenges such as slow kinetics of catalysts in oxygen evolution reaction (OER). These can be effectively improved by facilitating the migration of oxygen intermediates at the material's interface. In this work, we employed carbon dots to modify a heterophase Ir-based oxide catalyst (h-IrO2@CDs) to improve their acidic OER performance. Experimental and theoretical studies reveal that CDs enhances oxygen intermediate migration between rutile and 1T phases, enabling a synergistic oxidation pathway. The small amount addition of CDs reduces energy barriers in the rate-determining step and mitigates excessive oxidation, which significantly boost catalytic activity and stability of IrO2@CDs. The optimal h-IrO2@CDs-3 catalyst achieves a low overpotential (161 mV) for 10 mA/cm2 OER current and remains stable for > 762 h at 10 mA/cm2. The low cost and easy synthesis make CDs highly promising for enhancing overall performance in catalytic fields.
2026, 37(4): 110750
doi: 10.1016/j.cclet.2024.110750
摘要:
Proton-conducting materials are essential for energy and electronic technologies. Polyoxometalates (POMs), as molecularly well-defined metal oxide nanoclusters with high proton conductivity, are promising candidates for such applications. However, their intrinsic crystalline brittleness poses significant challenges for practical device processing. In this work, we present a strategy to incorporate POM nanoclusters into supramolecular ionic networks (SINs). By using synergistic electrostatic and hydrogen bonding interactions, we uniformly disperse POM nanoclusters into zwitterionic liquids, forming an ionic network structure. The resulting POM-based SIN electrolytes exhibit semi-solid flexibility and high proton conductivity of 2.0 × 10-3 S/cm. Notably, these electrolytes demonstrate strong adhesion with activated carbon electrodes, resulting in flexible supercapacitors with a stable electrolyte-electrode interface that retains 90% capacitance after 14,000 charge-discharge cycles and 10,000 bending cycles. This study provides a promising approach for developing nanocluster-based soft electrolyte materials for flexible devices.
Proton-conducting materials are essential for energy and electronic technologies. Polyoxometalates (POMs), as molecularly well-defined metal oxide nanoclusters with high proton conductivity, are promising candidates for such applications. However, their intrinsic crystalline brittleness poses significant challenges for practical device processing. In this work, we present a strategy to incorporate POM nanoclusters into supramolecular ionic networks (SINs). By using synergistic electrostatic and hydrogen bonding interactions, we uniformly disperse POM nanoclusters into zwitterionic liquids, forming an ionic network structure. The resulting POM-based SIN electrolytes exhibit semi-solid flexibility and high proton conductivity of 2.0 × 10-3 S/cm. Notably, these electrolytes demonstrate strong adhesion with activated carbon electrodes, resulting in flexible supercapacitors with a stable electrolyte-electrode interface that retains 90% capacitance after 14,000 charge-discharge cycles and 10,000 bending cycles. This study provides a promising approach for developing nanocluster-based soft electrolyte materials for flexible devices.
2026, 37(4): 110751
doi: 10.1016/j.cclet.2024.110751
摘要:
Lithium-ion batteries (LIBs) are essential energy storage devices widely used in portable electronics, transportation, and various other applications. However, current anode materials, with their low intercalation potentials and poor rate performance, struggle to balance energy density, power density, and safety, particularly under extreme conditions. In this work, we report a self-regulating micro-channel network that forms a three-dimensional (3D) composite electrode architecture without binders and conductive additives, offering a promising anode solution for fast-charging LIBs. Benefiting from the robust 3D architecture with abundant Li+ active sites and superior electronic conductivity, the niobium tungsten oxide@carbon nanotube (NWO/CNT) composite electrode demonstrates a high reversible capacity (246.6 mAh/g at 0.2 C), excellent rate capability (117.1 mAh/g at 60 C), and long-term durability (73.0% capacity retention after 10,000 cycles). Additionally, a thick electrode with high mass loading (10 mg/cm2) shows remarkable high-rate performance, retaining 51.7% capacity at 20 C. Notably, when paired with LiFePO4 (LFP) cathodes, the NWO@CNT//LFP@CNT full batteries exhibit impressive high-power capability (2.8 kW/kg), high energy density (394.2 Wh/kg), and exceptional cycle stability (82% capacity retention after 6000 cycles). Most importantly, this composite electrode architecture also enables the fabrication of a planar, miniaturized, all-solid-state lithium-ion battery with fast-charging capabilities.
Lithium-ion batteries (LIBs) are essential energy storage devices widely used in portable electronics, transportation, and various other applications. However, current anode materials, with their low intercalation potentials and poor rate performance, struggle to balance energy density, power density, and safety, particularly under extreme conditions. In this work, we report a self-regulating micro-channel network that forms a three-dimensional (3D) composite electrode architecture without binders and conductive additives, offering a promising anode solution for fast-charging LIBs. Benefiting from the robust 3D architecture with abundant Li+ active sites and superior electronic conductivity, the niobium tungsten oxide@carbon nanotube (NWO/CNT) composite electrode demonstrates a high reversible capacity (246.6 mAh/g at 0.2 C), excellent rate capability (117.1 mAh/g at 60 C), and long-term durability (73.0% capacity retention after 10,000 cycles). Additionally, a thick electrode with high mass loading (10 mg/cm2) shows remarkable high-rate performance, retaining 51.7% capacity at 20 C. Notably, when paired with LiFePO4 (LFP) cathodes, the NWO@CNT//LFP@CNT full batteries exhibit impressive high-power capability (2.8 kW/kg), high energy density (394.2 Wh/kg), and exceptional cycle stability (82% capacity retention after 6000 cycles). Most importantly, this composite electrode architecture also enables the fabrication of a planar, miniaturized, all-solid-state lithium-ion battery with fast-charging capabilities.
2026, 37(4): 110754
doi: 10.1016/j.cclet.2024.110754
摘要:
Ruthenium, possessing a comparable metal-hydrogen bond energy to Pt, has emerged as a promising electrocatalyst for the hydrogen oxidation reaction (HOR), but its practical applications are hindered by susceptibility to deactivation or dissolution under operating conditions of fuel cells. Herein, graphene-encapsulated Ru nanoparticles (Ru@NG) was employed as the HOR catalyst for high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). The graphene shells on the Ru can block effectively the surface adsorption of phosphoric acid in electrolyte and CO in anode fuel, but does not affect H2 free access to Ru sites, thus increase the activity expression and stability of catalysts under the high temperature, strong acid, and oxidation conditions of the HT-PEMFCs. With Ru@NG as the anode catalyst, the fuel cell delivers a peak power density of 760 mW/cm2 with pure H2, and additionally, it shows better tolerance to CO that the performance is 1.5 times that of the Pt/C catalysts with H2 fuel containing 1% CO. This work provides an alternative strategy to design the electrocatalysts for HT-PEMFCs.
Ruthenium, possessing a comparable metal-hydrogen bond energy to Pt, has emerged as a promising electrocatalyst for the hydrogen oxidation reaction (HOR), but its practical applications are hindered by susceptibility to deactivation or dissolution under operating conditions of fuel cells. Herein, graphene-encapsulated Ru nanoparticles (Ru@NG) was employed as the HOR catalyst for high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). The graphene shells on the Ru can block effectively the surface adsorption of phosphoric acid in electrolyte and CO in anode fuel, but does not affect H2 free access to Ru sites, thus increase the activity expression and stability of catalysts under the high temperature, strong acid, and oxidation conditions of the HT-PEMFCs. With Ru@NG as the anode catalyst, the fuel cell delivers a peak power density of 760 mW/cm2 with pure H2, and additionally, it shows better tolerance to CO that the performance is 1.5 times that of the Pt/C catalysts with H2 fuel containing 1% CO. This work provides an alternative strategy to design the electrocatalysts for HT-PEMFCs.
2026, 37(4): 110755
doi: 10.1016/j.cclet.2024.110755
摘要:
Ferroelastics have attracted considerable interest because of their promising uses in areas such as energy conversion, sensing technologies, and beyond. However, exploring ferroelastics with high-temperature dielectric switching and photoluminescence remains a challenge. Here, we have synthesized two ferroelastics (DMTP)PbBr3 (DMTP = N,N-dimethyl-1,2,3,6-tetrahydropyridine) and (DMTP)PbI3 under the guidance of halogen substitution strategy. (DMTP)PbI3 experiences the dielectric switching at 371 K, and upon halogen substitution, the strengthened intermolecular interactions lead to (DMTP)PbBr3 undergoing a similar switching at around 390 K. Additionally, two compounds both emit orange light under ultraviolet illumination. (DMTP)PbI3 has the photoluminescence quantum yield of 2.68%, while (DMTP)PbBr3, due to the increased distortion of the inorganic part after halogen substitution, achieves the higher quantum yield of 12%. This work offers meaningful perspectives on exploring the search for ferroelectrics with photoluminescence and high-temperature dielectric switching, and also demonstrates the rationality of the halogen substitution strategy.
Ferroelastics have attracted considerable interest because of their promising uses in areas such as energy conversion, sensing technologies, and beyond. However, exploring ferroelastics with high-temperature dielectric switching and photoluminescence remains a challenge. Here, we have synthesized two ferroelastics (DMTP)PbBr3 (DMTP = N,N-dimethyl-1,2,3,6-tetrahydropyridine) and (DMTP)PbI3 under the guidance of halogen substitution strategy. (DMTP)PbI3 experiences the dielectric switching at 371 K, and upon halogen substitution, the strengthened intermolecular interactions lead to (DMTP)PbBr3 undergoing a similar switching at around 390 K. Additionally, two compounds both emit orange light under ultraviolet illumination. (DMTP)PbI3 has the photoluminescence quantum yield of 2.68%, while (DMTP)PbBr3, due to the increased distortion of the inorganic part after halogen substitution, achieves the higher quantum yield of 12%. This work offers meaningful perspectives on exploring the search for ferroelectrics with photoluminescence and high-temperature dielectric switching, and also demonstrates the rationality of the halogen substitution strategy.
2026, 37(4): 110792
doi: 10.1016/j.cclet.2024.110792
摘要:
The application of commercial hard carbon (HC) materials in sodium-ion batteries (SIBs) is limited by their inferior rate capability (<5.0 A/g) and low tap density (<1.0 g/cm3). Alloying-type bismuth (Bi) offers a high theoretical volumetric capacity of 3800 mAh/cm3 and superb rate capability but suffers from large volume expansion (~244%) and undesirable structural pulverization. Herein, a hectogram-scale Bi-inlaid carbon skeleton (GC-Bi) composite was synthesized through a facile precipitation-carbonization method using low-cost industrial-grade chemical reagents. The as-prepared GC-Bi composite features a unique particle-nested-bulk architecture, achieving a high tap-density of 3.33 g/cm3, which is approximately 4.16 times greater than that of commercial HC. Besides, the carbon sheath enhances the electronic conductivity and accommodates the substantial volume swelling of the embedded Bi particles, contributing to the formation of a thin and stable solid electrolyte interface on the electrode. Consequently, the GC-Bi anode achieves a high volumetric capacity (1123 mAh/cm3), impressive rate capability (207.8 mAh/g at 80 A/g), together with long cyclability retaining 96.5% of its capacity after 5000 cycles in a Na//GC-Bi half-cell and 78% after 800 cycles in a GC-Bi//Na3V2(PO4)3 full-cell.
The application of commercial hard carbon (HC) materials in sodium-ion batteries (SIBs) is limited by their inferior rate capability (<5.0 A/g) and low tap density (<1.0 g/cm3). Alloying-type bismuth (Bi) offers a high theoretical volumetric capacity of 3800 mAh/cm3 and superb rate capability but suffers from large volume expansion (~244%) and undesirable structural pulverization. Herein, a hectogram-scale Bi-inlaid carbon skeleton (GC-Bi) composite was synthesized through a facile precipitation-carbonization method using low-cost industrial-grade chemical reagents. The as-prepared GC-Bi composite features a unique particle-nested-bulk architecture, achieving a high tap-density of 3.33 g/cm3, which is approximately 4.16 times greater than that of commercial HC. Besides, the carbon sheath enhances the electronic conductivity and accommodates the substantial volume swelling of the embedded Bi particles, contributing to the formation of a thin and stable solid electrolyte interface on the electrode. Consequently, the GC-Bi anode achieves a high volumetric capacity (1123 mAh/cm3), impressive rate capability (207.8 mAh/g at 80 A/g), together with long cyclability retaining 96.5% of its capacity after 5000 cycles in a Na//GC-Bi half-cell and 78% after 800 cycles in a GC-Bi//Na3V2(PO4)3 full-cell.
2026, 37(4): 110824
doi: 10.1016/j.cclet.2025.110824
摘要:
Reversible modulation of the transmittance in electrochromic devices (ECDs) holds tremendous potential for energy-saving windows. The choice of electrolyte significantly influences the optical modulation, coloring response speed, coloring efficiency, and cycling stability of electrochromic devices. Moreover, traditional electrolytes are prone to instability under extreme temperature conditions, leading to device failure and severely limiting the widespread application of smart electrochromic windows. This study introduces LiCl water-in-salt electrolyte (WiSE) into tungsten oxide-based ECDs. LiCl WiSE exhibits wide-temperature tolerance and excellent ion conductivity. Therefore, the constructed tungsten oxide ECD demonstrates large optical modulation (76.2%@700 nm), fast response time (tc = 2.0 s, tb = 1.8 s), and high cycling stability (95.8% retention after 1000 cycles). Especially, it operates efficiently over a wide temperature range of -30~80 ℃. This research provides a new approach for electrolyte selection in the fabrication of high-performance, wide-temperature-tolerant ECDs.
Reversible modulation of the transmittance in electrochromic devices (ECDs) holds tremendous potential for energy-saving windows. The choice of electrolyte significantly influences the optical modulation, coloring response speed, coloring efficiency, and cycling stability of electrochromic devices. Moreover, traditional electrolytes are prone to instability under extreme temperature conditions, leading to device failure and severely limiting the widespread application of smart electrochromic windows. This study introduces LiCl water-in-salt electrolyte (WiSE) into tungsten oxide-based ECDs. LiCl WiSE exhibits wide-temperature tolerance and excellent ion conductivity. Therefore, the constructed tungsten oxide ECD demonstrates large optical modulation (76.2%@700 nm), fast response time (tc = 2.0 s, tb = 1.8 s), and high cycling stability (95.8% retention after 1000 cycles). Especially, it operates efficiently over a wide temperature range of -30~80 ℃. This research provides a new approach for electrolyte selection in the fabrication of high-performance, wide-temperature-tolerant ECDs.
2026, 37(4): 110825
doi: 10.1016/j.cclet.2025.110825
摘要:
Birefringent crystals have gained increasing attention for versatile optical devices due to their inherent ability to modulate light polarization. However, the rational design of structures that exhibit high birefringence and deep-ultraviolet (DUV) transparency remains a formidable challenge. Here, a novel zinc borate birefringent crystal, Na2ZnB6O11 (NZBO), was identified by strategically assembling the π-conjugated [B3O7] functional units using the unprecedented antiparallel triangles formed by [ZnO3] motifs. Remarkably, through a tailored motif approach and optimized arrangement, NZBO achieves the largest birefringence (0.094) in the visible wavelength range among the borate-based crystals containing [B3O7] units, exceeding that of commercially available birefringent crystal MgF2 by approximately 8 times (0.012@532 nm). Furthermore, NZBO exhibits a notably short DUV absorption cutoff edge below 190 nm along with a wide band gap of 6.04 eV attributed to the elimination of dangling bonds. The origin of the optical anisotropy attributes of NZBO was elucidated through a combination of theoretical calculations and structural analyses. These findings highlight the good potential of NZBO in the manipulation of polarized light and offer valuable insights for tailoring new birefringent materials in the short-wave UV transparency region.
Birefringent crystals have gained increasing attention for versatile optical devices due to their inherent ability to modulate light polarization. However, the rational design of structures that exhibit high birefringence and deep-ultraviolet (DUV) transparency remains a formidable challenge. Here, a novel zinc borate birefringent crystal, Na2ZnB6O11 (NZBO), was identified by strategically assembling the π-conjugated [B3O7] functional units using the unprecedented antiparallel triangles formed by [ZnO3] motifs. Remarkably, through a tailored motif approach and optimized arrangement, NZBO achieves the largest birefringence (0.094) in the visible wavelength range among the borate-based crystals containing [B3O7] units, exceeding that of commercially available birefringent crystal MgF2 by approximately 8 times (0.012@532 nm). Furthermore, NZBO exhibits a notably short DUV absorption cutoff edge below 190 nm along with a wide band gap of 6.04 eV attributed to the elimination of dangling bonds. The origin of the optical anisotropy attributes of NZBO was elucidated through a combination of theoretical calculations and structural analyses. These findings highlight the good potential of NZBO in the manipulation of polarized light and offer valuable insights for tailoring new birefringent materials in the short-wave UV transparency region.
2026, 37(4): 110826
doi: 10.1016/j.cclet.2025.110826
摘要:
Ferroelectric plastic crystals have garnered significant attention in recent years due to their unique phase-transition behaviors and potential nonlinear optical properties. Nevertheless, most existing examples encounter challenges, such as inadequate transparency and diminished nonlinear optical signal, which constrain their broader applicability. In this study, we present a new ferroelectric plastic crystal, 1-azanorbornanium tetrachlorogallate, which crystallizes in the polar space group Pmc21 at room temperature and undergoes plastic phase transition at above 413 K. This phase transition endows this compound with nonlinear optical performance at polar room-temperature phase, while allowing highly-dynamic molecular rotation to provide excellent mechanical flexibility at high-temperature phase. Through hot-pressing the powder sample, a pressed tablet with an increased density that is 99.4% of crystallographic density (1.70 g/cm3) was obtained. Benefiting from the elimination of crystal grains, such a high-density tablet has significant improvements in light transmittance and second harmonic generation (SHG). Its SHG is increased by approximately 20 times and 6 times those of the loose powder form and referenced KH2PO4, respectively. This work demonstrated the potential of hot-pressing method on enhancing nonlinear optical performance of polar plastic crystals.
Ferroelectric plastic crystals have garnered significant attention in recent years due to their unique phase-transition behaviors and potential nonlinear optical properties. Nevertheless, most existing examples encounter challenges, such as inadequate transparency and diminished nonlinear optical signal, which constrain their broader applicability. In this study, we present a new ferroelectric plastic crystal, 1-azanorbornanium tetrachlorogallate, which crystallizes in the polar space group Pmc21 at room temperature and undergoes plastic phase transition at above 413 K. This phase transition endows this compound with nonlinear optical performance at polar room-temperature phase, while allowing highly-dynamic molecular rotation to provide excellent mechanical flexibility at high-temperature phase. Through hot-pressing the powder sample, a pressed tablet with an increased density that is 99.4% of crystallographic density (1.70 g/cm3) was obtained. Benefiting from the elimination of crystal grains, such a high-density tablet has significant improvements in light transmittance and second harmonic generation (SHG). Its SHG is increased by approximately 20 times and 6 times those of the loose powder form and referenced KH2PO4, respectively. This work demonstrated the potential of hot-pressing method on enhancing nonlinear optical performance of polar plastic crystals.
2026, 37(4): 111047
doi: 10.1016/j.cclet.2025.111047
摘要:
In the process of tumor treatment, chemotherapy drugs have been widely used in clinical practice due to their broad-spectrum and significant therapeutic effects. However, the serious side effects caused by off-target effects also limit the actual efficacy of such drugs in clinical. Here, we developed a series of small molecule-drug conjugates (SMDCs) with carbonic anhydrase IX (CAIX)-targeted unit, which can deliver chemotherapy drugs to CAIX-positive cancer cells and release them in the tumor microenvironment. These SMDCs can quickly captured by the highly expressed CAIX on the tumor membrane, forming a high local concentration difference that allows SMDCs to enter the tumor cells faster. The optimized SMDC (CAIXi-R-HCPT) with ROS-sensitive linker showed higher cytotoxicity than Irinotecan. In MDA-MB-231 solid tumor-bearing mice, CAIXi-R-HCPT showed higher tumor/normal tissue (T/N) ratio than the corresponding SMDC and Irinotecan control and it also exhibited in vivo anti-tumor activity comparable to HCPT at the same dosage, and there was no significant weight loss. These findings emphasize the potential of CAIXi-R-HCPT as a promising anti-cancer SMDC that exhibits targeted delivery, tumor-specific release, and strong anti-tumor effects.
In the process of tumor treatment, chemotherapy drugs have been widely used in clinical practice due to their broad-spectrum and significant therapeutic effects. However, the serious side effects caused by off-target effects also limit the actual efficacy of such drugs in clinical. Here, we developed a series of small molecule-drug conjugates (SMDCs) with carbonic anhydrase IX (CAIX)-targeted unit, which can deliver chemotherapy drugs to CAIX-positive cancer cells and release them in the tumor microenvironment. These SMDCs can quickly captured by the highly expressed CAIX on the tumor membrane, forming a high local concentration difference that allows SMDCs to enter the tumor cells faster. The optimized SMDC (CAIXi-R-HCPT) with ROS-sensitive linker showed higher cytotoxicity than Irinotecan. In MDA-MB-231 solid tumor-bearing mice, CAIXi-R-HCPT showed higher tumor/normal tissue (T/N) ratio than the corresponding SMDC and Irinotecan control and it also exhibited in vivo anti-tumor activity comparable to HCPT at the same dosage, and there was no significant weight loss. These findings emphasize the potential of CAIXi-R-HCPT as a promising anti-cancer SMDC that exhibits targeted delivery, tumor-specific release, and strong anti-tumor effects.
2026, 37(4): 111049
doi: 10.1016/j.cclet.2025.111049
摘要:
Heterodimerization of receptor tyrosine kinases (RTKs) plays unique roles in cell signaling and functions. However, engineering heterodimerization of multiple receptors remains largely unexplored. Herein, we developed an aptamer-based DNA Nano-windmill (TA3) to regulate heterodimerization of three different RTK families, simultaneously activating fibroblast growth factor receptor 1 (FGFR1), hepatocyte growth factor receptor (Met) and epidermal growth factor receptor (EGFR) signaling. It is the first DNA Nano-windmill that activates heterodimerization of FGFR1, Met and EGFR, leading to the down-stream signals transduction, such as the phosphorylation of protein kinase B (Akt) and extracellular regulated protein kinases (Erk), inducing the cell migration and proliferation. We further designed transformable DNA Nano-windmill (TMA) that can convert DNA Nano-windmill into DNA Nano-kite using complementary strands or small molecules to reduce the activation of specific receptor. We believe that the DNA Nano-windmill for heterodimerization of different RTK families have potential applications in biomedicine fields.
Heterodimerization of receptor tyrosine kinases (RTKs) plays unique roles in cell signaling and functions. However, engineering heterodimerization of multiple receptors remains largely unexplored. Herein, we developed an aptamer-based DNA Nano-windmill (TA3) to regulate heterodimerization of three different RTK families, simultaneously activating fibroblast growth factor receptor 1 (FGFR1), hepatocyte growth factor receptor (Met) and epidermal growth factor receptor (EGFR) signaling. It is the first DNA Nano-windmill that activates heterodimerization of FGFR1, Met and EGFR, leading to the down-stream signals transduction, such as the phosphorylation of protein kinase B (Akt) and extracellular regulated protein kinases (Erk), inducing the cell migration and proliferation. We further designed transformable DNA Nano-windmill (TMA) that can convert DNA Nano-windmill into DNA Nano-kite using complementary strands or small molecules to reduce the activation of specific receptor. We believe that the DNA Nano-windmill for heterodimerization of different RTK families have potential applications in biomedicine fields.
2026, 37(4): 111086
doi: 10.1016/j.cclet.2025.111086
摘要:
Bacitracin has been extensively studied for its antibacterial application due to its excellent anti-Gram-positive bacterial properties. However, its application of conventional bacitracin has been limited because of its limited antibacterial activity against Gram-negative bacteria, especially negative bacilli. In this study, we designed and synthesized bacitracin-zinc nanodrugs (BPNDs) through zinc coordination self-assembly of bacitracin, which exhibit potent antibacterial effects not only against Gram-positive bacterial Staphylococcus aureus but also against Escherichia coli, a typical Gram-negative bacillus. The morphological and antimicrobial properties of the self-assembled BPNDs with different molar ratios of bacitracin to zinc ions were investigated. The bacterial biofilm experiments confirmed the biofilm scavenging effect of BPNDs, further expanding the application of this antimicrobial agent. In-depth cell viability experiments indicated that this antimicrobial activity might be related to the penetration of BPNDs into bacterial cell membranes. This study reveals that the zinc-coordinated peptide self-assembly strategy expands the antibacterial spectrum of conventional bacitracin, making it a potential candidate for novel antimicrobial drugs to address the bacterial resistance dilemma and provide stable alternatives for a wide range of biomedical and related industries.
Bacitracin has been extensively studied for its antibacterial application due to its excellent anti-Gram-positive bacterial properties. However, its application of conventional bacitracin has been limited because of its limited antibacterial activity against Gram-negative bacteria, especially negative bacilli. In this study, we designed and synthesized bacitracin-zinc nanodrugs (BPNDs) through zinc coordination self-assembly of bacitracin, which exhibit potent antibacterial effects not only against Gram-positive bacterial Staphylococcus aureus but also against Escherichia coli, a typical Gram-negative bacillus. The morphological and antimicrobial properties of the self-assembled BPNDs with different molar ratios of bacitracin to zinc ions were investigated. The bacterial biofilm experiments confirmed the biofilm scavenging effect of BPNDs, further expanding the application of this antimicrobial agent. In-depth cell viability experiments indicated that this antimicrobial activity might be related to the penetration of BPNDs into bacterial cell membranes. This study reveals that the zinc-coordinated peptide self-assembly strategy expands the antibacterial spectrum of conventional bacitracin, making it a potential candidate for novel antimicrobial drugs to address the bacterial resistance dilemma and provide stable alternatives for a wide range of biomedical and related industries.
2026, 37(4): 111119
doi: 10.1016/j.cclet.2025.111119
摘要:
The performance of photosensitizers determines the effect of photodynamic therapy (PDT). At present, most photosensitizers are developed from fluorescent dyes, but it is difficult to possess both the good photophysical properties and photosensitive efficiency. In this work, an efficient strategy was developed to construct a cyanine-based near infrared (NIR) photosensitizer, 2LBCy5.5, with an enlarged and twisted D-π-A-π-D structure by connecting two classical Cy5.5 dyes smartly with a dual-cationic benzo[1,2-b:4,5-b']dipyrrole group. The 2LBCy5.5 exhibited a maximum absorption at 802 nm with a great molar extinction coefficient of 4.2 × 105 L mol−1 cm−1, compared with its parent Cy5.5 (692 nm with a molar extinction coefficient of 2.5 × 105 L mol−1 cm−1). Furthermore, 2LBCy5.5 exhibited narrow energy gap of singlet-triplet (ΔES-T) accelerated the intersystem crossing process (1.21 ns−1) with a high triplet-excited-state quantum yield (26.1%) under 808 nm excitation, greatly contributing to reactive oxygen species (ROS) generation in type-Ⅰ PDT. The excellent anti-tumor ability of 2LBCy5.5 was realized both under normoxic and hypoxic conditions. This study provides an effective and powerful approach for designing cyanine photosensitizers with strong capabilities in both photophysical properties (e.g., NIR light-harvesting) and highly antitumor efficiency.
The performance of photosensitizers determines the effect of photodynamic therapy (PDT). At present, most photosensitizers are developed from fluorescent dyes, but it is difficult to possess both the good photophysical properties and photosensitive efficiency. In this work, an efficient strategy was developed to construct a cyanine-based near infrared (NIR) photosensitizer, 2LBCy5.5, with an enlarged and twisted D-π-A-π-D structure by connecting two classical Cy5.5 dyes smartly with a dual-cationic benzo[1,2-b:4,5-b']dipyrrole group. The 2LBCy5.5 exhibited a maximum absorption at 802 nm with a great molar extinction coefficient of 4.2 × 105 L mol−1 cm−1, compared with its parent Cy5.5 (692 nm with a molar extinction coefficient of 2.5 × 105 L mol−1 cm−1). Furthermore, 2LBCy5.5 exhibited narrow energy gap of singlet-triplet (ΔES-T) accelerated the intersystem crossing process (1.21 ns−1) with a high triplet-excited-state quantum yield (26.1%) under 808 nm excitation, greatly contributing to reactive oxygen species (ROS) generation in type-Ⅰ PDT. The excellent anti-tumor ability of 2LBCy5.5 was realized both under normoxic and hypoxic conditions. This study provides an effective and powerful approach for designing cyanine photosensitizers with strong capabilities in both photophysical properties (e.g., NIR light-harvesting) and highly antitumor efficiency.
2026, 37(4): 111139
doi: 10.1016/j.cclet.2025.111139
摘要:
The photopharmacology incorporated with molecular photoswitches offers a promising solution to fundamentally address the problem of bacterial resistance, simultaneously realizes the spatiotemporal precision treatment through remote light control. However, most of reported photoswitchable drugs are limited by the need of ultraviolet (UV) light, which is often damaging and not suitable for tissue penetration. Therefore, the development of photopharmacological agents triggered by visible light, especially near-infrared (NIR) light is highly desirable for future photoswitchable antibiotics. Herein, a novel photopharmacological antibacterial agent DTE-FQ was designed and synthesized by the incorporation of dithienylethene (DTE) molecular photoswitch and fluoroquinolones (FQ) antimicrobial drug norfloxacin bridged by pyridinium group and flexible butyl chain. As expected, as-prepared DTE-FQ presents efficient photoswitching behavior in various solutions upon alternating irradiation with blue light (460–470 nm) and NIR light (730–740 nm). Simultaneously, it shows significant and reversible configurational transition by the synergistic effect of DTE photoswitch and flexible butyl chain. Most remarkably, DTE-FQ reveals an at least 4-fold difference in activity against Escherichia coli (E. coli) for ring-open and ring-closed isomers, and a distinct change in bacterial growth is observed by in situ irradiation with NIR light in the presence of E. coli. These results are further confirmed by the molecular docking to DNA gyrase. The chain-like configuration of DTE-FQ treated with NIR light, inserted between the double-stranded DNA restraining the replication of DNA. Whereas the coiled configuration obtained by blue light irradiation, remained in the vicinity of the double-stranded DNA showing weak antibacterial activity. As far as we know, it represents the first example of blue-/NIR light-triggered photopharmacological antibacterial agent based on DTE switch so far, indicating its potential for in vivo photopharmacological applications.
The photopharmacology incorporated with molecular photoswitches offers a promising solution to fundamentally address the problem of bacterial resistance, simultaneously realizes the spatiotemporal precision treatment through remote light control. However, most of reported photoswitchable drugs are limited by the need of ultraviolet (UV) light, which is often damaging and not suitable for tissue penetration. Therefore, the development of photopharmacological agents triggered by visible light, especially near-infrared (NIR) light is highly desirable for future photoswitchable antibiotics. Herein, a novel photopharmacological antibacterial agent DTE-FQ was designed and synthesized by the incorporation of dithienylethene (DTE) molecular photoswitch and fluoroquinolones (FQ) antimicrobial drug norfloxacin bridged by pyridinium group and flexible butyl chain. As expected, as-prepared DTE-FQ presents efficient photoswitching behavior in various solutions upon alternating irradiation with blue light (460–470 nm) and NIR light (730–740 nm). Simultaneously, it shows significant and reversible configurational transition by the synergistic effect of DTE photoswitch and flexible butyl chain. Most remarkably, DTE-FQ reveals an at least 4-fold difference in activity against Escherichia coli (E. coli) for ring-open and ring-closed isomers, and a distinct change in bacterial growth is observed by in situ irradiation with NIR light in the presence of E. coli. These results are further confirmed by the molecular docking to DNA gyrase. The chain-like configuration of DTE-FQ treated with NIR light, inserted between the double-stranded DNA restraining the replication of DNA. Whereas the coiled configuration obtained by blue light irradiation, remained in the vicinity of the double-stranded DNA showing weak antibacterial activity. As far as we know, it represents the first example of blue-/NIR light-triggered photopharmacological antibacterial agent based on DTE switch so far, indicating its potential for in vivo photopharmacological applications.
2026, 37(4): 111141
doi: 10.1016/j.cclet.2025.111141
摘要:
In this work, the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism is introduced into the near-infrared and highly photon-capturing heptamethine cyanine (Cy7) class to construct photosensitizer (PS) for photodynamic therapy (PDT) of tumor. The target PS AN–Cy7 shows an obviously improved singlet oxygen (1O2) quantum yield than the Food and Drug Administration (FDA)-approved indocyanine green (ICG) under 750 nm low-power photoirradiation (30 mW/cm2) while retaining strong fluorescence at ~805 nm. Importantly, the PS forms a 2:1 dye-human serum albumin (HSA) nanocomplex, ensuring its strong accumulation and retention at tumor site (up to five days) post intravenous injection. After a single PDT treatment, the nanocomplex almost completely ablates primary tumor while triggering an antitumor immune response to suppress the growth of distant tumors. Overall, the nanocomplex overcomes many shortcomings of clinically used PSs, thus being promising for future clinical translation.
In this work, the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism is introduced into the near-infrared and highly photon-capturing heptamethine cyanine (Cy7) class to construct photosensitizer (PS) for photodynamic therapy (PDT) of tumor. The target PS AN–Cy7 shows an obviously improved singlet oxygen (1O2) quantum yield than the Food and Drug Administration (FDA)-approved indocyanine green (ICG) under 750 nm low-power photoirradiation (30 mW/cm2) while retaining strong fluorescence at ~805 nm. Importantly, the PS forms a 2:1 dye-human serum albumin (HSA) nanocomplex, ensuring its strong accumulation and retention at tumor site (up to five days) post intravenous injection. After a single PDT treatment, the nanocomplex almost completely ablates primary tumor while triggering an antitumor immune response to suppress the growth of distant tumors. Overall, the nanocomplex overcomes many shortcomings of clinically used PSs, thus being promising for future clinical translation.
2026, 37(4): 111143
doi: 10.1016/j.cclet.2025.111143
摘要:
Sirtuin 2 (SIRT2) is one of the key members of sirtuins family that plays important role in regulating many physiological processes. Recent evidences have revealed that SIRT2 is associated with the development, progression and metastasis of ovarian cancer. In this study, guided by an in-depth analysis of the clinical characteristics of the expression pattern of SIRT2 in ovarian cancer patients, the first SIRT2-targeted hydrophobic tagging (HyT) degraders have been developed. These acyl thiourea degraders exhibited remarkable anti-proliferative activity in several ovarian cancer cells. Among them, the most effective compound Ⅱ-6 exhibited excellent anti-tumor activity both in vitro and in vivo (half maximal inhibitory concentration (IC50) = 0.002 ± 0.001 µmol/L). In addition, Ⅱ-6 was found to effectively suppress cancer cell proliferation and migration, as well as cell cycle arrest and apoptosis. Moreover, further investigation revealed that compound Ⅱ-6 indirectly induced DNA damage through the H4K20me2/53BP1 pathway by degradation of SIRT2. The study not only exemplifies the advantage of the novel HyT degradation strategy but also prove the great potential of SIRT2 as a promising target for drug development of ovarian cancer.
Sirtuin 2 (SIRT2) is one of the key members of sirtuins family that plays important role in regulating many physiological processes. Recent evidences have revealed that SIRT2 is associated with the development, progression and metastasis of ovarian cancer. In this study, guided by an in-depth analysis of the clinical characteristics of the expression pattern of SIRT2 in ovarian cancer patients, the first SIRT2-targeted hydrophobic tagging (HyT) degraders have been developed. These acyl thiourea degraders exhibited remarkable anti-proliferative activity in several ovarian cancer cells. Among them, the most effective compound Ⅱ-6 exhibited excellent anti-tumor activity both in vitro and in vivo (half maximal inhibitory concentration (IC50) = 0.002 ± 0.001 µmol/L). In addition, Ⅱ-6 was found to effectively suppress cancer cell proliferation and migration, as well as cell cycle arrest and apoptosis. Moreover, further investigation revealed that compound Ⅱ-6 indirectly induced DNA damage through the H4K20me2/53BP1 pathway by degradation of SIRT2. The study not only exemplifies the advantage of the novel HyT degradation strategy but also prove the great potential of SIRT2 as a promising target for drug development of ovarian cancer.
2026, 37(4): 111144
doi: 10.1016/j.cclet.2025.111144
摘要:
The vast majority of lanthanide-doped nanoparticles (LnNPs) exhibit a single mode of upconversion luminescence (UCL) or downshifting luminescence (DSL) for photodynamic therapy (PDT) or diagnostic imaging of tumors, respectively. In order to achieve both UCL and DSL, it is often necessary to dope the luminescent ions in different shell layers to prevent their luminescence quenching, resulting in tedious synthesis steps. Herein, upconversion-downshifting nanoparticles (UDNPs) co-doped with Er3+ and Ho3+ enable the simultaneous dual-wavelength DSL for in vivo near-infrared (NIR)-Ⅱ fluorescence imaging of tumors. On the other hand, the UCL of UDNPs could activate merocyanine photosensitizers (MC 540), resulting in the generation of reactive oxygen species (ROS) and the achievement of PDT. Importantly, Au NPs with glucose oxidase-like properties could consume glucose and promote H2O2 accumulation in tumor cells. Au-catalyzed UDNPs modified with Fe-tannic acid (FeTA) (UDNP-MC/Au-FeTA) could not only enhance the effect of PDT but also realize chemodynamic therapy (CDT) by reacting with Fe2+ generated from slightly acidic decomposition of FeTA to accelerate hydroxyl radical (•OH) generation. The combination of long- and short-acting dual-dynamic therapy could mutually reinforce and compensate for the lack of therapeutic efficacy resulting from luminescence quenching caused by co-doping luminescent ions. Therefore, UDNP-MC/Au-FeTA guided by NIR-Ⅱ fluorescence imaging could achieve efficient synergistic dual-dynamic therapy of tumors through differentially expressed genes associated with apoptosis and oxidative stress-related pathways. NIR-Ⅱ fluorescence imaging diagnostic and dual-dynamic therapeutic strategy, which employs Au-catalyzed lanthanide co-doped UDNPs represents a dexterous design concept for promising anti-tumor applications.
The vast majority of lanthanide-doped nanoparticles (LnNPs) exhibit a single mode of upconversion luminescence (UCL) or downshifting luminescence (DSL) for photodynamic therapy (PDT) or diagnostic imaging of tumors, respectively. In order to achieve both UCL and DSL, it is often necessary to dope the luminescent ions in different shell layers to prevent their luminescence quenching, resulting in tedious synthesis steps. Herein, upconversion-downshifting nanoparticles (UDNPs) co-doped with Er3+ and Ho3+ enable the simultaneous dual-wavelength DSL for in vivo near-infrared (NIR)-Ⅱ fluorescence imaging of tumors. On the other hand, the UCL of UDNPs could activate merocyanine photosensitizers (MC 540), resulting in the generation of reactive oxygen species (ROS) and the achievement of PDT. Importantly, Au NPs with glucose oxidase-like properties could consume glucose and promote H2O2 accumulation in tumor cells. Au-catalyzed UDNPs modified with Fe-tannic acid (FeTA) (UDNP-MC/Au-FeTA) could not only enhance the effect of PDT but also realize chemodynamic therapy (CDT) by reacting with Fe2+ generated from slightly acidic decomposition of FeTA to accelerate hydroxyl radical (•OH) generation. The combination of long- and short-acting dual-dynamic therapy could mutually reinforce and compensate for the lack of therapeutic efficacy resulting from luminescence quenching caused by co-doping luminescent ions. Therefore, UDNP-MC/Au-FeTA guided by NIR-Ⅱ fluorescence imaging could achieve efficient synergistic dual-dynamic therapy of tumors through differentially expressed genes associated with apoptosis and oxidative stress-related pathways. NIR-Ⅱ fluorescence imaging diagnostic and dual-dynamic therapeutic strategy, which employs Au-catalyzed lanthanide co-doped UDNPs represents a dexterous design concept for promising anti-tumor applications.
2026, 37(4): 111145
doi: 10.1016/j.cclet.2025.111145
摘要:
Accurate cancer diagnosis is essential for fluorescence surgical navigation to eliminate tumors. Second near-infrared (NIR-Ⅱ, 1000–1700 nm) probes with aggregation-induced emission (AIE) nature possess bright fluorescence in a biological environment. However, due to the large particle sizes, NIR-Ⅱ AIE probes usually lead to high liver retention, which is not conducive to tumor enrichment. Therefore, this work constructs a novel amphiphilic NIR-Ⅱ AIE molecule, TTB-PEG1000, which can self-assemble into ultra-small fluorescent dots (7 nm) in the aqueous environment with a maximum emission at 1080 nm. Based on its excellent photostability, morphological stability, and biocompatibility, TTB-PEG1000 shows a desirable definition of angiography capability with high signal-to-background (SBR) in the NIR-Ⅱ AIE window over 1300 nm. Notably, treatment with TTB-PEG1000 in the glioma-tumor mice results in a significant enhancement of the accumulation in the tumor and reduction of the retention in the liver, in which the fluorescent ratio between tumor and liver (T/L) is 32-fold higher than that of their contrast (TTB-COOH NPs) prepared by the nanoprecipitation method. This work is the first report of an amphiphilic AIE molecule with NIR-Ⅱ maximum emission and sub-10 nm size, which will promise for preclinical applications and inspire further exploration of NIR-Ⅱ fluorophores for advanced biomedical imaging.
Accurate cancer diagnosis is essential for fluorescence surgical navigation to eliminate tumors. Second near-infrared (NIR-Ⅱ, 1000–1700 nm) probes with aggregation-induced emission (AIE) nature possess bright fluorescence in a biological environment. However, due to the large particle sizes, NIR-Ⅱ AIE probes usually lead to high liver retention, which is not conducive to tumor enrichment. Therefore, this work constructs a novel amphiphilic NIR-Ⅱ AIE molecule, TTB-PEG1000, which can self-assemble into ultra-small fluorescent dots (7 nm) in the aqueous environment with a maximum emission at 1080 nm. Based on its excellent photostability, morphological stability, and biocompatibility, TTB-PEG1000 shows a desirable definition of angiography capability with high signal-to-background (SBR) in the NIR-Ⅱ AIE window over 1300 nm. Notably, treatment with TTB-PEG1000 in the glioma-tumor mice results in a significant enhancement of the accumulation in the tumor and reduction of the retention in the liver, in which the fluorescent ratio between tumor and liver (T/L) is 32-fold higher than that of their contrast (TTB-COOH NPs) prepared by the nanoprecipitation method. This work is the first report of an amphiphilic AIE molecule with NIR-Ⅱ maximum emission and sub-10 nm size, which will promise for preclinical applications and inspire further exploration of NIR-Ⅱ fluorophores for advanced biomedical imaging.
2026, 37(4): 111161
doi: 10.1016/j.cclet.2025.111161
摘要:
Penispirolactam (1) and penipyrroloindole (2), two highly modified paspaline-type indole diterpenoids (IDTs), along with three new (3–5) and two known (6 and 7) paspaline-type IDTs were obtained from the endophytic fungus Penicillium janthinellum H-6 guided by liquid chromatography-mass spectrometry (LC-MS)-based molecular network. Architecturally, penispirolactam (1) possesses a unique octacyclic skeleton (6/5/6/6/5/6/6/6) with a spiro core formed by the integration of a C6–C2 unit with the indole moiety, and penipyrroloindole (2) represents a rearranged octacyclic skeleton (6/5/6/5/5/6/6/6) with a pyrrolo[1,2-a]indole core fragment. Their structures, including absolute configurations, were established by detailed spectroscopic analysis, gauge-independent atomic orbital (GIAO) 1D nuclear magnetic resonance (NMR) (DP4+) calculation protocol, and electronic circular dichroism (ECD) calculation method. The plausible biosynthetic pathway of compounds 1 and 2 was also speculated. Additionally, the anti-hepatic fibrosis activity of all compounds was explored, and it was found that 1 could exert its effects by inhibiting the transforming growth factor-β (TGF-β)/Smad signaling pathway without cytotoxicity.
Penispirolactam (1) and penipyrroloindole (2), two highly modified paspaline-type indole diterpenoids (IDTs), along with three new (3–5) and two known (6 and 7) paspaline-type IDTs were obtained from the endophytic fungus Penicillium janthinellum H-6 guided by liquid chromatography-mass spectrometry (LC-MS)-based molecular network. Architecturally, penispirolactam (1) possesses a unique octacyclic skeleton (6/5/6/6/5/6/6/6) with a spiro core formed by the integration of a C6–C2 unit with the indole moiety, and penipyrroloindole (2) represents a rearranged octacyclic skeleton (6/5/6/5/5/6/6/6) with a pyrrolo[1,2-a]indole core fragment. Their structures, including absolute configurations, were established by detailed spectroscopic analysis, gauge-independent atomic orbital (GIAO) 1D nuclear magnetic resonance (NMR) (DP4+) calculation protocol, and electronic circular dichroism (ECD) calculation method. The plausible biosynthetic pathway of compounds 1 and 2 was also speculated. Additionally, the anti-hepatic fibrosis activity of all compounds was explored, and it was found that 1 could exert its effects by inhibiting the transforming growth factor-β (TGF-β)/Smad signaling pathway without cytotoxicity.
2026, 37(4): 111163
doi: 10.1016/j.cclet.2025.111163
摘要:
Up to now, aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ) have been widely used for fluorescence sensing, respectively. In our study, we covalently linked cyanine dye and 2-cyanobenzothiazole (CBT) to construct fluorescent probe NPCS. Through spectroscopic testing, it was found that the probe itself has both AIE and ACQ behavior. And these acts are borne by CBT and cyanine (CY) respectively. In this study, it was found that glutathione (GSH) showed aggregation and disaggregation effects on two parts of the probe, namely: low concentration of GSH mainly aggravated AIE, and high concentration of GSH disaggregated ACQ of the probe, both of which led to fluorescence enhancement effect and achieved turn-on fluorescence detection of high and low concentrations of GSH. Cysteine (Cys), on the other hand, can undergo a click reaction with the cyano group to generate a stable fluorescent signal. Since Cys does not have the ability to disaggregate, the probe can achieve non-competitive discrimination detection of Cys and GSH. Real-time discriminatory detection of changes in Cys and GSH levels was demonstrated in living cells. The results of this study provide a new perspective for the development of emerging recognition mechanisms and multi-functionality of probes.
Up to now, aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ) have been widely used for fluorescence sensing, respectively. In our study, we covalently linked cyanine dye and 2-cyanobenzothiazole (CBT) to construct fluorescent probe NPCS. Through spectroscopic testing, it was found that the probe itself has both AIE and ACQ behavior. And these acts are borne by CBT and cyanine (CY) respectively. In this study, it was found that glutathione (GSH) showed aggregation and disaggregation effects on two parts of the probe, namely: low concentration of GSH mainly aggravated AIE, and high concentration of GSH disaggregated ACQ of the probe, both of which led to fluorescence enhancement effect and achieved turn-on fluorescence detection of high and low concentrations of GSH. Cysteine (Cys), on the other hand, can undergo a click reaction with the cyano group to generate a stable fluorescent signal. Since Cys does not have the ability to disaggregate, the probe can achieve non-competitive discrimination detection of Cys and GSH. Real-time discriminatory detection of changes in Cys and GSH levels was demonstrated in living cells. The results of this study provide a new perspective for the development of emerging recognition mechanisms and multi-functionality of probes.
2026, 37(4): 111166
doi: 10.1016/j.cclet.2025.111166
摘要:
As fundamental chemicals, alkynes have been pivotal in synthesizing numerous value-added compounds. Direct manipulation of alkynes offers rapid access to diverse chemical spaces. Cleaving the alkyne triple bond has traditionally required harsh conditions due to its high bond dissociation energy. Here, we present a manganese-catalyzed electrochemical nitrogenation method for the direct cleavage of C≡C bonds, efficiently generating various nitriles under mild conditions. This reaction demonstrates extensive functional group tolerance and eliminates the need for stoichiometric chemical oxidants. CV experiments verified the role of Mn catalysis, and the N3 radical intermediate was confirmed by EPR spectroscopy. Our synthetic protocol provides a promising and versatile alternative for constructing nitrogen-containing compounds, potentially transforming approaches in chemical synthesis
As fundamental chemicals, alkynes have been pivotal in synthesizing numerous value-added compounds. Direct manipulation of alkynes offers rapid access to diverse chemical spaces. Cleaving the alkyne triple bond has traditionally required harsh conditions due to its high bond dissociation energy. Here, we present a manganese-catalyzed electrochemical nitrogenation method for the direct cleavage of C≡C bonds, efficiently generating various nitriles under mild conditions. This reaction demonstrates extensive functional group tolerance and eliminates the need for stoichiometric chemical oxidants. CV experiments verified the role of Mn catalysis, and the N3 radical intermediate was confirmed by EPR spectroscopy. Our synthetic protocol provides a promising and versatile alternative for constructing nitrogen-containing compounds, potentially transforming approaches in chemical synthesis
2026, 37(4): 111167
doi: 10.1016/j.cclet.2025.111167
摘要:
Amino acids are the building blocks of proteins and various bioactive molecules. Fluorination is a key strategy in medicinal chemistry, making the development of new and efficient methods for fluorinating amino acids highly desirable. While many fluorination reagents have been developed, their application on amino acid frameworks remains limited. In this study, we demonstrate that ethyl 3-bromo-2-((diphenylmethylene)amino)-3,3-difluoropropanoate is an effective gem-difluoroalkenes precursor for constructing a library of monofluoroolefin amino acids via a Pd-catalyzed cross-coupling reaction.
Amino acids are the building blocks of proteins and various bioactive molecules. Fluorination is a key strategy in medicinal chemistry, making the development of new and efficient methods for fluorinating amino acids highly desirable. While many fluorination reagents have been developed, their application on amino acid frameworks remains limited. In this study, we demonstrate that ethyl 3-bromo-2-((diphenylmethylene)amino)-3,3-difluoropropanoate is an effective gem-difluoroalkenes precursor for constructing a library of monofluoroolefin amino acids via a Pd-catalyzed cross-coupling reaction.
2026, 37(4): 111171
doi: 10.1016/j.cclet.2025.111171
摘要:
Orthogonal molecular orbitals (MOs) of donor-acceptor (D-A) pairs favor the spin-orbit charge transfer intersystem crossing (SOCT-ISC) transition, and herein 2-anthryl asymmetric aza-boradiazaindacene (aza-BODIPY) (AH-BDP) was designed and prepared. According to the X-ray crystallography, the steric hindrance in orthogonal molecule AH-BDP results in a large dihedral angle between the two MO planes. Since low ΔEst prefers to undertake ISC and efficiently produce reactive oxygen species (ROS), the calculated ΔEst for AH-BDP is 0.757 eV, significantly smaller than that of the aza-BDOPY without anthryl group DH-BDP (1.052 eV). AH-BDP as a heavy-atom-free photosensitizer not only produced the singlet oxygen, but also possessed photothermal conversion efficiency. Self-assembly AH-BDP nanoparticles (NPs) could efficiently induce HCT116 cells elimination in nude mice through ROS/heat-mediated pathways.
Orthogonal molecular orbitals (MOs) of donor-acceptor (D-A) pairs favor the spin-orbit charge transfer intersystem crossing (SOCT-ISC) transition, and herein 2-anthryl asymmetric aza-boradiazaindacene (aza-BODIPY) (AH-BDP) was designed and prepared. According to the X-ray crystallography, the steric hindrance in orthogonal molecule AH-BDP results in a large dihedral angle between the two MO planes. Since low ΔEst prefers to undertake ISC and efficiently produce reactive oxygen species (ROS), the calculated ΔEst for AH-BDP is 0.757 eV, significantly smaller than that of the aza-BDOPY without anthryl group DH-BDP (1.052 eV). AH-BDP as a heavy-atom-free photosensitizer not only produced the singlet oxygen, but also possessed photothermal conversion efficiency. Self-assembly AH-BDP nanoparticles (NPs) could efficiently induce HCT116 cells elimination in nude mice through ROS/heat-mediated pathways.
2026, 37(4): 111172
doi: 10.1016/j.cclet.2025.111172
摘要:
Alzheimer's disease (AD) is a complex and multifactorial neurodegenerative disorder, marked by a variety of pathological hallmarks such as oxidative stress (OS), metal accumulation, and the aggregation of amyloid-beta (Aβ) proteins. Erucin, a natural compound present in cruciferous plants, has demonstrated promising therapeutic potential in modulating neurodegenerative diseases, hinting at its neuroprotective capabilities. In this study, we engineered an innovative intracellular protein delivery system centered around erucin. This delivery platform operates through a cell membrane perforation mechanism, enabling the swift translocation of target proteins into the cytoplasm. As a result, it substantially shortens the time required for the proteins to exert their functions. Significantly, this delivery system inherently possesses the capacity to inhibit Aβ aggregation. In PC12 cell models, the delivery of the antioxidant enzyme superoxide dismutase (SOD) successfully mitigated the OS triggered by Aβ aggregation and decreased cytotoxicity. This multifaceted therapeutic strategy holds great promise as an effective approach for the treatment of AD.
Alzheimer's disease (AD) is a complex and multifactorial neurodegenerative disorder, marked by a variety of pathological hallmarks such as oxidative stress (OS), metal accumulation, and the aggregation of amyloid-beta (Aβ) proteins. Erucin, a natural compound present in cruciferous plants, has demonstrated promising therapeutic potential in modulating neurodegenerative diseases, hinting at its neuroprotective capabilities. In this study, we engineered an innovative intracellular protein delivery system centered around erucin. This delivery platform operates through a cell membrane perforation mechanism, enabling the swift translocation of target proteins into the cytoplasm. As a result, it substantially shortens the time required for the proteins to exert their functions. Significantly, this delivery system inherently possesses the capacity to inhibit Aβ aggregation. In PC12 cell models, the delivery of the antioxidant enzyme superoxide dismutase (SOD) successfully mitigated the OS triggered by Aβ aggregation and decreased cytotoxicity. This multifaceted therapeutic strategy holds great promise as an effective approach for the treatment of AD.
2026, 37(4): 111174
doi: 10.1016/j.cclet.2025.111174
摘要:
Aqueous zinc-ion batteries (AZIBs) have drawn numerous attention due to their low cost and environmental benefits. However, its commercialization process was hindered by issues, such as uncontrolled dendrite growth and parasitic side reactions. Inspired by the natural interaction between Zn2+ and amino acid chains in zinc finger proteins, we introduced L-proline (LP), a cost-effective additive, into the aqueous electrolyte to stabilize the Zn anode. In combination with experiments and theoretical calculation results, it is demonstrated that the LP additive tends to reshape the hydrated Zn2+ solvation sheath and weaken the free H2O activity, thereby restricting the water-induced parasitic reactions and drastic dendrite growth. Therefore, the Zn symmetrical cells with LP-containing electrolytes delivered an excellent superior electrochemical performance, including a long-term calendar lifespan of 3400 h at 2 mA/cm2 and nearly 450 h at 5 mA/cm2. Meanwhile, the as-assembled Zn||MnO2 full cells also showed desired cycling stability and rate performance with the assistance of LP additive, outperforming the ZnSO4 system. This intriguing bio-inspired strategy provides a valuable insight for improving the longevity of AZIBs and advancing their development in energy storage.
Aqueous zinc-ion batteries (AZIBs) have drawn numerous attention due to their low cost and environmental benefits. However, its commercialization process was hindered by issues, such as uncontrolled dendrite growth and parasitic side reactions. Inspired by the natural interaction between Zn2+ and amino acid chains in zinc finger proteins, we introduced L-proline (LP), a cost-effective additive, into the aqueous electrolyte to stabilize the Zn anode. In combination with experiments and theoretical calculation results, it is demonstrated that the LP additive tends to reshape the hydrated Zn2+ solvation sheath and weaken the free H2O activity, thereby restricting the water-induced parasitic reactions and drastic dendrite growth. Therefore, the Zn symmetrical cells with LP-containing electrolytes delivered an excellent superior electrochemical performance, including a long-term calendar lifespan of 3400 h at 2 mA/cm2 and nearly 450 h at 5 mA/cm2. Meanwhile, the as-assembled Zn||MnO2 full cells also showed desired cycling stability and rate performance with the assistance of LP additive, outperforming the ZnSO4 system. This intriguing bio-inspired strategy provides a valuable insight for improving the longevity of AZIBs and advancing their development in energy storage.
2026, 37(4): 111175
doi: 10.1016/j.cclet.2025.111175
摘要:
Aqueous zinc-ion hybrid capacitors (AZICs) combine the advantageous characteristics of the high energy density of aqueous zinc-ion batteries with the high power density of supercapacitors. However, their practical application is limited by the instability of the zinc anode and the relatively low capacity of the carbon cathode. To address these challenges, we propose the utilization of p-benzoquinone (BQ) as a bifunctional electrolyte additive. This additive adsorbs onto the zinc surface and modifies the Zn2+ solvation structure, effectively suppressing the growth of zinc dendrites and mitigating water-related side reactions. As a result, the lifespan of the zinc anode is significantly extended from 35 h to 1188 h at 0.5 mA/cm2 and 0.5 mAh/cm2, with a high average Coulombic efficiency of 99.30%. Additionally, the BQ additive enhances the specific capacity of the cathode through its rapid redox reactions on the cathode surface. The AZIC also demonstrates a notable increase in capacity, rising from 40 mAh/g to 140 mAh/g at 0.5 A/g, alongside improved rate performance and cycling stability. This study offers an efficient strategy to simultaneously address the stability and energy density limitations of AZICs.
Aqueous zinc-ion hybrid capacitors (AZICs) combine the advantageous characteristics of the high energy density of aqueous zinc-ion batteries with the high power density of supercapacitors. However, their practical application is limited by the instability of the zinc anode and the relatively low capacity of the carbon cathode. To address these challenges, we propose the utilization of p-benzoquinone (BQ) as a bifunctional electrolyte additive. This additive adsorbs onto the zinc surface and modifies the Zn2+ solvation structure, effectively suppressing the growth of zinc dendrites and mitigating water-related side reactions. As a result, the lifespan of the zinc anode is significantly extended from 35 h to 1188 h at 0.5 mA/cm2 and 0.5 mAh/cm2, with a high average Coulombic efficiency of 99.30%. Additionally, the BQ additive enhances the specific capacity of the cathode through its rapid redox reactions on the cathode surface. The AZIC also demonstrates a notable increase in capacity, rising from 40 mAh/g to 140 mAh/g at 0.5 A/g, alongside improved rate performance and cycling stability. This study offers an efficient strategy to simultaneously address the stability and energy density limitations of AZICs.
2026, 37(4): 111199
doi: 10.1016/j.cclet.2025.111199
摘要:
The inappropriate use of antibiotics has led to the emergence of drug-resistant bacteria and the formation of persistent biofilms, rendering conventional antibiotics ineffective against these infections. To address this challenge, the enzyme-like activity of nanozymes, particularly those with photothermal effects, is being explored. However, the development of nanozymes is hindered by the complex synthesis processes involved and the consumption of reactive oxygen species (ROS) by reducing products in bacteria. This article presents an interesting strategy utilizing near-infrared laser-enhanced oxidase-like (OXD-like) activity of manganese dioxide nanoparticles (MnO2 NPs) to combat subcutaneous infections caused by methicillin-resistant Staphylococcus aureus (MRSA). MnO2 NPs, characterized by flower-like morphology and broad near-infrared absorption, exhibited favorable OXD-like activity and a stable photothermal effect. Experiments in vitro revealed that the combined high thermal effect and the substantial production of ROS effectively targeted MRSA and disrupted biofilm. The efficacy of MnO2 in vivo was validated through the establishment of a subcutaneous abscess model. Additionally, a series of biosafety tests, including routine blood tests and blood biochemistry analyses, confirmed the safety of MnO2 in vivo. Collectively, these findings suggest that combination therapy involving MnO2 presents a promising therapeutic approach for addressing infections associated with biofilms and drug-resistant bacteria.
The inappropriate use of antibiotics has led to the emergence of drug-resistant bacteria and the formation of persistent biofilms, rendering conventional antibiotics ineffective against these infections. To address this challenge, the enzyme-like activity of nanozymes, particularly those with photothermal effects, is being explored. However, the development of nanozymes is hindered by the complex synthesis processes involved and the consumption of reactive oxygen species (ROS) by reducing products in bacteria. This article presents an interesting strategy utilizing near-infrared laser-enhanced oxidase-like (OXD-like) activity of manganese dioxide nanoparticles (MnO2 NPs) to combat subcutaneous infections caused by methicillin-resistant Staphylococcus aureus (MRSA). MnO2 NPs, characterized by flower-like morphology and broad near-infrared absorption, exhibited favorable OXD-like activity and a stable photothermal effect. Experiments in vitro revealed that the combined high thermal effect and the substantial production of ROS effectively targeted MRSA and disrupted biofilm. The efficacy of MnO2 in vivo was validated through the establishment of a subcutaneous abscess model. Additionally, a series of biosafety tests, including routine blood tests and blood biochemistry analyses, confirmed the safety of MnO2 in vivo. Collectively, these findings suggest that combination therapy involving MnO2 presents a promising therapeutic approach for addressing infections associated with biofilms and drug-resistant bacteria.
2026, 37(4): 111200
doi: 10.1016/j.cclet.2025.111200
摘要:
An efficient skeletal editing for the construction of 2-benzodiazepines from benzo[c]oxepines was developed through atom-swapping of oxygen atom to the nitrogen atom. This reaction integrated the sequential ring-opening/substitution/ring-closing in the continuous manufacturing one-pot synthesis. The reaction conditions are mild, transition metal-free, simple-operated and the substrates are widely applicable. The anti-tumor activity of some synthesized 2-benzodiazepine compounds shows this atom-swapping skeletal editing through the deconstruction-reconstruction of heterocycles is attractive and effective in the discovery of new drug skeletons.
An efficient skeletal editing for the construction of 2-benzodiazepines from benzo[c]oxepines was developed through atom-swapping of oxygen atom to the nitrogen atom. This reaction integrated the sequential ring-opening/substitution/ring-closing in the continuous manufacturing one-pot synthesis. The reaction conditions are mild, transition metal-free, simple-operated and the substrates are widely applicable. The anti-tumor activity of some synthesized 2-benzodiazepine compounds shows this atom-swapping skeletal editing through the deconstruction-reconstruction of heterocycles is attractive and effective in the discovery of new drug skeletons.
2026, 37(4): 111215
doi: 10.1016/j.cclet.2025.111215
摘要:
Zinc ions (Zn2+) play a crucial role in maintaining human health, and their imbalance has been associated with various diseases and environmental contamination. Although many fluorescent probes have been developed for Zn2+ detection, they often face challenges, including short emission wavelengths, narrow Stokes shifts, and particularly the poor selectivity. Here, aromatic rings with different electron densities including benzene, thiophene and furan rings, were introduced as aromatic π-conjugated bridges to connect dicyanoisophorone (DCI) and amide-di-2-picolylamine (DPA) based structures, and three probes L1, L2 and L3 for Zn2+ detection were developed. Our results demonstrated that compared with L1, L2 and L3, which inserting thiophene and furan rings, revealed near-infrared (NIR) emission at 651 nm, and a larger Stokes shift of 187 nm. Notably, different from L2, L3, which incorporated a furan ring with the highest electron density, exhibited the highest selectivity for Zn2+ with a low detection limit of 31 nmol/L. In addition, the binding mode of L3 with Zn2+ was confirmed in the form of an imidic acid tautomer. Furthermore, L3 was successfully applied in cellular imaging, validating its potential for in vivo bioimaging. This study presents a promising strategy for developing high-performance Zn2+ probes by simply modifying the aromatic π-conjugated bridges.
Zinc ions (Zn2+) play a crucial role in maintaining human health, and their imbalance has been associated with various diseases and environmental contamination. Although many fluorescent probes have been developed for Zn2+ detection, they often face challenges, including short emission wavelengths, narrow Stokes shifts, and particularly the poor selectivity. Here, aromatic rings with different electron densities including benzene, thiophene and furan rings, were introduced as aromatic π-conjugated bridges to connect dicyanoisophorone (DCI) and amide-di-2-picolylamine (DPA) based structures, and three probes L1, L2 and L3 for Zn2+ detection were developed. Our results demonstrated that compared with L1, L2 and L3, which inserting thiophene and furan rings, revealed near-infrared (NIR) emission at 651 nm, and a larger Stokes shift of 187 nm. Notably, different from L2, L3, which incorporated a furan ring with the highest electron density, exhibited the highest selectivity for Zn2+ with a low detection limit of 31 nmol/L. In addition, the binding mode of L3 with Zn2+ was confirmed in the form of an imidic acid tautomer. Furthermore, L3 was successfully applied in cellular imaging, validating its potential for in vivo bioimaging. This study presents a promising strategy for developing high-performance Zn2+ probes by simply modifying the aromatic π-conjugated bridges.
2026, 37(4): 111217
doi: 10.1016/j.cclet.2025.111217
摘要:
Density functional theory calculations were performed to investigate the iridium-catalyzed atroposelective intermolecular C-H silylation of 2-arylisoquinolines. The Ir(Ⅲ) hydride species was identified as the active catalyst species of the reaction. The computations show that the reaction occurs through the Ir(Ⅲ)/Ir(V) catalytic cycle. The C(sp2)-H oxidative addition represents the rate- and enantioselectivity-determining step. The distortion/interaction and structural analyses reveal that the BINEPINE skeleton of the PSiSi ligand creates an axially chiral pocket for the C-H oxidative addition, providing a ligand-enabled axial chirality transfer strategy responsible for the observed enantioselectivity. The match/mismatch in axial chirality between reacting 2-arylisoquinolines and the BINEPINE skeleton of the PSiSi ligand plays a key role in governing enantioselectivity.
Density functional theory calculations were performed to investigate the iridium-catalyzed atroposelective intermolecular C-H silylation of 2-arylisoquinolines. The Ir(Ⅲ) hydride species was identified as the active catalyst species of the reaction. The computations show that the reaction occurs through the Ir(Ⅲ)/Ir(V) catalytic cycle. The C(sp2)-H oxidative addition represents the rate- and enantioselectivity-determining step. The distortion/interaction and structural analyses reveal that the BINEPINE skeleton of the PSiSi ligand creates an axially chiral pocket for the C-H oxidative addition, providing a ligand-enabled axial chirality transfer strategy responsible for the observed enantioselectivity. The match/mismatch in axial chirality between reacting 2-arylisoquinolines and the BINEPINE skeleton of the PSiSi ligand plays a key role in governing enantioselectivity.
2026, 37(4): 111220
doi: 10.1016/j.cclet.2025.111220
摘要:
Ferroptosis has emerged as a significant pathway in various pathological conditions. Studying the effects of inhibiting ferroptosis on liver injury is instrumental in gaining a deeper understanding of the mechanisms. This study the design and synthesis of a multi-channel near-infrared emitting fluorescent probe TXVQ. When the probe TXVQ responds to HSO3−, the fluorescence intensity at 500 nm of TXVQ increases with the addition of HSO3−. As the concentration of H2O2 increases, the fluorescence intensity of TXVQ at 600 nm is enhanced. Concurrently, as viscosity rises, the fluorescence intensity of the probe TXVQ at 725 nm will gradually increase. The probe TXVQ, with its ability to monitor HSO3−, H2O2 and viscosity through three distinct fluorescent channels, is advantageous for its application in the biological field. Subsequently, cellular experiments have demonstrated that the probe TXVQ can monitor changes in intracellular HSO3−, H2O2 and viscosity. At the cellular level, it is found that inhibiting ferroptosis had no alleviating effect on drug-induced liver injury (DILI), but it had a certain alleviating effect on acute kidney injury (AKI). In a murine model, the effects of ferroptosis inhibition on DILI and AKI indicate that inhibiting ferroptosis reduced kidney injury but not liver injury, highlighting its potential in kidney therapeutics. TXVQ can detect various levels of HSO3−, H2O2 and viscosity through three different fluorescent channels, making it a powerful tool for diagnosing and treating kidney diseases, as well as deepening the understanding of the role of ferroptosis in liver and kidney pathologies.
Ferroptosis has emerged as a significant pathway in various pathological conditions. Studying the effects of inhibiting ferroptosis on liver injury is instrumental in gaining a deeper understanding of the mechanisms. This study the design and synthesis of a multi-channel near-infrared emitting fluorescent probe TXVQ. When the probe TXVQ responds to HSO3−, the fluorescence intensity at 500 nm of TXVQ increases with the addition of HSO3−. As the concentration of H2O2 increases, the fluorescence intensity of TXVQ at 600 nm is enhanced. Concurrently, as viscosity rises, the fluorescence intensity of the probe TXVQ at 725 nm will gradually increase. The probe TXVQ, with its ability to monitor HSO3−, H2O2 and viscosity through three distinct fluorescent channels, is advantageous for its application in the biological field. Subsequently, cellular experiments have demonstrated that the probe TXVQ can monitor changes in intracellular HSO3−, H2O2 and viscosity. At the cellular level, it is found that inhibiting ferroptosis had no alleviating effect on drug-induced liver injury (DILI), but it had a certain alleviating effect on acute kidney injury (AKI). In a murine model, the effects of ferroptosis inhibition on DILI and AKI indicate that inhibiting ferroptosis reduced kidney injury but not liver injury, highlighting its potential in kidney therapeutics. TXVQ can detect various levels of HSO3−, H2O2 and viscosity through three different fluorescent channels, making it a powerful tool for diagnosing and treating kidney diseases, as well as deepening the understanding of the role of ferroptosis in liver and kidney pathologies.
2026, 37(4): 111225
doi: 10.1016/j.cclet.2025.111225
摘要:
In this study, we report a palladium-catalyzed carbene C-H insertion reaction of non-activated arenes using N-tosylhydrazones as both carbene and olefin precursors. This method consists of a two-step, one-pot process, where the arenes are first thianthrenated and then undergo migratory insertion/β-H elimination with N-tosylhydrazones to form aryl alkenes. This highly site-selective C-H alkenylation of arenes demonstrates a relatively broad substrate scope and exhibits high tolerance for halogen substituents. Importantly, this transformation allows for the modification of the arene moiety in commercially available bioactive molecules, underscoring its significant potential for late-stage functionalization of arene-containing pharmaceuticals.
In this study, we report a palladium-catalyzed carbene C-H insertion reaction of non-activated arenes using N-tosylhydrazones as both carbene and olefin precursors. This method consists of a two-step, one-pot process, where the arenes are first thianthrenated and then undergo migratory insertion/β-H elimination with N-tosylhydrazones to form aryl alkenes. This highly site-selective C-H alkenylation of arenes demonstrates a relatively broad substrate scope and exhibits high tolerance for halogen substituents. Importantly, this transformation allows for the modification of the arene moiety in commercially available bioactive molecules, underscoring its significant potential for late-stage functionalization of arene-containing pharmaceuticals.
2026, 37(4): 111235
doi: 10.1016/j.cclet.2025.111235
摘要:
Colon cancer is one of the malignant tumors with high morbidity and mortality worldwide, and its etiology is closely related to high levels of hydrogen sulfide (H2S). To date, H2S-activated near-infrared (NIR) fluorescent (FL) probes with high tumor tropism are still scarce. In this work, we created a new NIR FL probes (Cy-DG) that enables colon cancer targeted imaging and rapid fecal optical analysis by introducing an H2S-recognition moiety and two D-glucosamine fragments on the scaffold of QCy7. Cy-DG exhibits excellent properties, including specific "off-on" response toward H2S, intense NIR emission at 703 nm, large Stokes shift (118 nm), and high sensitivity (limit of detection (LOD), 0.48 µmol/L). Notably, the presence of D-glucosamine allows Cy-DG to be preferentially taken up by cancer cells. After intravenous administration, Cy-DG was able to efficiently accumulate in a MC38 intestinal cancer model and sensitively detect endogenous H2S in vivo, showing 5.94-fold higher fluorescence intensity in small tumors < 5 mm. Furthermore, Cy-DG was successfully used to detect H2S in feces samples from colon cancer-bearing mice. We believe that Cy-DG has great potential as a powerful diagnostic tool for H2S-related disorder and stool examinations in the future.
Colon cancer is one of the malignant tumors with high morbidity and mortality worldwide, and its etiology is closely related to high levels of hydrogen sulfide (H2S). To date, H2S-activated near-infrared (NIR) fluorescent (FL) probes with high tumor tropism are still scarce. In this work, we created a new NIR FL probes (Cy-DG) that enables colon cancer targeted imaging and rapid fecal optical analysis by introducing an H2S-recognition moiety and two D-glucosamine fragments on the scaffold of QCy7. Cy-DG exhibits excellent properties, including specific "off-on" response toward H2S, intense NIR emission at 703 nm, large Stokes shift (118 nm), and high sensitivity (limit of detection (LOD), 0.48 µmol/L). Notably, the presence of D-glucosamine allows Cy-DG to be preferentially taken up by cancer cells. After intravenous administration, Cy-DG was able to efficiently accumulate in a MC38 intestinal cancer model and sensitively detect endogenous H2S in vivo, showing 5.94-fold higher fluorescence intensity in small tumors < 5 mm. Furthermore, Cy-DG was successfully used to detect H2S in feces samples from colon cancer-bearing mice. We believe that Cy-DG has great potential as a powerful diagnostic tool for H2S-related disorder and stool examinations in the future.
2026, 37(4): 111250
doi: 10.1016/j.cclet.2025.111250
摘要:
The single-electron transfer-induced oxidative transformation of indoles has been extensively explored in recent years. However, research toward high enantioselective control in this reaction is rare. Herein, we report an enantioselective catalytic single-electron transfer-induced oxidative rearrangement of cyclic indoles enabled by dual chiral copper/phosphoric acid catalysis. Using atmospheric oxygen (O2) as the terminal oxidant, the reactions of tetrahydro-β-carbolines, tetrahydropyrano[3,4-b]indoles and the challenging tetrahydrocarbazoles are all realized, providing diverse rearrangement products including pyrrolidinyl-, tetrahydrofuranyl- and cyclopentyl-bearing spiroindolinones in good yields with high enantioselectivities. The synthetic utility of this protocol was demonstrated in a concise synthesis of (+)-coerulescine and (+)-horsfiline. These findings would provide new insights and opportunities for future asymmetric oxidative radical reaction design.
The single-electron transfer-induced oxidative transformation of indoles has been extensively explored in recent years. However, research toward high enantioselective control in this reaction is rare. Herein, we report an enantioselective catalytic single-electron transfer-induced oxidative rearrangement of cyclic indoles enabled by dual chiral copper/phosphoric acid catalysis. Using atmospheric oxygen (O2) as the terminal oxidant, the reactions of tetrahydro-β-carbolines, tetrahydropyrano[3,4-b]indoles and the challenging tetrahydrocarbazoles are all realized, providing diverse rearrangement products including pyrrolidinyl-, tetrahydrofuranyl- and cyclopentyl-bearing spiroindolinones in good yields with high enantioselectivities. The synthetic utility of this protocol was demonstrated in a concise synthesis of (+)-coerulescine and (+)-horsfiline. These findings would provide new insights and opportunities for future asymmetric oxidative radical reaction design.
2026, 37(4): 111259
doi: 10.1016/j.cclet.2025.111259
摘要:
Available online-The enantioselective chlorination is a continuing challenge owing to the highly reactive nature of chloronium ions. Herein, tertiary ammonium salt catalysis for asymmetric chloro– and selenocyclization of 2-alkenyl anilides with high enantioselectivities were achieved at room temperature. This approach affords the green and atom-economical access to chiral 4H-3,1-benzoxazines with excellent functional-group tolerance. The catalyst could be reused for 3 runs, no obvious loss in catalytic activity and enantioselectivity was observed. This catalytic system can be applied to late-stage modification of pharmaceuticals and natural products. Computational mechanistic studies revealed that the non-classical hydrogen bond (C-H…O) between the phosphate anion and ammonium cation plays crucial role in the stereocontrol of the reaction.
Available online-The enantioselective chlorination is a continuing challenge owing to the highly reactive nature of chloronium ions. Herein, tertiary ammonium salt catalysis for asymmetric chloro– and selenocyclization of 2-alkenyl anilides with high enantioselectivities were achieved at room temperature. This approach affords the green and atom-economical access to chiral 4H-3,1-benzoxazines with excellent functional-group tolerance. The catalyst could be reused for 3 runs, no obvious loss in catalytic activity and enantioselectivity was observed. This catalytic system can be applied to late-stage modification of pharmaceuticals and natural products. Computational mechanistic studies revealed that the non-classical hydrogen bond (C-H…O) between the phosphate anion and ammonium cation plays crucial role in the stereocontrol of the reaction.
2026, 37(4): 111276
doi: 10.1016/j.cclet.2025.111276
摘要:
An efficient method for the three-component azidopyridylation of unactivated alkenes to access β-pyridyl azides has been developed. The overall process involves a visible light-mediated radical-relay sequence that begins with an in situ generated methoxy radical, which may facilitate Si−N3 bond activation to generate azidyl radical under mild conditions. The ensuing azidyl radical adds to the alkenes to furnish the carbon-centered radicals which themselves add, in an intermolecular sense, to pyridinium salts. This three-component photocatalytic strategy is effective for a broad range of alkenes and N-heterocycles, and readily affords synthetically useful azidyl- and pyridyl-containing building blocks. This method provides new insights into methoxy radical-initiated relay reactions as well as access to a range of new molecular scaffolds.
An efficient method for the three-component azidopyridylation of unactivated alkenes to access β-pyridyl azides has been developed. The overall process involves a visible light-mediated radical-relay sequence that begins with an in situ generated methoxy radical, which may facilitate Si−N3 bond activation to generate azidyl radical under mild conditions. The ensuing azidyl radical adds to the alkenes to furnish the carbon-centered radicals which themselves add, in an intermolecular sense, to pyridinium salts. This three-component photocatalytic strategy is effective for a broad range of alkenes and N-heterocycles, and readily affords synthetically useful azidyl- and pyridyl-containing building blocks. This method provides new insights into methoxy radical-initiated relay reactions as well as access to a range of new molecular scaffolds.
2026, 37(4): 111277
doi: 10.1016/j.cclet.2025.111277
摘要:
Selective activation of C-C bonds via molecular editing is a fundamental challenge in organic synthesis. Among the various strategies, metathesis reactions have emerged as powerful tools for constructing new molecular architectures due to their well-established mechanisms. However, these reactions have largely been limited to the same types of covalent bonds, such as σ-σ or π-π bonds, leaving σ-π cross-metathesis reactions unexplored. Perhaps the bond redistribution between the σ and π bonds is highly difficult due to the lack of p orbital in σ bonds. Herein, we report the first example of a transition metal-free σ-π cross-metathesis reaction that converts methyl ketones into the corresponding carboxylic acids along with the formation of 11H-benzo[b]fluoren-11-one. A comprehensive mechanistic investigation, supported by DFT calculations, was conducted to elucidate the unique reaction pathway. This study not only provides compelling evidence for the first σ-π cross-metathesis reaction but also demonstrates the formation of a key oxetan-2-olate intermediate and its utility in organic transformations. This novel concept and strategy expand the scope of traditional metathesis reactions, offering new possibilities for selective C-C bond activation in a redox-neutral manner.
Selective activation of C-C bonds via molecular editing is a fundamental challenge in organic synthesis. Among the various strategies, metathesis reactions have emerged as powerful tools for constructing new molecular architectures due to their well-established mechanisms. However, these reactions have largely been limited to the same types of covalent bonds, such as σ-σ or π-π bonds, leaving σ-π cross-metathesis reactions unexplored. Perhaps the bond redistribution between the σ and π bonds is highly difficult due to the lack of p orbital in σ bonds. Herein, we report the first example of a transition metal-free σ-π cross-metathesis reaction that converts methyl ketones into the corresponding carboxylic acids along with the formation of 11H-benzo[b]fluoren-11-one. A comprehensive mechanistic investigation, supported by DFT calculations, was conducted to elucidate the unique reaction pathway. This study not only provides compelling evidence for the first σ-π cross-metathesis reaction but also demonstrates the formation of a key oxetan-2-olate intermediate and its utility in organic transformations. This novel concept and strategy expand the scope of traditional metathesis reactions, offering new possibilities for selective C-C bond activation in a redox-neutral manner.
2026, 37(4): 111278
doi: 10.1016/j.cclet.2025.111278
摘要:
Cell-penetrating peptides (CPPs) hold great potential as a tool using non-invasive delivery of therapeutic or diagnostic molecules into mammalian cells, but their broad application has been limited by poor endosomal escape. Thus, the rational design and selection of CPPs remains a challenge and calls for deeper mechanistic understandings. Here, we developed novel stapled cell-penetrating peptides based on the highly positively charged HIV Tat47-57 peptide using decafluorobiphenyl-cysteine SNAr chemistry which selectively disrupt endosomal membranes. A series of stapled peptides with a cross-linked structure were synthesized and investigated their cellular uptake, endosomal escape and intracellular delivery of cargoes. Among these peptides, analogues P3 and P6 demonstrated the highest cellular uptake and endosomal escape activities with efficiencies 3.5−9-fold higher than that of Tat47-57. Notably, the results demonstrated that the decafluorobiphenyl bridge of stapled peptides exhibited significant ability for cellular uptake and endosomal escape. Moreover, we found that fluorine atoms of decafluorobiphenyl bridge played a key role for disrupting endosomal membranes. Finally, the utility of this strategy has been demonstrated by the intracellular delivery of biomacromolecules (avidin and negatively charged phosphopeptides). Together, these results suggest that the decafluorobiphenyl-cysteine SNAr chemistry may be an efficient strategy for the development of novel stapled CPPs.
Cell-penetrating peptides (CPPs) hold great potential as a tool using non-invasive delivery of therapeutic or diagnostic molecules into mammalian cells, but their broad application has been limited by poor endosomal escape. Thus, the rational design and selection of CPPs remains a challenge and calls for deeper mechanistic understandings. Here, we developed novel stapled cell-penetrating peptides based on the highly positively charged HIV Tat47-57 peptide using decafluorobiphenyl-cysteine SNAr chemistry which selectively disrupt endosomal membranes. A series of stapled peptides with a cross-linked structure were synthesized and investigated their cellular uptake, endosomal escape and intracellular delivery of cargoes. Among these peptides, analogues P3 and P6 demonstrated the highest cellular uptake and endosomal escape activities with efficiencies 3.5−9-fold higher than that of Tat47-57. Notably, the results demonstrated that the decafluorobiphenyl bridge of stapled peptides exhibited significant ability for cellular uptake and endosomal escape. Moreover, we found that fluorine atoms of decafluorobiphenyl bridge played a key role for disrupting endosomal membranes. Finally, the utility of this strategy has been demonstrated by the intracellular delivery of biomacromolecules (avidin and negatively charged phosphopeptides). Together, these results suggest that the decafluorobiphenyl-cysteine SNAr chemistry may be an efficient strategy for the development of novel stapled CPPs.
2026, 37(4): 111279
doi: 10.1016/j.cclet.2025.111279
摘要:
Hierarchical assembly provides a rational procedure to acquire complex supramolecular architectures from basic building blocks. In this work, a novel kind of double-stranded polyrotaxane motif was reported by Ag+-directed coordination-driven assembly following the preassembly of a four-connected pseudorotaxane (cpb)2CB8 linker. Moreover, supramolecular isomerism is observed in crystalline compounds based on double-stranded polyrotaxane motifs due to differences in lattice stacking mode. Interestingly, the resultant supramolecular isomers, cross-Ag-DSP-1 and para-Ag-DSP-1, show dual thermo- and anion-responsiveness. Benefiting from high crystallinity of these coordination assemblies, a combination of characterization techniques, especially X-ray diffraction, was used to unveil precise molecular mechanisms related to the inherent dynamic behavior of these assemblies, which can be attributed to remarkable lattice rearrangement and crystal transformations as temperature increases or after anion exchange, reflecting the adaptive adjustment ability of these supramolecular architectures in response to external stimuli. Based on the anion exchange capability, these two supramolecular materials show fast removal kinetics and high sorption capacity for perrhenate (ReO4-) anion, a surrogate of radioactive pertechnetate (TcO4-) in nuclear waste eluents. This work provides a feasible way to supramolecular assemblies with customized structures and stimuli-responsiveness, and is helpful to design and synthesize more functional supramolecular systems with complex structures and tailored functions.
Hierarchical assembly provides a rational procedure to acquire complex supramolecular architectures from basic building blocks. In this work, a novel kind of double-stranded polyrotaxane motif was reported by Ag+-directed coordination-driven assembly following the preassembly of a four-connected pseudorotaxane (cpb)2CB8 linker. Moreover, supramolecular isomerism is observed in crystalline compounds based on double-stranded polyrotaxane motifs due to differences in lattice stacking mode. Interestingly, the resultant supramolecular isomers, cross-Ag-DSP-1 and para-Ag-DSP-1, show dual thermo- and anion-responsiveness. Benefiting from high crystallinity of these coordination assemblies, a combination of characterization techniques, especially X-ray diffraction, was used to unveil precise molecular mechanisms related to the inherent dynamic behavior of these assemblies, which can be attributed to remarkable lattice rearrangement and crystal transformations as temperature increases or after anion exchange, reflecting the adaptive adjustment ability of these supramolecular architectures in response to external stimuli. Based on the anion exchange capability, these two supramolecular materials show fast removal kinetics and high sorption capacity for perrhenate (ReO4-) anion, a surrogate of radioactive pertechnetate (TcO4-) in nuclear waste eluents. This work provides a feasible way to supramolecular assemblies with customized structures and stimuli-responsiveness, and is helpful to design and synthesize more functional supramolecular systems with complex structures and tailored functions.
2026, 37(4): 111304
doi: 10.1016/j.cclet.2025.111304
摘要:
Alkene cross-coupling provides a simple and efficient approach for constructing C–C bonds using readily accessible alkene feedstocks. Despite significant progress in C–C bonds formation through the difunctionalization of alkenes, analogous reaction involving two distinct alkenes remains extremely limited. Herein, we report the excited-state palladium(0) catalyzed alkenylcarboxylation of two distinct alkenes with CO2, delivering a variety of carboxylic acids in moderate to excellent yields. This reaction features high regio- & chemoselectivity, broad substrate scope (> 70 examples), and facile derivatization of products. Mechanistic studies indicate that the key step for this new strategy lies in the reductive activation of electron-deficient alkenes with the excited-state palladium complex to generate alkene radical anions. The current single-electron reduction strategy for alkenes catalyzed by photoexcited palladium(0) not only broadens the scope of excited palladium chemistry but also provides a mild approach for alkenes activation. Furthermore, this method serves as an efficient tool for the rapid construction of multiple C–C bonds in a one-pot operation using two distinct alkenes.
Alkene cross-coupling provides a simple and efficient approach for constructing C–C bonds using readily accessible alkene feedstocks. Despite significant progress in C–C bonds formation through the difunctionalization of alkenes, analogous reaction involving two distinct alkenes remains extremely limited. Herein, we report the excited-state palladium(0) catalyzed alkenylcarboxylation of two distinct alkenes with CO2, delivering a variety of carboxylic acids in moderate to excellent yields. This reaction features high regio- & chemoselectivity, broad substrate scope (> 70 examples), and facile derivatization of products. Mechanistic studies indicate that the key step for this new strategy lies in the reductive activation of electron-deficient alkenes with the excited-state palladium complex to generate alkene radical anions. The current single-electron reduction strategy for alkenes catalyzed by photoexcited palladium(0) not only broadens the scope of excited palladium chemistry but also provides a mild approach for alkenes activation. Furthermore, this method serves as an efficient tool for the rapid construction of multiple C–C bonds in a one-pot operation using two distinct alkenes.
2026, 37(4): 111317
doi: 10.1016/j.cclet.2025.111317
摘要:
Long-wavelength fluorescent dyes have revolutionized in vivo fluorescence imaging by offering unparalleled spatial resolution. Nevertheless, the majority of organic fluorescent dyes documented to date exhibit emission wavelengths predominantly within the range of 1000–1100 nm, with scarcely any surpassing the 1200 nm threshold. Herein, we introduce a heptamethine cyanine dye that boasts a remarkable fluorescence wavelength of 1239 nm. To our knowledge, this represents the longest fluorescence wavelength for heptamethine benzindole derivative. We have meticulously analyzed its photophysical characteristics and solvatochromic behavior, and assessed its efficacy in vivo fluorescence imaging applications.
Long-wavelength fluorescent dyes have revolutionized in vivo fluorescence imaging by offering unparalleled spatial resolution. Nevertheless, the majority of organic fluorescent dyes documented to date exhibit emission wavelengths predominantly within the range of 1000–1100 nm, with scarcely any surpassing the 1200 nm threshold. Herein, we introduce a heptamethine cyanine dye that boasts a remarkable fluorescence wavelength of 1239 nm. To our knowledge, this represents the longest fluorescence wavelength for heptamethine benzindole derivative. We have meticulously analyzed its photophysical characteristics and solvatochromic behavior, and assessed its efficacy in vivo fluorescence imaging applications.
2026, 37(4): 111320
doi: 10.1016/j.cclet.2025.111320
摘要:
Bile salt hydrolase (BSH), a gatekeeper enzyme in bile acid metabolism, regulates the host's bile acid profile and is closely associated with various metabolic diseases. However, suitable methods for measuring its activity in living systems remain scarce. Herein, a novel far-red fluorogenic substrate (CA-ABEI) for BSH was designed and developed by conjugating cholic acid with an aminocoumarin fluorophore. Under physiological conditions, CA-ABEI can be rapidly hydrolyzed by BSH from various bacterial sources to form ABEI, triggering strong fluorescence enhancement at 620 nm. Specifically activated by BSH, CA-ABEI enables accurate detection of BSH activity in biospecimens, including pure enzymes, bacteria and intact fecal slurries, and the first bioimaging of BSH activity in both BSH-expressing engineered Escherichia coli and natural intestinal microbiota. Moreover, a high-throughput screening platform was established using CA-ABEI, enabling the evaluation of BSH inhibitory effects from 96 herbal extracts. Pu-erh tea emerged as a potent BSH inhibitor and its active components were subsequently characterized, aiding the discovery of novel BSH inhibitors. Collectively, CA-ABEI proved to be a powerful tool for monitoring BSH activity in complex biological systems with value for exploring physiological functions and rapid screening of inhibitors.
Bile salt hydrolase (BSH), a gatekeeper enzyme in bile acid metabolism, regulates the host's bile acid profile and is closely associated with various metabolic diseases. However, suitable methods for measuring its activity in living systems remain scarce. Herein, a novel far-red fluorogenic substrate (CA-ABEI) for BSH was designed and developed by conjugating cholic acid with an aminocoumarin fluorophore. Under physiological conditions, CA-ABEI can be rapidly hydrolyzed by BSH from various bacterial sources to form ABEI, triggering strong fluorescence enhancement at 620 nm. Specifically activated by BSH, CA-ABEI enables accurate detection of BSH activity in biospecimens, including pure enzymes, bacteria and intact fecal slurries, and the first bioimaging of BSH activity in both BSH-expressing engineered Escherichia coli and natural intestinal microbiota. Moreover, a high-throughput screening platform was established using CA-ABEI, enabling the evaluation of BSH inhibitory effects from 96 herbal extracts. Pu-erh tea emerged as a potent BSH inhibitor and its active components were subsequently characterized, aiding the discovery of novel BSH inhibitors. Collectively, CA-ABEI proved to be a powerful tool for monitoring BSH activity in complex biological systems with value for exploring physiological functions and rapid screening of inhibitors.
2026, 37(4): 111351
doi: 10.1016/j.cclet.2025.111351
摘要:
To promote the advantages of near-infrared-Ⅱ (NIR-Ⅱ) imaging, researchers have developed various types of NIR-Ⅱ imaging contrast agents, with conjugated dyes being one of the most important categories. However, hydrophobic dyes often rely on encapsulation with amphiphilic polymers for biological applications, which lead to brightness quenching and instability in vivo. To address this, we proposed a covalent encapsulation strategy to transform the hydrophobic dye from organic solvent to aqueous solution. To achieve this, we designed a chlorine-containing NIR-Ⅱ cyanine dye (C7–1080), which covalently binds to human serum albumin (HSA), forming a stable NIR-Ⅱ fluorescent probe, HSA@C7–1080. The HSA@C7–1080 has precise molecular weight and spatial structure, making dye monodispersing in the albumin pocket with improved fluorescence and stability. This NIR-Ⅱ fluorescent probe provides high-resolution NIR-Ⅱ imaging in various biological systems. Our strategy offers a promising alternative for the clinical translation of hydrophobic NIR-Ⅱ dyes, improving their biocompatibility and imaging performance in fluorescence-guided surgery.
To promote the advantages of near-infrared-Ⅱ (NIR-Ⅱ) imaging, researchers have developed various types of NIR-Ⅱ imaging contrast agents, with conjugated dyes being one of the most important categories. However, hydrophobic dyes often rely on encapsulation with amphiphilic polymers for biological applications, which lead to brightness quenching and instability in vivo. To address this, we proposed a covalent encapsulation strategy to transform the hydrophobic dye from organic solvent to aqueous solution. To achieve this, we designed a chlorine-containing NIR-Ⅱ cyanine dye (C7–1080), which covalently binds to human serum albumin (HSA), forming a stable NIR-Ⅱ fluorescent probe, HSA@C7–1080. The HSA@C7–1080 has precise molecular weight and spatial structure, making dye monodispersing in the albumin pocket with improved fluorescence and stability. This NIR-Ⅱ fluorescent probe provides high-resolution NIR-Ⅱ imaging in various biological systems. Our strategy offers a promising alternative for the clinical translation of hydrophobic NIR-Ⅱ dyes, improving their biocompatibility and imaging performance in fluorescence-guided surgery.
2026, 37(4): 111352
doi: 10.1016/j.cclet.2025.111352
摘要:
The cycloaddition of epoxides and CO2 has been achieved by using the designed upper-rim functionalized calix[4]arene organocatalyst in aqueous at a mild temperature under normal pressure. The upper rim of this novel calix[4]arene organocatalyst contains two hemisquaramides at the 1,4-positions. A variety of cyclic carbonate derivatives were obtained in good yields, demonstrating excellent compatibility with various functional groups. The π···π supramolecular interaction between the calixarene cavity and epoxide substrate may also play a significant role in facilitating this cycloaddition process. Additionally, this novel reaction offers a valuable complementary approach to synthesizing cyclic carbonates from epoxides and CO2.
The cycloaddition of epoxides and CO2 has been achieved by using the designed upper-rim functionalized calix[4]arene organocatalyst in aqueous at a mild temperature under normal pressure. The upper rim of this novel calix[4]arene organocatalyst contains two hemisquaramides at the 1,4-positions. A variety of cyclic carbonate derivatives were obtained in good yields, demonstrating excellent compatibility with various functional groups. The π···π supramolecular interaction between the calixarene cavity and epoxide substrate may also play a significant role in facilitating this cycloaddition process. Additionally, this novel reaction offers a valuable complementary approach to synthesizing cyclic carbonates from epoxides and CO2.
2026, 37(4): 111354
doi: 10.1016/j.cclet.2025.111354
摘要:
Here, Friedel–Crafts (FC) reaction is used to synthesize a purely organic cage in a one-pot manner. The trigonal prismatic cage is composed of two trisfuran platforms, bridged by three phenanthrene pillars each bearing two methoxy (OMe) units. The organic cage exhibited good kinetic inertness, allowing for a synthetic post-functionalization. During this transforming process, the electron-donating methoxy (OMe) groups were converted into electron-withdrawing carbonyl groups without any degradation on the cage framework. The cage exhibits multiple guest recognition modes. The oxygen atoms as the Lewis base present in either methoxy or carbonyl before and after post-functionalization, endow the cage with the ability to recognize Lewis acidic guests such as alkali cations. The OMe and carbonyl units grated on the phenanthrene pillars endow the cage with an π-electron-rich and π-electron-deficient cavity, respectively, where π-electron-deficient and π-electron-rich guests can be accommodated.
Here, Friedel–Crafts (FC) reaction is used to synthesize a purely organic cage in a one-pot manner. The trigonal prismatic cage is composed of two trisfuran platforms, bridged by three phenanthrene pillars each bearing two methoxy (OMe) units. The organic cage exhibited good kinetic inertness, allowing for a synthetic post-functionalization. During this transforming process, the electron-donating methoxy (OMe) groups were converted into electron-withdrawing carbonyl groups without any degradation on the cage framework. The cage exhibits multiple guest recognition modes. The oxygen atoms as the Lewis base present in either methoxy or carbonyl before and after post-functionalization, endow the cage with the ability to recognize Lewis acidic guests such as alkali cations. The OMe and carbonyl units grated on the phenanthrene pillars endow the cage with an π-electron-rich and π-electron-deficient cavity, respectively, where π-electron-deficient and π-electron-rich guests can be accommodated.
2026, 37(4): 111377
doi: 10.1016/j.cclet.2025.111377
摘要:
Polyfunctionalized axial-chiral 2-arylpyridines are important class of chiral entities in organic synthesis and drug discovery. However, practical synthesis of such structures remains underdeveloped. Herein, we report a novel synthetic method via simple cobalt-catalyzed [2 + 2 + 2] cycloaddition reactions of easily accessible diynes with nitriles. A wide range of polyfunctionalized axial-chiral 2-arylpyridine derivatives were obtained with high enantioselectivities and atom economy by using 2-methyl tetrahydrofuran (2-MeTHF) as a green solvent. Notably, the axial-chiral 2-arylpyridine N-oxide compounds and chiral bispyridine derivatives have been accessible in high efficiency using this simple protocol. The mechanism and origin of regioselectivity of this reaction was revealed using DFT calculation profiles.
Polyfunctionalized axial-chiral 2-arylpyridines are important class of chiral entities in organic synthesis and drug discovery. However, practical synthesis of such structures remains underdeveloped. Herein, we report a novel synthetic method via simple cobalt-catalyzed [2 + 2 + 2] cycloaddition reactions of easily accessible diynes with nitriles. A wide range of polyfunctionalized axial-chiral 2-arylpyridine derivatives were obtained with high enantioselectivities and atom economy by using 2-methyl tetrahydrofuran (2-MeTHF) as a green solvent. Notably, the axial-chiral 2-arylpyridine N-oxide compounds and chiral bispyridine derivatives have been accessible in high efficiency using this simple protocol. The mechanism and origin of regioselectivity of this reaction was revealed using DFT calculation profiles.
2026, 37(4): 111433
doi: 10.1016/j.cclet.2025.111433
摘要:
Core-shell magnetic polymer microspheres with mesoporous organic shells hold immense potential in diverse applications, encompassing adsorption, separation, delivery/immobilization of guest molecules in catalysis and controlled drug release. Herein, magnetic mesoporous melamine-formaldehyde resin microspheres (Fe3O4@SiO2@mMF) are constructed via a nanoemulsion-assisted interfacial co-assembly and polymerization strategy, using Pluronic F127 as a template agent and soluble melamine-formaldehyde (MF) oligomer as the precursor. The resulting microspheres possess radially oriented mesopores, superparamagnetic properties, and abundant N-containing active sites (nitrogen content: 15.02 wt%). The as-synthesized Fe3O4@SiO2@mMF microspheres as ideal catalyst supports, exhibit exceptional loading capacity for phosphotungstic acid (PTA). The as-formed Fe3O4@SiO2@mMF/PTA composites demonstrate not only good catalytic performance in the esterification reaction of n-butanol and acetic acid with a high conversion of 92% (to acetic acid) but also excellent antimicrobial performance against Staphylococcus aureus and Escherichia coli with viabilities of 11.58% and 7.35%, respectively.
Core-shell magnetic polymer microspheres with mesoporous organic shells hold immense potential in diverse applications, encompassing adsorption, separation, delivery/immobilization of guest molecules in catalysis and controlled drug release. Herein, magnetic mesoporous melamine-formaldehyde resin microspheres (Fe3O4@SiO2@mMF) are constructed via a nanoemulsion-assisted interfacial co-assembly and polymerization strategy, using Pluronic F127 as a template agent and soluble melamine-formaldehyde (MF) oligomer as the precursor. The resulting microspheres possess radially oriented mesopores, superparamagnetic properties, and abundant N-containing active sites (nitrogen content: 15.02 wt%). The as-synthesized Fe3O4@SiO2@mMF microspheres as ideal catalyst supports, exhibit exceptional loading capacity for phosphotungstic acid (PTA). The as-formed Fe3O4@SiO2@mMF/PTA composites demonstrate not only good catalytic performance in the esterification reaction of n-butanol and acetic acid with a high conversion of 92% (to acetic acid) but also excellent antimicrobial performance against Staphylococcus aureus and Escherichia coli with viabilities of 11.58% and 7.35%, respectively.
2026, 37(4): 111453
doi: 10.1016/j.cclet.2025.111453
摘要:
The deficiency of reliable and physiologically relevant distal lung models has been regarded as a crucial issue for drug research on non small cell lung cancer (NSCLC). In this study, an inverse opal structure-based lung-on-a-chip was established to replicate the geometric dimensions and topography of the native lung alveoli, and two lateral microchambers were designed to induce pressure-driven stretching for the simulation of respiratory movement. Further, a concentration gradient generator was applied to connect with lung-on-a-chip for the creation of different enzyme environments to mimic the individual variability of P450s enzymes in lung patients. Based on this microfluidic platform, the Osimertinib implications in NSLC was investigated from the aspect of metabolism and adapted resistance. The results suggested that Osimertinib exhibited discernible difference in metabolism under diverse enzyme condition. Additionally, in contrast with the control group, all groups with Osimertinib treatment triggered the alterations of amino acid metabolisms and energy supply, indicating that targeting energy supply process might be an effective measure to prevent tumor cells from generating drug resistance.
The deficiency of reliable and physiologically relevant distal lung models has been regarded as a crucial issue for drug research on non small cell lung cancer (NSCLC). In this study, an inverse opal structure-based lung-on-a-chip was established to replicate the geometric dimensions and topography of the native lung alveoli, and two lateral microchambers were designed to induce pressure-driven stretching for the simulation of respiratory movement. Further, a concentration gradient generator was applied to connect with lung-on-a-chip for the creation of different enzyme environments to mimic the individual variability of P450s enzymes in lung patients. Based on this microfluidic platform, the Osimertinib implications in NSLC was investigated from the aspect of metabolism and adapted resistance. The results suggested that Osimertinib exhibited discernible difference in metabolism under diverse enzyme condition. Additionally, in contrast with the control group, all groups with Osimertinib treatment triggered the alterations of amino acid metabolisms and energy supply, indicating that targeting energy supply process might be an effective measure to prevent tumor cells from generating drug resistance.
2026, 37(4): 111463
doi: 10.1016/j.cclet.2025.111463
摘要:
Carbon nitride (CN)-based photocatalytic processes hold promise for water decontamination, during which the widely acknowledged charge transfer pathway is unfortunately characterized by severe chemical stability challenges. Herein, the intensive yet underestimated energy transfer pathway is achieved in CN nanosheets for durable, efficient, and sustainable water purification. Upon simple oxygen activation in air, the synthesized nanosheets come with an optimal pollutant removal rate constant of 0.18 min−1 under visible light irradiation, far exceeding that of state-of-the-art photocatalysts. It is revealed that the enhanced exciton binding energy inside the CN nanosheets triggers strong exciton effects, promoting the accumulation of triplet-state excitons by regulating the energy gap. The accumulated triplet excitons almost accomplish the transition from oxygen exclusively to singlet oxygen via the energy transfer pathway, which ultimately contributes to the robust degradation of the pollutants. This work proposes a viable strategy to enhance the exciton effect within CN, upon which efficient water treatment technology driven by energy transfer pathways can be expected.
Carbon nitride (CN)-based photocatalytic processes hold promise for water decontamination, during which the widely acknowledged charge transfer pathway is unfortunately characterized by severe chemical stability challenges. Herein, the intensive yet underestimated energy transfer pathway is achieved in CN nanosheets for durable, efficient, and sustainable water purification. Upon simple oxygen activation in air, the synthesized nanosheets come with an optimal pollutant removal rate constant of 0.18 min−1 under visible light irradiation, far exceeding that of state-of-the-art photocatalysts. It is revealed that the enhanced exciton binding energy inside the CN nanosheets triggers strong exciton effects, promoting the accumulation of triplet-state excitons by regulating the energy gap. The accumulated triplet excitons almost accomplish the transition from oxygen exclusively to singlet oxygen via the energy transfer pathway, which ultimately contributes to the robust degradation of the pollutants. This work proposes a viable strategy to enhance the exciton effect within CN, upon which efficient water treatment technology driven by energy transfer pathways can be expected.
2026, 37(4): 111488
doi: 10.1016/j.cclet.2025.111488
摘要:
Cervical cancer remains a leading cause of cancer-related mortality in women, underscoring the urgent need for advanced diagnostic and therapeutic strategies. Current imaging techniques face significant limitations, including radiation exposure, high costs, and inadequate sensitivity for detecting early metastases, particularly in imaging and diagnosing tumor metastatic lesions. To overcome these challenges, we developed a multimodal imaging strategy that combined near-infrared fluorescence (NIRF, 750–1700 nm) imaging with X-ray imaging, with assistance of innovative nanomaterial to achieve precise tumor targeting and comprehensive diagnostic. Specifically, we synthesized a folate acid-functionalized polydopamine-modified ICG-Bi2Se3 nanocomposite (FA-PDA@ICG-Bi2Se3, FPBI), which integrated the complementary advantages of NIRF, X-ray, and computerized tomography imaging. The FPBI nanocomposite leveraged the targeting capability of folate acid for specific identification of cervical cancer lesions and metastatic lymph node. Furthermore, it demonstrated robust photothermal therapeutic efficacy under near-infrared (808 nm) excitation, achieving significant tumor ablation effects. This work provides an innovative nanoplatform based strategy for multimodal imaging, precise diagnosis, and targeted therapy of cervical cancer, paving the way for improved detection and management of metastatic lesions.
Cervical cancer remains a leading cause of cancer-related mortality in women, underscoring the urgent need for advanced diagnostic and therapeutic strategies. Current imaging techniques face significant limitations, including radiation exposure, high costs, and inadequate sensitivity for detecting early metastases, particularly in imaging and diagnosing tumor metastatic lesions. To overcome these challenges, we developed a multimodal imaging strategy that combined near-infrared fluorescence (NIRF, 750–1700 nm) imaging with X-ray imaging, with assistance of innovative nanomaterial to achieve precise tumor targeting and comprehensive diagnostic. Specifically, we synthesized a folate acid-functionalized polydopamine-modified ICG-Bi2Se3 nanocomposite (FA-PDA@ICG-Bi2Se3, FPBI), which integrated the complementary advantages of NIRF, X-ray, and computerized tomography imaging. The FPBI nanocomposite leveraged the targeting capability of folate acid for specific identification of cervical cancer lesions and metastatic lymph node. Furthermore, it demonstrated robust photothermal therapeutic efficacy under near-infrared (808 nm) excitation, achieving significant tumor ablation effects. This work provides an innovative nanoplatform based strategy for multimodal imaging, precise diagnosis, and targeted therapy of cervical cancer, paving the way for improved detection and management of metastatic lesions.
2026, 37(4): 111492
doi: 10.1016/j.cclet.2025.111492
摘要:
Photovoltaic micron-silicon scrap (m-Si) has attracted attention as an anode material for lithium-ion batteries due to its high purity and low cost. However, its large particle size hinders the practical application. Herein, we propose an electrochemical etching process in molten KCl-LiCl to reduce its size. A novel electrode pair was developed by combining m-Si (anode) and spent lithium iron phosphate (LFP, cathode) material from spent lithium-ion batteries (LIBs). The m-Si was reduced from 10 µm to <5 µm at a cell voltage of 3.0 V by electrochemical etching without chlorine gas and was porous. The obtained e-Si-50 anode exhibits a high specific capacity of 1061.2 mAh/g at 2.0 A/g after 800 cycles in lithium-ion batteries. The Li3PO4, Fe, and carbon are derived by the electrochemical reduction of the LFP, and are efficiently separated via magnetic separation in water without acid/base treatment. This process combines the recycling of photovoltaic micro-silicon scrap and spent LIBs, providing both environmental and economic benefits.
Photovoltaic micron-silicon scrap (m-Si) has attracted attention as an anode material for lithium-ion batteries due to its high purity and low cost. However, its large particle size hinders the practical application. Herein, we propose an electrochemical etching process in molten KCl-LiCl to reduce its size. A novel electrode pair was developed by combining m-Si (anode) and spent lithium iron phosphate (LFP, cathode) material from spent lithium-ion batteries (LIBs). The m-Si was reduced from 10 µm to <5 µm at a cell voltage of 3.0 V by electrochemical etching without chlorine gas and was porous. The obtained e-Si-50 anode exhibits a high specific capacity of 1061.2 mAh/g at 2.0 A/g after 800 cycles in lithium-ion batteries. The Li3PO4, Fe, and carbon are derived by the electrochemical reduction of the LFP, and are efficiently separated via magnetic separation in water without acid/base treatment. This process combines the recycling of photovoltaic micro-silicon scrap and spent LIBs, providing both environmental and economic benefits.
2026, 37(4): 111516
doi: 10.1016/j.cclet.2025.111516
摘要:
Supramolecular architectures exhibiting cascade energy transfer characteristics represent pivotal model systems for advancing biomimetic light-harvesting systems (LHS) that emulate the natural photosynthesis. To now, the engineering of aqueous-phase artificial LHS with optimized energy transfer cascades is still a challenge. In this study, we designed and synthesized two tetraphenylethylene (TPE)-based macrocyclic compounds (namely TPE-1 and TPE-2) with different cavity sizes as supramolecular scaffolds to study their energy transfer behaviors. As a control model, a linear molecule TPE-3 was also prepared. The bigger-cavity macrocycle TPE-1 can emit green fluorescence and self-assemble into nanospherical structures in aqueous media, acting as an energy donor. Through self-assembly with eosin Y (EY) and a red-emitting fluorophore (TPE-Se), a sequential Förster resonance energy transfer (FRET) cascade: TPE-1→EY→TPE-Se was achieved thanks to their excellent spectral overlap and proximity between the donor and acceptors. The optimized ternary system (TPE-1/EY/TPE-Se) with a ratio of 1000:90:60 afforded a high energy transfer efficiency (ΦET) of 95%. Then, the artificial LHS platform catalyzed the oxidative coupling of benzylamines with 93% yield in aqueous media. Moreover, the system demonstrated broad catalytic utility oxidation reactions, the good conversion of methylthiobenzyl ester to methylbenzene sulfoxide and the aerobic cross-dehydrogenation coupling reaction of N-phenyltetrahydroisoquinoline with indole. These results robustly demonstrate the promising potential of this artificial LHS in the field of aqueous photocatalysis.
Supramolecular architectures exhibiting cascade energy transfer characteristics represent pivotal model systems for advancing biomimetic light-harvesting systems (LHS) that emulate the natural photosynthesis. To now, the engineering of aqueous-phase artificial LHS with optimized energy transfer cascades is still a challenge. In this study, we designed and synthesized two tetraphenylethylene (TPE)-based macrocyclic compounds (namely TPE-1 and TPE-2) with different cavity sizes as supramolecular scaffolds to study their energy transfer behaviors. As a control model, a linear molecule TPE-3 was also prepared. The bigger-cavity macrocycle TPE-1 can emit green fluorescence and self-assemble into nanospherical structures in aqueous media, acting as an energy donor. Through self-assembly with eosin Y (EY) and a red-emitting fluorophore (TPE-Se), a sequential Förster resonance energy transfer (FRET) cascade: TPE-1→EY→TPE-Se was achieved thanks to their excellent spectral overlap and proximity between the donor and acceptors. The optimized ternary system (TPE-1/EY/TPE-Se) with a ratio of 1000:90:60 afforded a high energy transfer efficiency (ΦET) of 95%. Then, the artificial LHS platform catalyzed the oxidative coupling of benzylamines with 93% yield in aqueous media. Moreover, the system demonstrated broad catalytic utility oxidation reactions, the good conversion of methylthiobenzyl ester to methylbenzene sulfoxide and the aerobic cross-dehydrogenation coupling reaction of N-phenyltetrahydroisoquinoline with indole. These results robustly demonstrate the promising potential of this artificial LHS in the field of aqueous photocatalysis.
2026, 37(4): 111522
doi: 10.1016/j.cclet.2025.111522
摘要:
The design of covalent organic frameworks (COFs) with strong fluorescence in both solid and solution states present a significant challenge for white-light-emitting diode (WLED) applications, primarily due to the difficulty of balancing aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ). Here, we report the synthesis of a 7-fold interpenetrated three-dimensional COF (3D COF) with a pts topology, termed ZJUT-M, constructed by co-condensation of a T4-symmetric monomer with two D2h-symmetric fluorophores exhibiting distinct emission behaviors. ZJUT-M displays robust fluorescence in both solid and solution states, enabling its use in WLEDs. Mechanistic studies reveal that the dual-mode emission is driven by the synergistic integration of high-degree-of-freedom chromophores, which promote AIE emission in the solid state, and conformationally restricted fluorophores, which suppress ACQ effect in solution. These findings provide a strategic pathway for achieving multi-state emissive COFs, opening avenues for their application in advanced optoelectronic devices, including next-generation LEDs.
The design of covalent organic frameworks (COFs) with strong fluorescence in both solid and solution states present a significant challenge for white-light-emitting diode (WLED) applications, primarily due to the difficulty of balancing aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ). Here, we report the synthesis of a 7-fold interpenetrated three-dimensional COF (3D COF) with a pts topology, termed ZJUT-M, constructed by co-condensation of a T4-symmetric monomer with two D2h-symmetric fluorophores exhibiting distinct emission behaviors. ZJUT-M displays robust fluorescence in both solid and solution states, enabling its use in WLEDs. Mechanistic studies reveal that the dual-mode emission is driven by the synergistic integration of high-degree-of-freedom chromophores, which promote AIE emission in the solid state, and conformationally restricted fluorophores, which suppress ACQ effect in solution. These findings provide a strategic pathway for achieving multi-state emissive COFs, opening avenues for their application in advanced optoelectronic devices, including next-generation LEDs.
2026, 37(4): 111538
doi: 10.1016/j.cclet.2025.111538
摘要:
This study employed the ferrate(Ⅵ)/sulfur(Ⅳ) (Fe(Ⅵ)/S(Ⅳ)) system to degrade aromatic organoarsenic compounds, with a focus on elucidating the role of in situ-formed Fe(Ⅲ) flocs. The introduction of S(Ⅳ) significantly enhanced oxidative degradation efficiency compared to Fe(Ⅵ) alone, achieving 94.8% p-arsanilic acid (p-ASA) degradation within 3 min. The evolution of active species under varying S(Ⅳ) dosages was systematically investigated via radical quenching experiments and probe compound analysis. SO4•−, •OH and Fe(Ⅳ)/Fe(Ⅴ) were identified as the dominant reactive species in the Fe(Ⅵ)/S(Ⅳ) system, with Fe(Ⅳ)/Fe(Ⅴ) serving as the primary driver of p-ASA degradation. Characterization revealed that Fe(Ⅲ) flocs contributed to arsenic (As) adsorption. While S(Ⅳ) addition altered the morphology and structure of Fe(Ⅲ) flocs, these changes exerted negligible effects on As adsorption capacity. A plausible degradation pathway for p-ASA was proposed, supported by density functional theory (DFT) calculations and degradation product analysis. The system demonstrated robust resistance to common interfering ions, while the low toxicity of degradation byproducts highlighted its potential as a sustainable technology for AOCs elimination. This work elucidated structural modifications in Fe(Ⅲ) flocs induced by S(Ⅳ) and underscored the pivotal role of Fe(Ⅳ)/Fe(Ⅴ), positioning the Fe(Ⅵ)/S(Ⅳ) system as a promising strategy for AOCs degradation.
This study employed the ferrate(Ⅵ)/sulfur(Ⅳ) (Fe(Ⅵ)/S(Ⅳ)) system to degrade aromatic organoarsenic compounds, with a focus on elucidating the role of in situ-formed Fe(Ⅲ) flocs. The introduction of S(Ⅳ) significantly enhanced oxidative degradation efficiency compared to Fe(Ⅵ) alone, achieving 94.8% p-arsanilic acid (p-ASA) degradation within 3 min. The evolution of active species under varying S(Ⅳ) dosages was systematically investigated via radical quenching experiments and probe compound analysis. SO4•−, •OH and Fe(Ⅳ)/Fe(Ⅴ) were identified as the dominant reactive species in the Fe(Ⅵ)/S(Ⅳ) system, with Fe(Ⅳ)/Fe(Ⅴ) serving as the primary driver of p-ASA degradation. Characterization revealed that Fe(Ⅲ) flocs contributed to arsenic (As) adsorption. While S(Ⅳ) addition altered the morphology and structure of Fe(Ⅲ) flocs, these changes exerted negligible effects on As adsorption capacity. A plausible degradation pathway for p-ASA was proposed, supported by density functional theory (DFT) calculations and degradation product analysis. The system demonstrated robust resistance to common interfering ions, while the low toxicity of degradation byproducts highlighted its potential as a sustainable technology for AOCs elimination. This work elucidated structural modifications in Fe(Ⅲ) flocs induced by S(Ⅳ) and underscored the pivotal role of Fe(Ⅳ)/Fe(Ⅴ), positioning the Fe(Ⅵ)/S(Ⅳ) system as a promising strategy for AOCs degradation.
2026, 37(4): 111547
doi: 10.1016/j.cclet.2025.111547
摘要:
Species at the air-water interface of microdroplets often display distinct acidity compared to the bulk. In this study, we report that pyrrole, imidazole, pyrazole, and 2H-1,2,3-triazole, a group of five-membered, planar, aromatic, nitrogen heterocyclic compounds that are basic in bulk water, exhibit strong acidity on microdroplets. The deprotonated anions of pyrrole, imidazole, and pyrazole can further react with CO2 to generate the corresponding carboxylic acids, but the triazole anion does not react with CO2. Calculation shows that partial solvation and the electric field on the air-water interface of the microdroplets are the main causes for the increased acidity, and the unique solvation structure of the triazole anion at the interface causes the reactive sites to be shielded by interfacial water molecules, thereby hindering reaction with CO2. These results demonstrate that the electric field and solvation structure of ions at the air-water interface play a decisive role in microdroplet chemistry for these compounds. We anticipate that the unique acidity and reactivity on microdroplets provide a new avenue that is rich in opportunities for green chemistry.
Species at the air-water interface of microdroplets often display distinct acidity compared to the bulk. In this study, we report that pyrrole, imidazole, pyrazole, and 2H-1,2,3-triazole, a group of five-membered, planar, aromatic, nitrogen heterocyclic compounds that are basic in bulk water, exhibit strong acidity on microdroplets. The deprotonated anions of pyrrole, imidazole, and pyrazole can further react with CO2 to generate the corresponding carboxylic acids, but the triazole anion does not react with CO2. Calculation shows that partial solvation and the electric field on the air-water interface of the microdroplets are the main causes for the increased acidity, and the unique solvation structure of the triazole anion at the interface causes the reactive sites to be shielded by interfacial water molecules, thereby hindering reaction with CO2. These results demonstrate that the electric field and solvation structure of ions at the air-water interface play a decisive role in microdroplet chemistry for these compounds. We anticipate that the unique acidity and reactivity on microdroplets provide a new avenue that is rich in opportunities for green chemistry.
2026, 37(4): 111567
doi: 10.1016/j.cclet.2025.111567
摘要:
The development of a high-performance pH-universal electrocatalyst for hydrogen evolution reaction (HER) is a vital step toward hydrogen economy but remains a major challenge. Herein, the Pd, Cu, and Ni three elements were confined in a nanoparticle via the microemulsion method. Morphology and structural analysis reveal that PdCuNi nanoparticles are nearly spherical in shape with slight aggregation, and are mainly composed of metallic Pd and Cu, as well as Ni oxide. The electrochemical tests show that PdCuNi exhibits favorable HER catalytic activity in acid (ŋ10: 45 mV; Tafel slopes: 33 mV/dec) and neutral (ŋ10: 71 mV; Tafel slopes: 87 mV/dec) media, and alkaline (ŋ10: 66 mV; Tafel slopes: 116 mV/dec) media. The mechanism analysis implies that the synergistic effect of Pd, Cu, and Ni can improve the inherent conductivity of the catalyst and accelerate the charge transfer process. Furthermore, over 30 h long-term stability has been achieved without significant attenuation. This work provides a strategy for developing versatile and robust multimetallic catalysts towards pH-universal HER.
The development of a high-performance pH-universal electrocatalyst for hydrogen evolution reaction (HER) is a vital step toward hydrogen economy but remains a major challenge. Herein, the Pd, Cu, and Ni three elements were confined in a nanoparticle via the microemulsion method. Morphology and structural analysis reveal that PdCuNi nanoparticles are nearly spherical in shape with slight aggregation, and are mainly composed of metallic Pd and Cu, as well as Ni oxide. The electrochemical tests show that PdCuNi exhibits favorable HER catalytic activity in acid (ŋ10: 45 mV; Tafel slopes: 33 mV/dec) and neutral (ŋ10: 71 mV; Tafel slopes: 87 mV/dec) media, and alkaline (ŋ10: 66 mV; Tafel slopes: 116 mV/dec) media. The mechanism analysis implies that the synergistic effect of Pd, Cu, and Ni can improve the inherent conductivity of the catalyst and accelerate the charge transfer process. Furthermore, over 30 h long-term stability has been achieved without significant attenuation. This work provides a strategy for developing versatile and robust multimetallic catalysts towards pH-universal HER.
2026, 37(4): 111581
doi: 10.1016/j.cclet.2025.111581
摘要:
Cocatalysts are pivotal in realizing photocatalytic overall water splitting (POWS) by mitigating carrier recombination and expediting reaction kinetics. Nevertheless, conventional cocatalysts still faces with challenges in balancing high efficiency and low cost. Herein, adjacent CoP and CoOOH, as noble-metal-free dual cocatalysts for hydrogen/oxygen evolution, are introduced onto the surface of Al-doped SrTiO3 (Al: STO), achieving stable and efficient POWS, with a hydrogen and oxygen evolution rate of 4.86 and 2.30 mmol h-1 g-1, respectively, and an apparent quantum yield of 12.7% at 350 ± 10 nm. The superior performance is attributed to the unique adjacent structure of CoP and CoOOH dual cocatalysts. Functioning as critical reactive sites for hydrogen and oxygen evolution, respectively, co-modification of CoP and CoOOH effectively promotes the surface redox reaction. Notably, due to the Schottky junction form between CoP and CoOOH, the uniformly distributed and tightly attached adjacent CoP-CoOOH dual cocatalysts shortened the distance of both charge-carrier migration from bulk to the surface of photocatalyst and proton transfer from oxidation sites to reduction sites, thereby enhancing the charge-separation efficiency and protecting CoP against oxidation during photocatalytic overall water splitting process. This work offers innovative insights for designing efficient, noble-metal-free cocatalysts for POWS.
Cocatalysts are pivotal in realizing photocatalytic overall water splitting (POWS) by mitigating carrier recombination and expediting reaction kinetics. Nevertheless, conventional cocatalysts still faces with challenges in balancing high efficiency and low cost. Herein, adjacent CoP and CoOOH, as noble-metal-free dual cocatalysts for hydrogen/oxygen evolution, are introduced onto the surface of Al-doped SrTiO3 (Al: STO), achieving stable and efficient POWS, with a hydrogen and oxygen evolution rate of 4.86 and 2.30 mmol h-1 g-1, respectively, and an apparent quantum yield of 12.7% at 350 ± 10 nm. The superior performance is attributed to the unique adjacent structure of CoP and CoOOH dual cocatalysts. Functioning as critical reactive sites for hydrogen and oxygen evolution, respectively, co-modification of CoP and CoOOH effectively promotes the surface redox reaction. Notably, due to the Schottky junction form between CoP and CoOOH, the uniformly distributed and tightly attached adjacent CoP-CoOOH dual cocatalysts shortened the distance of both charge-carrier migration from bulk to the surface of photocatalyst and proton transfer from oxidation sites to reduction sites, thereby enhancing the charge-separation efficiency and protecting CoP against oxidation during photocatalytic overall water splitting process. This work offers innovative insights for designing efficient, noble-metal-free cocatalysts for POWS.
2026, 37(4): 111619
doi: 10.1016/j.cclet.2025.111619
摘要:
Calcium hydride (CaH2) is a hydrogen storage material with high hydrogen storage density that is easy to transport and store. However, its hydrogen generation process is intense and liquid water causes uneven reactions in CaH2. These two issues make the reaction of CaH2 hard to control. To resolve the issues, a gel/nonwoven fabric composite material was prepared using nonwoven fabric and poly(vinyl alcohol)/polyacrylamide (PVA/PAM) hydrogel, and applied to a compact hydrogen generator. Water absorption and evaporation tests on composite membranes confirm that the membrane can control the water transport rate by adjusting the gel content, thereby regulating the hydrogen production of CaH2. During the hydrolysis of CaH2, the heat released promotes water evaporation, which absorbs some of this heat and helps maintain both temperature and water balance. When the gel content was 10%, the height of the separator was 1 mm, and the mass of CaH2 was 1.5 g, the hydrogen generator achieved the fastest hydrogen production rate of 58.7 mL/min. Moreover, after expanding the size of the hydrogen generator, it can continuously produce hydrogen for over 260 min at room temperature. Finally, hydrogen was supplied to a proton exchange membrane fuel cell (PEMFC) stack. This research provides a new concept for controllable hydrogen production and portable fuel cells.
Calcium hydride (CaH2) is a hydrogen storage material with high hydrogen storage density that is easy to transport and store. However, its hydrogen generation process is intense and liquid water causes uneven reactions in CaH2. These two issues make the reaction of CaH2 hard to control. To resolve the issues, a gel/nonwoven fabric composite material was prepared using nonwoven fabric and poly(vinyl alcohol)/polyacrylamide (PVA/PAM) hydrogel, and applied to a compact hydrogen generator. Water absorption and evaporation tests on composite membranes confirm that the membrane can control the water transport rate by adjusting the gel content, thereby regulating the hydrogen production of CaH2. During the hydrolysis of CaH2, the heat released promotes water evaporation, which absorbs some of this heat and helps maintain both temperature and water balance. When the gel content was 10%, the height of the separator was 1 mm, and the mass of CaH2 was 1.5 g, the hydrogen generator achieved the fastest hydrogen production rate of 58.7 mL/min. Moreover, after expanding the size of the hydrogen generator, it can continuously produce hydrogen for over 260 min at room temperature. Finally, hydrogen was supplied to a proton exchange membrane fuel cell (PEMFC) stack. This research provides a new concept for controllable hydrogen production and portable fuel cells.
2026, 37(4): 111624
doi: 10.1016/j.cclet.2025.111624
摘要:
Carbohydrates play essential roles in the physiological and pathological functions of cells. However, carbohydrate structures involve numerous levels of isomerism, which has posed significant challenges to advancements in glycomics. The technique for carbohydrate recognition needs to be precise in determining all aspects of the stereodiversity for both fundamental research and practical applications. Via quantum tunneling simulations and model analysis, we show that a carbon nanotube based nanopore as a molecular tweezer to trap a single target analyte with controlled dwell time achieved through reversible flexoelectric gating. Under mechanical deformation, the pore walls act as dynamic electrostatic binding sites to capture analyte enabling ample but fast sampling. After establishing Fano resonance as the sensing mechanism to quantitatively evaluate the interaction between the pore wall and analyte, random forest classifier algorithm is employed to classify the quantum transport data. This sensing strategy provides a general discrimination accuracy of higher than 99.4% for identifying carbohydrate isomers. Our findings highlight the efficacy of this combined physics and machine learning-based method in addressing the stereochemical complexity of carbohydrates. The approach not only improves observation time per molecule but also operates in a high-throughput format, offering a powerful artificial intelligence (AI)-empowered biomolecule sensing tool for glycomics research.
Carbohydrates play essential roles in the physiological and pathological functions of cells. However, carbohydrate structures involve numerous levels of isomerism, which has posed significant challenges to advancements in glycomics. The technique for carbohydrate recognition needs to be precise in determining all aspects of the stereodiversity for both fundamental research and practical applications. Via quantum tunneling simulations and model analysis, we show that a carbon nanotube based nanopore as a molecular tweezer to trap a single target analyte with controlled dwell time achieved through reversible flexoelectric gating. Under mechanical deformation, the pore walls act as dynamic electrostatic binding sites to capture analyte enabling ample but fast sampling. After establishing Fano resonance as the sensing mechanism to quantitatively evaluate the interaction between the pore wall and analyte, random forest classifier algorithm is employed to classify the quantum transport data. This sensing strategy provides a general discrimination accuracy of higher than 99.4% for identifying carbohydrate isomers. Our findings highlight the efficacy of this combined physics and machine learning-based method in addressing the stereochemical complexity of carbohydrates. The approach not only improves observation time per molecule but also operates in a high-throughput format, offering a powerful artificial intelligence (AI)-empowered biomolecule sensing tool for glycomics research.
2026, 37(4): 111626
doi: 10.1016/j.cclet.2025.111626
摘要:
Sustainable photochemical CO2 conversion represents a promising strategy for mitigating excess CO2 emissions and achieving "carbon neutrality". The development of advanced catalysts with an abundance of active sites and efficient separation of photo-generated charge carriers remains a significant challenge. Here, we present a high-entropy (HE) photocatalyst by integrating five metals into Prussian blue (PB) to afford Kx(MnFeCoNiCu)[Fe(CN)6] (HE-PBA) which exhibits a high concentration of active centers and rapid electron transfer, enabling superior CO2-to-CO photoreduction performance. The HE-PBA composite catalyst delivered a high CO yield (up to 1220.5 µmol g-1 h-1), achieving near 100% product selectivity. A mechanistic analysis has revealed strong coupling and overlapping multi-atomic orbitals, which facilitates local electron redistribution and a readjustment of electron density. This effect serves to generate abundant reactive sites with CO2 interactions that facilitate C-O bond activation. Additionally, an efficient electron transfer driven by the disparity in metal electronegativity inhibits unwanted recombination of electron-hole pairs. More significantly, the photoelectrons migrate and accumulate on the HE-PBA surface, exhibiting extended long lifetimes and robust reduction ability. The findings of this study provide important insights that can contribute to the development of high-entropy materials rich in transition metals with far-ranging potential applications.
Sustainable photochemical CO2 conversion represents a promising strategy for mitigating excess CO2 emissions and achieving "carbon neutrality". The development of advanced catalysts with an abundance of active sites and efficient separation of photo-generated charge carriers remains a significant challenge. Here, we present a high-entropy (HE) photocatalyst by integrating five metals into Prussian blue (PB) to afford Kx(MnFeCoNiCu)[Fe(CN)6] (HE-PBA) which exhibits a high concentration of active centers and rapid electron transfer, enabling superior CO2-to-CO photoreduction performance. The HE-PBA composite catalyst delivered a high CO yield (up to 1220.5 µmol g-1 h-1), achieving near 100% product selectivity. A mechanistic analysis has revealed strong coupling and overlapping multi-atomic orbitals, which facilitates local electron redistribution and a readjustment of electron density. This effect serves to generate abundant reactive sites with CO2 interactions that facilitate C-O bond activation. Additionally, an efficient electron transfer driven by the disparity in metal electronegativity inhibits unwanted recombination of electron-hole pairs. More significantly, the photoelectrons migrate and accumulate on the HE-PBA surface, exhibiting extended long lifetimes and robust reduction ability. The findings of this study provide important insights that can contribute to the development of high-entropy materials rich in transition metals with far-ranging potential applications.
2026, 37(4): 111627
doi: 10.1016/j.cclet.2025.111627
摘要:
Extensive research has been devoted to single-atom activation of persulfates in recent years. However, mechanistic understanding of the distinct interactions between different persulfates (i.e., peroxymonosulfate (PMS) and peroxydisulfate (PDS)) and the coordination environments of single-atom catalysts (SACs) remains critical for advancing their practical applications. Herein, we developed a Fe-N4 SAC exhibiting dual activation capabilities for both PMS and PDS. Intriguingly, experimental results revealed divergent activation mechanisms: PMS activation was predominantly mediated via single-site reactions generating singlet oxygen (1O2), whereas PDS activation proceeded through both dual-site and single-site pathways involving concurrent 1O2 generation and electron transfer processes. Density functional theory calculations further demonstrated that the geometric alignment between the inter-site distances of Fe-N4 centers and the molecular dimensions of PDS serves as the key determinant for enabling the electron transfer pathway. This fundamental structure-reactivity correlation suggests that the intrinsic molecular-scale differences between PMS and PDS govern their distinct interaction mechanisms with Fe-N4 SACs. Finally, the scale-up experiments realized nearly complete sulfamethoxazole degradation during 120 h continuous operation without obvious decline in both the Fe-N4/PMS and Fe-N4/PDS systems. This work provides fundamental insights into molecular-scale effects on persulfate activation mechanisms, establishing new design principles for SACs optimization in advanced oxidation processes.
Extensive research has been devoted to single-atom activation of persulfates in recent years. However, mechanistic understanding of the distinct interactions between different persulfates (i.e., peroxymonosulfate (PMS) and peroxydisulfate (PDS)) and the coordination environments of single-atom catalysts (SACs) remains critical for advancing their practical applications. Herein, we developed a Fe-N4 SAC exhibiting dual activation capabilities for both PMS and PDS. Intriguingly, experimental results revealed divergent activation mechanisms: PMS activation was predominantly mediated via single-site reactions generating singlet oxygen (1O2), whereas PDS activation proceeded through both dual-site and single-site pathways involving concurrent 1O2 generation and electron transfer processes. Density functional theory calculations further demonstrated that the geometric alignment between the inter-site distances of Fe-N4 centers and the molecular dimensions of PDS serves as the key determinant for enabling the electron transfer pathway. This fundamental structure-reactivity correlation suggests that the intrinsic molecular-scale differences between PMS and PDS govern their distinct interaction mechanisms with Fe-N4 SACs. Finally, the scale-up experiments realized nearly complete sulfamethoxazole degradation during 120 h continuous operation without obvious decline in both the Fe-N4/PMS and Fe-N4/PDS systems. This work provides fundamental insights into molecular-scale effects on persulfate activation mechanisms, establishing new design principles for SACs optimization in advanced oxidation processes.
2026, 37(4): 111630
doi: 10.1016/j.cclet.2025.111630
摘要:
The Fenton-like activation of peroxymonosulfate (PMS) is an effective oxidation strategy for water decontamination, however, Fe(Ⅱ)-mediated Fenton-like reactions suffer from limitations of sluggish iron species cycling and iron sludge accumulation. Herein, molybdenum pentaboride (Mo2B5) was innovatively employed as a dual-functional co-catalyst to address these challenges via synergistically direct and indirect routes for activating PMS. Mo2B5 can promptly enhance Fe(Ⅲ)/PMS to entirely degrade sulfamethoxazole within 4 min, superior to conventional reducing agents and carbon-based co-catalysts. Based on mechanism investigations (reactive oxygen species analysis, iron species variation, surface chemistry characterizations), the distinctive electronic configuration of Mo2B5 can direct activate PMS for generating hydroxyl radical (•OH), while simultaneously enhance Fe(Ⅱ) regeneration to facilitate subsequent Fenton-like processes to produce sulfate radicals (SO4•−) and ferryl species (Fe(Ⅳ)). The system thus demonstrated broad applicability for degrading diverse pollutants with high rate constants, while the substrate specific reactivities are dependent on the electron-donating capacities of pollutants. In addition, Mo2B5 exhibits exceptional stability over consecutive cycle tests, attributed to its self-cleaning surface and retained crystallinity.
The Fenton-like activation of peroxymonosulfate (PMS) is an effective oxidation strategy for water decontamination, however, Fe(Ⅱ)-mediated Fenton-like reactions suffer from limitations of sluggish iron species cycling and iron sludge accumulation. Herein, molybdenum pentaboride (Mo2B5) was innovatively employed as a dual-functional co-catalyst to address these challenges via synergistically direct and indirect routes for activating PMS. Mo2B5 can promptly enhance Fe(Ⅲ)/PMS to entirely degrade sulfamethoxazole within 4 min, superior to conventional reducing agents and carbon-based co-catalysts. Based on mechanism investigations (reactive oxygen species analysis, iron species variation, surface chemistry characterizations), the distinctive electronic configuration of Mo2B5 can direct activate PMS for generating hydroxyl radical (•OH), while simultaneously enhance Fe(Ⅱ) regeneration to facilitate subsequent Fenton-like processes to produce sulfate radicals (SO4•−) and ferryl species (Fe(Ⅳ)). The system thus demonstrated broad applicability for degrading diverse pollutants with high rate constants, while the substrate specific reactivities are dependent on the electron-donating capacities of pollutants. In addition, Mo2B5 exhibits exceptional stability over consecutive cycle tests, attributed to its self-cleaning surface and retained crystallinity.
2026, 37(4): 111636
doi: 10.1016/j.cclet.2025.111636
摘要:
The integration of advanced sensing materials as channel layers in devices is essential for constructing field-effect transistor (FET) biosensors. In this study, we synthesized high-crystallinity bimetallic M3(hexaaminotriphenylene)2 (M = Co, Ni) thin films as FET channel materials via an in-situ growth method using a mixed solvent system of water and N,N-dimethylformamide (DMF). This bimetallic metal-organic framework (MOF)-based FET then served as a glucose biosensor, achieving a high sensitivity and an ultra-wide detection range from 10 nmol/L to 10 mmol/L. Further studies reveal that the success of in-situ growth of the high-crystalline bimetallic MOF film can be attributed to the coordination solvent exchange reaction between the metal atomic center, DMF, and water. Furthermore, the introduction of bimetallic centers enhances the number of active sites within the MOF, thereby achieving an ultra-low detection limit and an ultra-wide detection range. This work presents a versatile approach for constructing high performance FET biosensors.
The integration of advanced sensing materials as channel layers in devices is essential for constructing field-effect transistor (FET) biosensors. In this study, we synthesized high-crystallinity bimetallic M3(hexaaminotriphenylene)2 (M = Co, Ni) thin films as FET channel materials via an in-situ growth method using a mixed solvent system of water and N,N-dimethylformamide (DMF). This bimetallic metal-organic framework (MOF)-based FET then served as a glucose biosensor, achieving a high sensitivity and an ultra-wide detection range from 10 nmol/L to 10 mmol/L. Further studies reveal that the success of in-situ growth of the high-crystalline bimetallic MOF film can be attributed to the coordination solvent exchange reaction between the metal atomic center, DMF, and water. Furthermore, the introduction of bimetallic centers enhances the number of active sites within the MOF, thereby achieving an ultra-low detection limit and an ultra-wide detection range. This work presents a versatile approach for constructing high performance FET biosensors.
2026, 37(4): 111644
doi: 10.1016/j.cclet.2025.111644
摘要:
Elucidating the synergistic influence mechanism of catalysts composition and pollutants structure on the treatment system is a necessary way to further expand the application potential of heterogeneous iron-based Fenton-like technology in the field of water treatment from catalytic source and degradation end. In this study, a nitrogen-doped iron-carbon material (Fe-NC-4%) was synthesized to effectively activate peroxymonosulfate (PMS) to remove different organic pollutants, thus further exploring the synergistic effects of material and pollutant structures on degradation performance and mechanism. A combination of characterization analysis, experimental demonstration and density functional theory calculation showed that the more graphitic nitrogen in Fe-NC-4% assisted the Fe active centers to adsorb PMS more easily and further form the Fe-NC-4%-PMS* complex with high activity and stability. And the Fe-NC-4%-PMS* complex could efficiently and selectively degraded electron-donating organics by electron transfer process (ETP). The degradation rate of ofloxacin (OFL) with stronger electron-donating ability could reach 0.405 min−1 in the Fe-NC-4%/PMS system. In addition, the Fe-NC-4%/PMS system possessed strong environmental adaptability, safety and practical application potential. This study would provide technical and theoretical guidance for the top-down analysis of specific reaction mechanisms in Fenton-like systems, including catalyst structure design, reactive species generation and selective pollutant degradation.
Elucidating the synergistic influence mechanism of catalysts composition and pollutants structure on the treatment system is a necessary way to further expand the application potential of heterogeneous iron-based Fenton-like technology in the field of water treatment from catalytic source and degradation end. In this study, a nitrogen-doped iron-carbon material (Fe-NC-4%) was synthesized to effectively activate peroxymonosulfate (PMS) to remove different organic pollutants, thus further exploring the synergistic effects of material and pollutant structures on degradation performance and mechanism. A combination of characterization analysis, experimental demonstration and density functional theory calculation showed that the more graphitic nitrogen in Fe-NC-4% assisted the Fe active centers to adsorb PMS more easily and further form the Fe-NC-4%-PMS* complex with high activity and stability. And the Fe-NC-4%-PMS* complex could efficiently and selectively degraded electron-donating organics by electron transfer process (ETP). The degradation rate of ofloxacin (OFL) with stronger electron-donating ability could reach 0.405 min−1 in the Fe-NC-4%/PMS system. In addition, the Fe-NC-4%/PMS system possessed strong environmental adaptability, safety and practical application potential. This study would provide technical and theoretical guidance for the top-down analysis of specific reaction mechanisms in Fenton-like systems, including catalyst structure design, reactive species generation and selective pollutant degradation.
2026, 37(4): 111648
doi: 10.1016/j.cclet.2025.111648
摘要:
Lithium–sulfur (Li–S) batteries with the high theoretical capacity of 1675 mAh/g have attracted attention as next-generation energy storage systems. Understanding the dynamic evolution and reaction mechanisms at the interface between sulfur cathodes and the electrolyte is crucial to achieve a high reversible capacity of Li−S batteries. However, due to the challenges in probing the complex Li–S redox reaction, the structural and morphological changes from active sulfur to insoluble lithium sulfide (Li2S) under operating conditions remain poorly understood. Here, the behaviors during sulfur dissolution and Li2S deposition/decomposition under realistic conditions were investigated via in situ atomic force microscopy (AFM). Direct visualizations revealed that tightly stacked sulfur particles hinder essential electronic pathways within the cathode. Furthermore constructing a conductive framework promotes more uniform Li2S deposition, which was previously dispersed across the electrode surface, thus accelerating Li2S conversion kinetics during the subsequent charge process. PeakForce tunneling atomic force microscopy (TUNA) measurements effectively elucidated the correlation between nanoscale structural features and electrical conductivity under varying potentials. Real-time observations reveal the dynamic evolution and reaction mechanisms of sulfur cathodes, offering profound insights into the Li−S redox processes and guiding the rational design of advanced cathodes.
Lithium–sulfur (Li–S) batteries with the high theoretical capacity of 1675 mAh/g have attracted attention as next-generation energy storage systems. Understanding the dynamic evolution and reaction mechanisms at the interface between sulfur cathodes and the electrolyte is crucial to achieve a high reversible capacity of Li−S batteries. However, due to the challenges in probing the complex Li–S redox reaction, the structural and morphological changes from active sulfur to insoluble lithium sulfide (Li2S) under operating conditions remain poorly understood. Here, the behaviors during sulfur dissolution and Li2S deposition/decomposition under realistic conditions were investigated via in situ atomic force microscopy (AFM). Direct visualizations revealed that tightly stacked sulfur particles hinder essential electronic pathways within the cathode. Furthermore constructing a conductive framework promotes more uniform Li2S deposition, which was previously dispersed across the electrode surface, thus accelerating Li2S conversion kinetics during the subsequent charge process. PeakForce tunneling atomic force microscopy (TUNA) measurements effectively elucidated the correlation between nanoscale structural features and electrical conductivity under varying potentials. Real-time observations reveal the dynamic evolution and reaction mechanisms of sulfur cathodes, offering profound insights into the Li−S redox processes and guiding the rational design of advanced cathodes.
2026, 37(4): 111654
doi: 10.1016/j.cclet.2025.111654
摘要:
Flexible gas sensors show promise in wearable health monitoring and toxic gas detection due to mechanical flexibility and system integration, but they still face challenges such as slow response/recovery dynamics and poor stability. Here, a novel aqueous ink consisting of n-type mesoporous tin oxide (mSnO2) colloids and p-type poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (abbreviated as PEDOT:PSS) was designed and deposited on oxygen plasma treated polyimine (PI) substrate with pre-printed electrodes and heater via automatic dispension printing followed with a subsequent freeze-drying treatment, resuling in hierarchically porous sensing layer with mesopore channels and macroporous framework on the flexible PI substrate. The resultant SnO2/PEDOT:PSS sensor showed excellent sensing performance (6%-30.5%) toward low-concentration ammonia (1–100 ppm), rapid response/recovery speed (61 s/25 s) and superior mechanical stability. Furthermore, the sensor was integrated into a Bluetooth-enabled smart bracelet, achieving real-time monitoring of environmetal ammonia concentration and showcasing its potential for wearable electronics in dectecting volatile harmful gases.
Flexible gas sensors show promise in wearable health monitoring and toxic gas detection due to mechanical flexibility and system integration, but they still face challenges such as slow response/recovery dynamics and poor stability. Here, a novel aqueous ink consisting of n-type mesoporous tin oxide (mSnO2) colloids and p-type poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (abbreviated as PEDOT:PSS) was designed and deposited on oxygen plasma treated polyimine (PI) substrate with pre-printed electrodes and heater via automatic dispension printing followed with a subsequent freeze-drying treatment, resuling in hierarchically porous sensing layer with mesopore channels and macroporous framework on the flexible PI substrate. The resultant SnO2/PEDOT:PSS sensor showed excellent sensing performance (6%-30.5%) toward low-concentration ammonia (1–100 ppm), rapid response/recovery speed (61 s/25 s) and superior mechanical stability. Furthermore, the sensor was integrated into a Bluetooth-enabled smart bracelet, achieving real-time monitoring of environmetal ammonia concentration and showcasing its potential for wearable electronics in dectecting volatile harmful gases.
2026, 37(4): 111667
doi: 10.1016/j.cclet.2025.111667
摘要:
The exposure of specific facets in catalysts plays a pivotal role in surface/interface reactions. This study systematically explores facet engineering as a novel approach to enhancing the piezoelectric and piezo-photocatalytic capabilities of metal-organic frameworks (MOFs), with a focus on ZIF-8 as a model compound. By selectively exposing specific facets-(100), (110), and a combination of both in mixed configurations, this research examines how facet orientation affects piezoelectric properties, charge separation efficiency, and catalytic performance. The ZIF-8 samples, identified as ZIF-8-RD, ZIF-8-CUBE, ZIF-8-TRD1, and ZIF-8-TRD2 demonstrated distinct catalytic activities in photocatalysis, piezocatalysis, and piezo-photocatalysis. Notably, ZIF-8-TRDs, with the mixed-facet exposure, showed superior catalytic performance, achieving up to 94% degradation of tetracycline (TC) in piezo-photocatalysis, a substantial improvement over the single-facet variant. This enhanced performance is attributed to the mixed facets' higher carrier concentration and superior charge separation facilitated by the increased internal piezoelectric potential. Density functional theory (DFT) calculations corroborate the experimental results, revealing that mixed facets contribute to a larger dipole moment, indicating greater structural asymmetry and piezoelectric efficiency. The findings underscore facet engineering as an effective strategy to optimize MOF-based catalysts, opening avenues for high-performance materials tailored for environmental remediation and sustainable energy applications. This work not only pioneers facet engineering in MOF piezo-photocatalysts but also opens new avenues for the development and enhancement of high-performance MOF in piezoelectricity.
The exposure of specific facets in catalysts plays a pivotal role in surface/interface reactions. This study systematically explores facet engineering as a novel approach to enhancing the piezoelectric and piezo-photocatalytic capabilities of metal-organic frameworks (MOFs), with a focus on ZIF-8 as a model compound. By selectively exposing specific facets-(100), (110), and a combination of both in mixed configurations, this research examines how facet orientation affects piezoelectric properties, charge separation efficiency, and catalytic performance. The ZIF-8 samples, identified as ZIF-8-RD, ZIF-8-CUBE, ZIF-8-TRD1, and ZIF-8-TRD2 demonstrated distinct catalytic activities in photocatalysis, piezocatalysis, and piezo-photocatalysis. Notably, ZIF-8-TRDs, with the mixed-facet exposure, showed superior catalytic performance, achieving up to 94% degradation of tetracycline (TC) in piezo-photocatalysis, a substantial improvement over the single-facet variant. This enhanced performance is attributed to the mixed facets' higher carrier concentration and superior charge separation facilitated by the increased internal piezoelectric potential. Density functional theory (DFT) calculations corroborate the experimental results, revealing that mixed facets contribute to a larger dipole moment, indicating greater structural asymmetry and piezoelectric efficiency. The findings underscore facet engineering as an effective strategy to optimize MOF-based catalysts, opening avenues for high-performance materials tailored for environmental remediation and sustainable energy applications. This work not only pioneers facet engineering in MOF piezo-photocatalysts but also opens new avenues for the development and enhancement of high-performance MOF in piezoelectricity.
2026, 37(4): 111668
doi: 10.1016/j.cclet.2025.111668
摘要:
With the continuous detection of new pollutants in the water environment, their potential harm cannot be ignored. In order to explore an effective method to remove contaminants from wastewater, this paper presents an underwater bubble plasma (UBP) activated peroxymonosulfate (PMS) strategy for rapidly degrading the typical emerging contaminant tetracycline hydrochloride (TC) in water. The results indicate that, compared with UBP alone (41.1%), the UBP-PMS system (98.6%) exhibits significantly enhanced degradation ability, achieving a 57.5% increase in TC degradation rate under identical conditions while enabling long-term self-purification of wastewater without energy input within this system. In addition, we studied the effects of initial TC concentration, the type of working gas, the initial pH value of the solution, and the water matrix on the degradation performance of the UBP-PMS system. The anti-interference performance of the UBP-PMS system is proven to be strong, as six inorganic anions (HCO3−, CO32−, NO3−, HPO42−, SO42− and Cl−) are added respectively to simulate the actual water environment. The contribution of different reactive species to the degradation process was evaluated qualitatively and quantitatively by electron spin resonance (ESR) and scavenger experiments, of which the largest contribution was •OH, followed by 1O2, ONOOH/O2•-, SO4•‒ and hydrated electrons. The potential degradation pathways of TC were analyzed, and the toxicity of the degradation intermediates was evaluated by quantitative structure-activity relationship (QSAR) analysis, revealing a gradual reduction in TC toxicity under the co-treatment of UBP-PMS. This study provides a novel activation strategy involving UBP-PMS and provides valuable insights into the degradation properties and mechanisms of emerging pollutants in actual water bodies.
With the continuous detection of new pollutants in the water environment, their potential harm cannot be ignored. In order to explore an effective method to remove contaminants from wastewater, this paper presents an underwater bubble plasma (UBP) activated peroxymonosulfate (PMS) strategy for rapidly degrading the typical emerging contaminant tetracycline hydrochloride (TC) in water. The results indicate that, compared with UBP alone (41.1%), the UBP-PMS system (98.6%) exhibits significantly enhanced degradation ability, achieving a 57.5% increase in TC degradation rate under identical conditions while enabling long-term self-purification of wastewater without energy input within this system. In addition, we studied the effects of initial TC concentration, the type of working gas, the initial pH value of the solution, and the water matrix on the degradation performance of the UBP-PMS system. The anti-interference performance of the UBP-PMS system is proven to be strong, as six inorganic anions (HCO3−, CO32−, NO3−, HPO42−, SO42− and Cl−) are added respectively to simulate the actual water environment. The contribution of different reactive species to the degradation process was evaluated qualitatively and quantitatively by electron spin resonance (ESR) and scavenger experiments, of which the largest contribution was •OH, followed by 1O2, ONOOH/O2•-, SO4•‒ and hydrated electrons. The potential degradation pathways of TC were analyzed, and the toxicity of the degradation intermediates was evaluated by quantitative structure-activity relationship (QSAR) analysis, revealing a gradual reduction in TC toxicity under the co-treatment of UBP-PMS. This study provides a novel activation strategy involving UBP-PMS and provides valuable insights into the degradation properties and mechanisms of emerging pollutants in actual water bodies.
2026, 37(4): 111670
doi: 10.1016/j.cclet.2025.111670
摘要:
Chemodynamic therapy (CDT) based on nanozyme has received much attention for safe and effective cancer treatment. However, the catalytic ability of nanozyme and insufficient intracellular H2O2 levels severely limit their therapeutic effect. To overcome these limitations, we construct tumor microenvironment-responsive hybrid cascade systems, where single-atom Cu nanozymes (CuNC SANs) with high peroxidase (POD)-like activity were synthesized to immobilize glucose oxidase (GOx). To enhance their biological performance and stability, polyethylene glycol (DSPE-PEG-NH2) is further modified. After endocytosis into tumor cells, the immobilized GOx of cascade systems reacts with intracellular glucose to produce H2O2 in situ. The H2O2 with elevated concentration can be further catalyzed by CuNC SANs and increase ROS yield after cascade reaction, thus amplifying the effect of CDT. In addition, the consumption of glucose cuts off the energy supply of the tumor, realizing starvation therapy. Significantly, the photothermal properties of CuNC SANs not only accelerate the cascade reaction but also enable photothermal therapy (PTT) for cancer treatment. This study proposes a promising PTT/CDT/starvation triple therapy strategy for high-efficiency cancer therapy.
Chemodynamic therapy (CDT) based on nanozyme has received much attention for safe and effective cancer treatment. However, the catalytic ability of nanozyme and insufficient intracellular H2O2 levels severely limit their therapeutic effect. To overcome these limitations, we construct tumor microenvironment-responsive hybrid cascade systems, where single-atom Cu nanozymes (CuNC SANs) with high peroxidase (POD)-like activity were synthesized to immobilize glucose oxidase (GOx). To enhance their biological performance and stability, polyethylene glycol (DSPE-PEG-NH2) is further modified. After endocytosis into tumor cells, the immobilized GOx of cascade systems reacts with intracellular glucose to produce H2O2 in situ. The H2O2 with elevated concentration can be further catalyzed by CuNC SANs and increase ROS yield after cascade reaction, thus amplifying the effect of CDT. In addition, the consumption of glucose cuts off the energy supply of the tumor, realizing starvation therapy. Significantly, the photothermal properties of CuNC SANs not only accelerate the cascade reaction but also enable photothermal therapy (PTT) for cancer treatment. This study proposes a promising PTT/CDT/starvation triple therapy strategy for high-efficiency cancer therapy.
2026, 37(4): 111674
doi: 10.1016/j.cclet.2025.111674
摘要:
The melt-transesterification polycondensation method necessitates elevated reaction temperatures and protracted reaction times in the copolymerization of modified isosorbide-based polycarbonates. This results in a decline in molecular weight and color degradation of the copolymerized IS-PC. In this paper, the process of polyethylene glycol (PEG) modification was introduced in the synthesis of isosorbide-based copolycarbonate (PEXHDCYC) by means of a melt chain extension method. As demonstrated by experimental findings, this method has the capacity to reduce the reaction temperature and shorten the reaction time. Additionally, it has been observed to enhance the molecular weight and overall properties of the material. Through the optimization of reaction conditions, a series of PEXHDCYC with weight average molecular weight (Mw) ranging from 19,004 g/mol to 73,294 g/mol were synthesized. The results demonstrated that the glass transition temperature (Tg) of PEXHDCYC decreased in conjunction with an increase in the PEG1000 content. It is noteworthy that the PEXHDCYC synthesized by this method exhibits an exceptional elongation at break, reaching up to 135.45% ± 24%. Furthermore, PEXHDCYC demonstrates superior optical properties in comparison to bisphenol A polycarbonate (BPA-PC).
The melt-transesterification polycondensation method necessitates elevated reaction temperatures and protracted reaction times in the copolymerization of modified isosorbide-based polycarbonates. This results in a decline in molecular weight and color degradation of the copolymerized IS-PC. In this paper, the process of polyethylene glycol (PEG) modification was introduced in the synthesis of isosorbide-based copolycarbonate (PEXHDCYC) by means of a melt chain extension method. As demonstrated by experimental findings, this method has the capacity to reduce the reaction temperature and shorten the reaction time. Additionally, it has been observed to enhance the molecular weight and overall properties of the material. Through the optimization of reaction conditions, a series of PEXHDCYC with weight average molecular weight (Mw) ranging from 19,004 g/mol to 73,294 g/mol were synthesized. The results demonstrated that the glass transition temperature (Tg) of PEXHDCYC decreased in conjunction with an increase in the PEG1000 content. It is noteworthy that the PEXHDCYC synthesized by this method exhibits an exceptional elongation at break, reaching up to 135.45% ± 24%. Furthermore, PEXHDCYC demonstrates superior optical properties in comparison to bisphenol A polycarbonate (BPA-PC).
2026, 37(4): 111675
doi: 10.1016/j.cclet.2025.111675
摘要:
The electrocatalytic reduction of carbon dioxide (CO2) into fuels holds significant promise for addressing energy and environmental challenges, albeit hindered by constraints in conversion efficiency, production rates, and electrode stability. Metal diborides are considered as promising electrocatalysts that may demonstrate superior CO2 electroreduction performance due to their distinctive electronic properties. Herein, a series of novel bulk metal diborides, encompassing transition metals from group IVB to group VIIB elements, were fabricated using a high pressure-high temperature technique, which were directly utilized as self-supporting electrodes for electrocatalytic reduction of CO2. The zirconium diboride (ZrB2) electrode stood out in metal diborides with superior electrocatalytic activity in generating carbon monoxide (CO), achieving a Faradaic efficiency of 92.2% at −2.2 V vs. Ag/Ag+ in ionic liquid-based electrolytes. Impressively, the ZrB2 electrode demonstrated stable catalysis of CO2 reduction to CO over a nearly 60-h electrolysis period. Furthermore, the ZrB2 electrode and ionic liquid-based electrolytes could synergistically catalyze the reduction of CO2 to CO. Experimental results and density functional theory calculations support the notion that exposed metal sites on the ZrB2 (001) surface could enhance *CO desorption and restrain the hydrogen evolution reaction, thereby facilitating the conversion of CO2 into CO.
The electrocatalytic reduction of carbon dioxide (CO2) into fuels holds significant promise for addressing energy and environmental challenges, albeit hindered by constraints in conversion efficiency, production rates, and electrode stability. Metal diborides are considered as promising electrocatalysts that may demonstrate superior CO2 electroreduction performance due to their distinctive electronic properties. Herein, a series of novel bulk metal diborides, encompassing transition metals from group IVB to group VIIB elements, were fabricated using a high pressure-high temperature technique, which were directly utilized as self-supporting electrodes for electrocatalytic reduction of CO2. The zirconium diboride (ZrB2) electrode stood out in metal diborides with superior electrocatalytic activity in generating carbon monoxide (CO), achieving a Faradaic efficiency of 92.2% at −2.2 V vs. Ag/Ag+ in ionic liquid-based electrolytes. Impressively, the ZrB2 electrode demonstrated stable catalysis of CO2 reduction to CO over a nearly 60-h electrolysis period. Furthermore, the ZrB2 electrode and ionic liquid-based electrolytes could synergistically catalyze the reduction of CO2 to CO. Experimental results and density functional theory calculations support the notion that exposed metal sites on the ZrB2 (001) surface could enhance *CO desorption and restrain the hydrogen evolution reaction, thereby facilitating the conversion of CO2 into CO.
2026, 37(4): 111703
doi: 10.1016/j.cclet.2025.111703
摘要:
Hydroxyethyl starch 130/0.4 (HES130/0.4) is a macromolecular polysaccharide with polydispersity, which is widely used as a plasma expander. Full-profile bioanalysis of HES130/0.4 is required to characterize its plasma pharmacokinetics, yet current analytical technologies struggle with this task due to its complex structure and composition. To address this existing lacuna within the realm of analytical science, we propose a liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) methodology for the full-profile bioanalysis of HES130/0.4. Amide column separation with gradient optimization eluted polydisperse HES130/0.4 as a single symmetric peak. In-source collision-induced dissociation (IS-CID) converted the numerous precursor ions of HES130/0.4 into a limited number of characteristic fragment ions, from which m/z 597.4 was selected as the "pseudo-precursor ion" for MRM quantification. The ion transition m/z 597.4 → 435.3 was identified as the quantitative ion pair. The method demonstrated a linear calibration curve from 40 µg/mL to 4000 µg/mL, with accuracy and precision meeting acceptance criteria, confirming its reliability and reproducibility. Subsequently, the workflow was successfully applied to investigate the pharmacokinetics of HES130/0.4 in rat, revealing its large distribution volume and rapid elimination within 24 h. This work provides a straightforward approach for the full-profile quantification of HES130/0.4 in biological samples, overcoming the limitations of traditional methods in terms of poor specificity, low sensitivity and narrow linear range, and providing a reference for the in vivo full-profile bioanalysis of HES130/0.4 and other polysaccharides.
Hydroxyethyl starch 130/0.4 (HES130/0.4) is a macromolecular polysaccharide with polydispersity, which is widely used as a plasma expander. Full-profile bioanalysis of HES130/0.4 is required to characterize its plasma pharmacokinetics, yet current analytical technologies struggle with this task due to its complex structure and composition. To address this existing lacuna within the realm of analytical science, we propose a liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) methodology for the full-profile bioanalysis of HES130/0.4. Amide column separation with gradient optimization eluted polydisperse HES130/0.4 as a single symmetric peak. In-source collision-induced dissociation (IS-CID) converted the numerous precursor ions of HES130/0.4 into a limited number of characteristic fragment ions, from which m/z 597.4 was selected as the "pseudo-precursor ion" for MRM quantification. The ion transition m/z 597.4 → 435.3 was identified as the quantitative ion pair. The method demonstrated a linear calibration curve from 40 µg/mL to 4000 µg/mL, with accuracy and precision meeting acceptance criteria, confirming its reliability and reproducibility. Subsequently, the workflow was successfully applied to investigate the pharmacokinetics of HES130/0.4 in rat, revealing its large distribution volume and rapid elimination within 24 h. This work provides a straightforward approach for the full-profile quantification of HES130/0.4 in biological samples, overcoming the limitations of traditional methods in terms of poor specificity, low sensitivity and narrow linear range, and providing a reference for the in vivo full-profile bioanalysis of HES130/0.4 and other polysaccharides.
2026, 37(4): 111704
doi: 10.1016/j.cclet.2025.111704
摘要:
Foodborne bacterial infection is a serious threat to food safety, especially live pathogens causing outbreaks of most diseases. Thus developing live bacterial detection methods is important for public health. In this study, a microfluidic biosensor was developed for rapid detection of live Salmonella typhimurium, in which immune magnetic particle chains in microchannels were used to separate and enrich target bacteria, antibody-conjugated gold nanorods (GNRs) were applied for photothermal lysis of target live bacteria under near-infrared (NIR) irradiation, and a photon-counting detector was used for measuring adenosine triphosphate (ATP) bioluminescence in the presence of firefly luciferin/luciferase. This biosensor was proved to be able to quantitatively detect S. typhimurium from 5.0 × 102 CFU/mL to 5.0 × 106 CFU/mL in 60 min (magnetic separation 20 min; GNRs combination 20 min; NIR irradiation, 8 min) with limit of detection (LOD) of 495 CFU/mL. This biosensor showed an excellent specificity in the coexistence of other foodborne bacteria, and target bacteria were successfully measured even in the matrix interference of milk sample with mean recovery of 121.17%. This biosensor might be a promising tool for on-site assessment foodborne bacteria.
Foodborne bacterial infection is a serious threat to food safety, especially live pathogens causing outbreaks of most diseases. Thus developing live bacterial detection methods is important for public health. In this study, a microfluidic biosensor was developed for rapid detection of live Salmonella typhimurium, in which immune magnetic particle chains in microchannels were used to separate and enrich target bacteria, antibody-conjugated gold nanorods (GNRs) were applied for photothermal lysis of target live bacteria under near-infrared (NIR) irradiation, and a photon-counting detector was used for measuring adenosine triphosphate (ATP) bioluminescence in the presence of firefly luciferin/luciferase. This biosensor was proved to be able to quantitatively detect S. typhimurium from 5.0 × 102 CFU/mL to 5.0 × 106 CFU/mL in 60 min (magnetic separation 20 min; GNRs combination 20 min; NIR irradiation, 8 min) with limit of detection (LOD) of 495 CFU/mL. This biosensor showed an excellent specificity in the coexistence of other foodborne bacteria, and target bacteria were successfully measured even in the matrix interference of milk sample with mean recovery of 121.17%. This biosensor might be a promising tool for on-site assessment foodborne bacteria.
2026, 37(4): 111705
doi: 10.1016/j.cclet.2025.111705
摘要:
E. coli O157:H7 and Staphylococcus aureus have emerged as significant foodborne pathogens, characterized by considerable incidence rates and mortality. Despite advancements, current detection methods are hindered by challenges in enhancing specificity and sensitivity. Herein, we introduced a cutting-edge biosensor that employs a novel CHA-coupled CRISPR multi-stage signal amplification technique for the rapid and ultra-sensitive detection of these two pathogens. This microfluidic device consisted of an upstream serpentine mixing channel and a downstream boat-shaped microcavity equipped with a micro-column array, facilitating efficient reagent mixing, robust CHA amplification, and CRISPR reactions. Multiple signal amplification was achieved through bacterial competitive binding triggered by catalytic hairpin assembly (CHA) and crRNA-mediated CRISPR reactions. Based on this platform, the detection of target bacteria is transformed into nucleic acid detection, with a maximum detection range of 134 CFU/mL for E. coli O157:H7 and 181 CFU/mL for Staphylococcus aureus, which were better or comparable to previously reported biosensors. The entire assay was completed within approximately 1.5 h, with a minimal sample volume requirement of just 10 µL. The biosensor exhibited a high recovery rate, ranging from 95% to 115%, and demonstrated excellent specificity towards the target bacteria. In summary, this biosensor offers a rapid, accurate, and highly sensitive tool for food safety and clinical diagnostics.
E. coli O157:H7 and Staphylococcus aureus have emerged as significant foodborne pathogens, characterized by considerable incidence rates and mortality. Despite advancements, current detection methods are hindered by challenges in enhancing specificity and sensitivity. Herein, we introduced a cutting-edge biosensor that employs a novel CHA-coupled CRISPR multi-stage signal amplification technique for the rapid and ultra-sensitive detection of these two pathogens. This microfluidic device consisted of an upstream serpentine mixing channel and a downstream boat-shaped microcavity equipped with a micro-column array, facilitating efficient reagent mixing, robust CHA amplification, and CRISPR reactions. Multiple signal amplification was achieved through bacterial competitive binding triggered by catalytic hairpin assembly (CHA) and crRNA-mediated CRISPR reactions. Based on this platform, the detection of target bacteria is transformed into nucleic acid detection, with a maximum detection range of 134 CFU/mL for E. coli O157:H7 and 181 CFU/mL for Staphylococcus aureus, which were better or comparable to previously reported biosensors. The entire assay was completed within approximately 1.5 h, with a minimal sample volume requirement of just 10 µL. The biosensor exhibited a high recovery rate, ranging from 95% to 115%, and demonstrated excellent specificity towards the target bacteria. In summary, this biosensor offers a rapid, accurate, and highly sensitive tool for food safety and clinical diagnostics.
2026, 37(4): 111708
doi: 10.1016/j.cclet.2025.111708
摘要:
Dielectric barrier discharge (DBD) plasma combined with Fe2+ for periodate (PI) activation was proposed for emerging contaminants treatment. The feasible, activation mechanism, degradation mechanism were comprehensively analyzed. Results showed that within 6 min treatment time, the degradation efficiency of sulfadiazine (SDZ) could reach 68.1%, 78.5% and 90.2% in DBD, DBD/PI and DBD/PI/Fe2+, respectively. The energy efficiency can also be improved from 47.24 mg/kWh (DBD) to 78.43 mg/kWh (DBD/PI/Fe2+). Compared with DBD system, the PI activation energy barrier in DBD/Fe2+ system is significantly decreased. Electron spin resonance (ESR) proved the existence of •OH, 1O2 and •O2− in DBD/PI/Fe2+ system, and the corresponding intensity are higher than that of DBD/PI system. The quenching experiments shown that •OH, 1O2, •O2− and electron play important role for SDZ degradation. Reactive species dominant to SDZ degradation was explored by LC–MS and density functional theory (DFT) analysis. Higher input power, acid condition and higher conductivity were favorable to SDZ degradation. DBD/PI/Fe2+ system has good effect in treating other emerging contaminants and obtains good environmental adaptability.
Dielectric barrier discharge (DBD) plasma combined with Fe2+ for periodate (PI) activation was proposed for emerging contaminants treatment. The feasible, activation mechanism, degradation mechanism were comprehensively analyzed. Results showed that within 6 min treatment time, the degradation efficiency of sulfadiazine (SDZ) could reach 68.1%, 78.5% and 90.2% in DBD, DBD/PI and DBD/PI/Fe2+, respectively. The energy efficiency can also be improved from 47.24 mg/kWh (DBD) to 78.43 mg/kWh (DBD/PI/Fe2+). Compared with DBD system, the PI activation energy barrier in DBD/Fe2+ system is significantly decreased. Electron spin resonance (ESR) proved the existence of •OH, 1O2 and •O2− in DBD/PI/Fe2+ system, and the corresponding intensity are higher than that of DBD/PI system. The quenching experiments shown that •OH, 1O2, •O2− and electron play important role for SDZ degradation. Reactive species dominant to SDZ degradation was explored by LC–MS and density functional theory (DFT) analysis. Higher input power, acid condition and higher conductivity were favorable to SDZ degradation. DBD/PI/Fe2+ system has good effect in treating other emerging contaminants and obtains good environmental adaptability.
2026, 37(4): 111729
doi: 10.1016/j.cclet.2025.111729
摘要:
NH4V4O10 has attracted significant attention as a cathode material for aqueous zinc-ion batteries (AZIBs) due to its adjustable interlayer spacing (~9.5 Å) and high theoretical specific capacity (~400 mAh/g). However, its development is hindered by sluggish Zn2+ kinetics and structural instability. In this work, a glycine (Gly) intercalation strategy is demonstrated, which establishes three stabilization mechanisms in the Gly-NVO cathode: (1) Gly pillars are shown to expand the interlayer spacing to 1.21 nm; (2) Hydrogen-bonding networks are formed between layers; (3) Reversible NH4+ (de)intercalation behavior is observed. The Gly-NVO cathode delivers a capacity of 520 mAh/g at 0.2 A/g (393 Wh/kg energy density), along with outstanding rate capability (400 and 150 mAh/g at 10 and 50 A/g, corresponding to power densities of 5688 and 24.3 kW/kg, respectively). A capacity retention of 88.2% is maintained after 10,000 cycles at 50 A/g. DFT calculations confirm that the introduction of Gly significantly enhances the electrical conductivity of NVO while effectively weakening electrostatic interactions, and energy barrier for Zn2+ intercalation and vanadium dissolution are reduced by Gly. Additionally, due to the reversible NH4+ (de)intercalation behavior in Gly-NVO, the assembled aqueous ammonium-ion batteries (AAIBs) exhibit stable cycling ability. This work highlights organic molecule pre-intercalation as a viable strategy for optimizing the durability of ammonium vanadate cathodes.
NH4V4O10 has attracted significant attention as a cathode material for aqueous zinc-ion batteries (AZIBs) due to its adjustable interlayer spacing (~9.5 Å) and high theoretical specific capacity (~400 mAh/g). However, its development is hindered by sluggish Zn2+ kinetics and structural instability. In this work, a glycine (Gly) intercalation strategy is demonstrated, which establishes three stabilization mechanisms in the Gly-NVO cathode: (1) Gly pillars are shown to expand the interlayer spacing to 1.21 nm; (2) Hydrogen-bonding networks are formed between layers; (3) Reversible NH4+ (de)intercalation behavior is observed. The Gly-NVO cathode delivers a capacity of 520 mAh/g at 0.2 A/g (393 Wh/kg energy density), along with outstanding rate capability (400 and 150 mAh/g at 10 and 50 A/g, corresponding to power densities of 5688 and 24.3 kW/kg, respectively). A capacity retention of 88.2% is maintained after 10,000 cycles at 50 A/g. DFT calculations confirm that the introduction of Gly significantly enhances the electrical conductivity of NVO while effectively weakening electrostatic interactions, and energy barrier for Zn2+ intercalation and vanadium dissolution are reduced by Gly. Additionally, due to the reversible NH4+ (de)intercalation behavior in Gly-NVO, the assembled aqueous ammonium-ion batteries (AAIBs) exhibit stable cycling ability. This work highlights organic molecule pre-intercalation as a viable strategy for optimizing the durability of ammonium vanadate cathodes.
2026, 37(4): 111732
doi: 10.1016/j.cclet.2025.111732
摘要:
Materials with blue-shifted and enhanced emission exhibit extensive applications in information encryption, solar ultraviolet sensing and ink-free printing, however, preparing blue-shifted and enhanced emission from photo-responsive material remains a significant challenge. Herein, we designed and synthesized successfully the photo-responsive ionic-bonded organic crystals (IOC) using tetraphenylethylene (TPE)-based multidentate imidazolium salt and sulfonic acid. Impressively, the discernible response of IOC to UV light is evidenced by a blue shift and an enhancement in dilute solution. Specifically, this has resulted in a significant increase in the absolute quantum yield, from 7.0% to 41.3%. This remarkable efficiency can be attributed to the cooperative effect that reduces non-radiative processes, the restriction of intermolecular motions (RIM) and the modulation of charge transfer (CT) behavior. This work first reports blue-shifted and enhanced emission from ionic crystal, providing a new strategy to achieve photochromic materials.
Materials with blue-shifted and enhanced emission exhibit extensive applications in information encryption, solar ultraviolet sensing and ink-free printing, however, preparing blue-shifted and enhanced emission from photo-responsive material remains a significant challenge. Herein, we designed and synthesized successfully the photo-responsive ionic-bonded organic crystals (IOC) using tetraphenylethylene (TPE)-based multidentate imidazolium salt and sulfonic acid. Impressively, the discernible response of IOC to UV light is evidenced by a blue shift and an enhancement in dilute solution. Specifically, this has resulted in a significant increase in the absolute quantum yield, from 7.0% to 41.3%. This remarkable efficiency can be attributed to the cooperative effect that reduces non-radiative processes, the restriction of intermolecular motions (RIM) and the modulation of charge transfer (CT) behavior. This work first reports blue-shifted and enhanced emission from ionic crystal, providing a new strategy to achieve photochromic materials.
2026, 37(4): 111743
doi: 10.1016/j.cclet.2025.111743
摘要:
Piezocatalysis offers an efficient approach for producing H2O2, a sustainable fuel and oxidant with a wide range of applications. Natural tourmaline, known for its exceptional piezoelectric properties, stands out as a promising green catalyst compared to other synthetic catalysts. In this study, natural tourmaline was modified using a simple acid treatment to remove iron, achieving effective piezocatalytic H2O2 synthesis at a rate of 513.7 µmol g−1 h−1 under ambient conditions. In-depth studies demonstrated that the Fe-free tourmaline exhibited a stronger polarization electric field due to the enhanced polyhedron distortion, compared to the Fe-containing tourmaline. The influence of temperature on their piezoresponse was also investigated. This study provides new insights into the mechanisms of piezoelectric H2O2 production using natural tourmaline.
Piezocatalysis offers an efficient approach for producing H2O2, a sustainable fuel and oxidant with a wide range of applications. Natural tourmaline, known for its exceptional piezoelectric properties, stands out as a promising green catalyst compared to other synthetic catalysts. In this study, natural tourmaline was modified using a simple acid treatment to remove iron, achieving effective piezocatalytic H2O2 synthesis at a rate of 513.7 µmol g−1 h−1 under ambient conditions. In-depth studies demonstrated that the Fe-free tourmaline exhibited a stronger polarization electric field due to the enhanced polyhedron distortion, compared to the Fe-containing tourmaline. The influence of temperature on their piezoresponse was also investigated. This study provides new insights into the mechanisms of piezoelectric H2O2 production using natural tourmaline.
2026, 37(4): 111754
doi: 10.1016/j.cclet.2025.111754
摘要:
Hydrogel electrolyte have attracted widely interest for aqueous zinc-ion batteries because of their multi-functionality and intrinsic safety. However, the unstable anode/electrolyte interface by dendrite and side reaction (HER) restricted the cycling of Zn anode, especially at high utilization. Herein, we propose an interface engineering strategy by introducing dimethylformamide (DMF) to polyacrylamide (PAM) electrolyte which could construct the polymer-inorganic bilayer solid electrolyte interphase (SEI) to improve the interface stability and compatibility. Internal Zn5(OH)6(CO3)2 provided high modulus to suppress the dendrite physically and external polymer exhibited flexibility to accommodate the volume change of Zn during cycles. Meanwhile, larger polymer clusters were induced by enhanced hydrogen-bond interactions, resulted in higher shear strength and interfacial adhesion. Additionally, DMF regulated the crystal orientation along (100) crystal plane and solvation structure of Zn2+ with PAM, enabling dense deposition and reduced by-products. Consequently, the Zn anode could provide an impressive lifespan (0.5 mA/cm2@0.5 mAh/cm2, 4000 h; 30 mA/cm2@15 mAh/cm2, 650 h). More importantly, high utilization (68%) was achieved using ultra-thin Zn (10 µm) with superior stability (2 mA/cm2@4 mAh/cm2, 1200 h). Coupled with iodine cathode, the Zn-I2 cell could provide an initial capacity of 184.5 mAh/g at the low ratio of anode/cathode capacity (N/P: 4.3) and ~86.4% retention over 500 cycles. This work provides a promising approach to construct robust interface by hydrogel electrolyte towards practical zinc-ion batteries.
Hydrogel electrolyte have attracted widely interest for aqueous zinc-ion batteries because of their multi-functionality and intrinsic safety. However, the unstable anode/electrolyte interface by dendrite and side reaction (HER) restricted the cycling of Zn anode, especially at high utilization. Herein, we propose an interface engineering strategy by introducing dimethylformamide (DMF) to polyacrylamide (PAM) electrolyte which could construct the polymer-inorganic bilayer solid electrolyte interphase (SEI) to improve the interface stability and compatibility. Internal Zn5(OH)6(CO3)2 provided high modulus to suppress the dendrite physically and external polymer exhibited flexibility to accommodate the volume change of Zn during cycles. Meanwhile, larger polymer clusters were induced by enhanced hydrogen-bond interactions, resulted in higher shear strength and interfacial adhesion. Additionally, DMF regulated the crystal orientation along (100) crystal plane and solvation structure of Zn2+ with PAM, enabling dense deposition and reduced by-products. Consequently, the Zn anode could provide an impressive lifespan (0.5 mA/cm2@0.5 mAh/cm2, 4000 h; 30 mA/cm2@15 mAh/cm2, 650 h). More importantly, high utilization (68%) was achieved using ultra-thin Zn (10 µm) with superior stability (2 mA/cm2@4 mAh/cm2, 1200 h). Coupled with iodine cathode, the Zn-I2 cell could provide an initial capacity of 184.5 mAh/g at the low ratio of anode/cathode capacity (N/P: 4.3) and ~86.4% retention over 500 cycles. This work provides a promising approach to construct robust interface by hydrogel electrolyte towards practical zinc-ion batteries.
2026, 37(4): 111776
doi: 10.1016/j.cclet.2025.111776
摘要:
The first example of heterogeneous direct benzylation of N-heterocycles (quinoxalin-2(1H)-ones and quinoxalines) with benzaldehydes has been accomplished via the sequence of a NaDT-photocatalyzed HAT, a single electron transfer reduction and a proton transfer, a spin-center shift and a back-HAT. Utilizing this strategy, a diverse array of benzylated N-heterocycles (29 examples) can be produced with high yields. Importantly, the DT-photocatalyzed direct benzylation with benzaldehydes would be a useful complement to the more extensively studied DT-photocatalyzed acylation and hydroxyalkylation, expanding the scope of DT photocatalysis.
The first example of heterogeneous direct benzylation of N-heterocycles (quinoxalin-2(1H)-ones and quinoxalines) with benzaldehydes has been accomplished via the sequence of a NaDT-photocatalyzed HAT, a single electron transfer reduction and a proton transfer, a spin-center shift and a back-HAT. Utilizing this strategy, a diverse array of benzylated N-heterocycles (29 examples) can be produced with high yields. Importantly, the DT-photocatalyzed direct benzylation with benzaldehydes would be a useful complement to the more extensively studied DT-photocatalyzed acylation and hydroxyalkylation, expanding the scope of DT photocatalysis.
2026, 37(4): 111781
doi: 10.1016/j.cclet.2025.111781
摘要:
Thermo-photocatalytic CO2 conversion to C2 products exhibits high research value and industrial potential. Enhancing the catalyst's adsorption activation for CO2 and H2O, along with multistep proton-coupled electron transfer (PCET) and C-C coupling, is crucial for achieving thermo-photocatalytic CO2 reduction conversion to C2 products with H2O as a proton source in a continuous process. In this paper, we explore a novel approach utilizing biochar to obtain catalysts with more defects and combine reducing biochar with MOF Materials (ZIF-67) to get a composite (ZIF-67/PC) with substantial CO2 and H2O adsorption activation capabilities and electron density gradients. Compared to PC and ZIF-67, the ZIF-67/PC exhibited excellent catalytic performance, particularly in obtaining a certain amount of C2 products (yield 5.59 µmol g-1 h-1, selectivity 55.96%). We also investigated the structure-function relationship of the catalyst and the contributions of thermal and light effects to the catalytic reaction, aiming to guide the establishment of efficient, high-throughput catalytic CO2 conversion technologies.
Thermo-photocatalytic CO2 conversion to C2 products exhibits high research value and industrial potential. Enhancing the catalyst's adsorption activation for CO2 and H2O, along with multistep proton-coupled electron transfer (PCET) and C-C coupling, is crucial for achieving thermo-photocatalytic CO2 reduction conversion to C2 products with H2O as a proton source in a continuous process. In this paper, we explore a novel approach utilizing biochar to obtain catalysts with more defects and combine reducing biochar with MOF Materials (ZIF-67) to get a composite (ZIF-67/PC) with substantial CO2 and H2O adsorption activation capabilities and electron density gradients. Compared to PC and ZIF-67, the ZIF-67/PC exhibited excellent catalytic performance, particularly in obtaining a certain amount of C2 products (yield 5.59 µmol g-1 h-1, selectivity 55.96%). We also investigated the structure-function relationship of the catalyst and the contributions of thermal and light effects to the catalytic reaction, aiming to guide the establishment of efficient, high-throughput catalytic CO2 conversion technologies.
2026, 37(4): 111788
doi: 10.1016/j.cclet.2025.111788
摘要:
Digital microfluidics (DMF) shows great promise in addressing the need for miniaturization and automation in immunoassay detection. Despite recent advances, an automatically operated, multiplexed heterogeneous immunoassay platform powered by DMF remains underdeveloped. Here we present a DMF platform for automated and multiplexed heterogeneous immunoassay detection by coupling spatial barcoding with automatic and uniform droplet dispensing. FluoroPel was selected as a robust hydrophobic reagent for coating the DMF top plate, and it also served as the substrate for the immuno-reaction. Its mechanical robustness was further enhanced with a Cytop CTL-809A adhesive layer under the top hydrophobic layer. Hourglass-shaped electrode patterns ensured consistent and uniform distribution of immunoassay reagents, with volume variation down to 1.0%. The analysis duration was significantly reduced from 75 min to 20 min after a heating module was integrated to elevate the immuno-reaction temperature to 37 °C. Utilizing a compact instrument featuring a multi-droplet manipulation protocol, we successfully implemented fully operated, multi-sample, multiplexed immunoassays using recombinant proteins on cell culture supernatants on the DMF platform. This innovative platform significantly enhances the efficiency, reliability, and degree of automation of DMF-actuated multiplexed heterogeneous immunoassays, potentially providing a viable solution for field deployment and multi-sample parallel diagnosis.
Digital microfluidics (DMF) shows great promise in addressing the need for miniaturization and automation in immunoassay detection. Despite recent advances, an automatically operated, multiplexed heterogeneous immunoassay platform powered by DMF remains underdeveloped. Here we present a DMF platform for automated and multiplexed heterogeneous immunoassay detection by coupling spatial barcoding with automatic and uniform droplet dispensing. FluoroPel was selected as a robust hydrophobic reagent for coating the DMF top plate, and it also served as the substrate for the immuno-reaction. Its mechanical robustness was further enhanced with a Cytop CTL-809A adhesive layer under the top hydrophobic layer. Hourglass-shaped electrode patterns ensured consistent and uniform distribution of immunoassay reagents, with volume variation down to 1.0%. The analysis duration was significantly reduced from 75 min to 20 min after a heating module was integrated to elevate the immuno-reaction temperature to 37 °C. Utilizing a compact instrument featuring a multi-droplet manipulation protocol, we successfully implemented fully operated, multi-sample, multiplexed immunoassays using recombinant proteins on cell culture supernatants on the DMF platform. This innovative platform significantly enhances the efficiency, reliability, and degree of automation of DMF-actuated multiplexed heterogeneous immunoassays, potentially providing a viable solution for field deployment and multi-sample parallel diagnosis.
2026, 37(4): 111805
doi: 10.1016/j.cclet.2025.111805
摘要:
The extensive use of various antibiotics and organic dyes has led to increasingly severe environmental issues and posed a significant threat to human health. Developing an efficient and safe dual-functional photocatalytic material for degradation and antibacterial purposes is the key to solving environmental pollution problems. Polythiophene and covalent organic frameworks (COFs) possess excellent photophysical properties, high stability, and ease of modification, offering broad application prospects and significant development potential in the removal of organic pollutants and antibiotic-resistant bacteria (ARB). A high-performance conductive polymer PTET-T-COOH (PThC) was prepared via the Stille coupling reaction, and a bipyridine (Bpy) covalent organic framework Bpy-COF was synthesized through acid-catalyzed imine condensation. By utilizing the π-π stacking and hydrogen bonding interactions between Bpy-COF and PThC, a novel Bpy-COF/PThC all-organic heterojunction was successfully fabricated. Compared to Bpy-COF and PThC, the composite exhibits a broadened spectral response range and higher carrier separation efficiency. The 30% Bpy-COF/PThC demonstrates the best photocatalytic performance, achieving a 99.96% inactivation rate of methicillin-resistant Staphylococcus aureus (MRSA) with a cell density of 7.23 log and a 95.28% bactericidal rate of Escherichia coli (E. coli) with a cell density of 7.50 log within 60 min. Under natural light, it not only exhibits good inactivation effects on both MRSA and E. coli, but also shows excellent degradation performance for rhodamine B, methylene blue, and tetracycline. The cytotoxicity experiment demonstrates that the composite exhibits good biocompatibility and potential for practical applications. The research results provide new design ideas for constructing efficient and safe organic photocatalysts, and offer a theoretical basis for the treatment of water pollution.
The extensive use of various antibiotics and organic dyes has led to increasingly severe environmental issues and posed a significant threat to human health. Developing an efficient and safe dual-functional photocatalytic material for degradation and antibacterial purposes is the key to solving environmental pollution problems. Polythiophene and covalent organic frameworks (COFs) possess excellent photophysical properties, high stability, and ease of modification, offering broad application prospects and significant development potential in the removal of organic pollutants and antibiotic-resistant bacteria (ARB). A high-performance conductive polymer PTET-T-COOH (PThC) was prepared via the Stille coupling reaction, and a bipyridine (Bpy) covalent organic framework Bpy-COF was synthesized through acid-catalyzed imine condensation. By utilizing the π-π stacking and hydrogen bonding interactions between Bpy-COF and PThC, a novel Bpy-COF/PThC all-organic heterojunction was successfully fabricated. Compared to Bpy-COF and PThC, the composite exhibits a broadened spectral response range and higher carrier separation efficiency. The 30% Bpy-COF/PThC demonstrates the best photocatalytic performance, achieving a 99.96% inactivation rate of methicillin-resistant Staphylococcus aureus (MRSA) with a cell density of 7.23 log and a 95.28% bactericidal rate of Escherichia coli (E. coli) with a cell density of 7.50 log within 60 min. Under natural light, it not only exhibits good inactivation effects on both MRSA and E. coli, but also shows excellent degradation performance for rhodamine B, methylene blue, and tetracycline. The cytotoxicity experiment demonstrates that the composite exhibits good biocompatibility and potential for practical applications. The research results provide new design ideas for constructing efficient and safe organic photocatalysts, and offer a theoretical basis for the treatment of water pollution.
2026, 37(4): 111881
doi: 10.1016/j.cclet.2025.111881
摘要:
Quinone-based electrode materials hold significant promise for next-generation sodium-ion batteries due to their structurally tailorable frameworks, high theoretical capacities, and favorable redox potentials. However, dissolution in organic electrolytes and structural instability during cycling critically impair their capacity retention and cycling durability. Herein, we designed and synthesized two novel acylimide materials N,N'-bis(2,6-anthraquinone diamine)-biphenyl diimide (DQ-BDI) and N,N'-bis(anthraquinone-2,6-diamine)-perylenyl diimide (DQ-PDI) with the gradual enhancement of π-conjugation. Electrochemical characterization reveals exceptional performance in DQ-PDI. At the current density of 50 mA/g, the DQ-PDI delivered the first discharge specific capacity of 158 mAh/g, and the capacity retention of 99% after 100 cycles, with the coulombic efficiency of nearly 100%. At a high current density of 500 mA/g, the DQ-PDI displays a high discharge capacity of 152 mAh/g. The reduction peaks of DQ-PDI located at 2.28 V and 1.34 V are the insertion reactions of sodium ion from the carbonyl groups on PTCDA unit and on DAAQ unit at both ends, respectively, and the two oxidation peaks at 2.58 V and 1.53 V corresponds to extraction reactions. Compared with DQ-BDI, DQ-PDI exhibits a larger π-conjugation plane, which significantly enhances the intermolecular π-π interactions. It can well reduce the dissolution of the material in organic electrolyte, resulting in a higher discharge capacity, superior cycling stability and accelerated reaction kinetics. Our π-conjugation extension strategy establishes a new paradigm for designing dissolution-resistant, high-performance organic electrodes.
Quinone-based electrode materials hold significant promise for next-generation sodium-ion batteries due to their structurally tailorable frameworks, high theoretical capacities, and favorable redox potentials. However, dissolution in organic electrolytes and structural instability during cycling critically impair their capacity retention and cycling durability. Herein, we designed and synthesized two novel acylimide materials N,N'-bis(2,6-anthraquinone diamine)-biphenyl diimide (DQ-BDI) and N,N'-bis(anthraquinone-2,6-diamine)-perylenyl diimide (DQ-PDI) with the gradual enhancement of π-conjugation. Electrochemical characterization reveals exceptional performance in DQ-PDI. At the current density of 50 mA/g, the DQ-PDI delivered the first discharge specific capacity of 158 mAh/g, and the capacity retention of 99% after 100 cycles, with the coulombic efficiency of nearly 100%. At a high current density of 500 mA/g, the DQ-PDI displays a high discharge capacity of 152 mAh/g. The reduction peaks of DQ-PDI located at 2.28 V and 1.34 V are the insertion reactions of sodium ion from the carbonyl groups on PTCDA unit and on DAAQ unit at both ends, respectively, and the two oxidation peaks at 2.58 V and 1.53 V corresponds to extraction reactions. Compared with DQ-BDI, DQ-PDI exhibits a larger π-conjugation plane, which significantly enhances the intermolecular π-π interactions. It can well reduce the dissolution of the material in organic electrolyte, resulting in a higher discharge capacity, superior cycling stability and accelerated reaction kinetics. Our π-conjugation extension strategy establishes a new paradigm for designing dissolution-resistant, high-performance organic electrodes.
2026, 37(4): 111899
doi: 10.1016/j.cclet.2025.111899
摘要:
The stability of cathode catalyst layers (CCLs) in proton exchange membrane fuel cells (PEMFCs) is critically undermined by Pt dissolution and the loss of effective gas-water management associated with carbon support corrosion. In this work, we develop a porous TiN nanotube−supported Pt (i.e., Pt/TiN NTs) CCL that integrates robust Pt–Ti interfacial bonding with a highly accessible nanotube network to address these persistent challenges. The formation of abundant Pt–Ti bonds at the interface markedly strengthens Pt anchoring, resulting in a 2.3−fold reduction in Pt dissolution and minimal particle coarsening after accelerated durability testing compared to nanoflows-based controls dominated by Pt–N−Ti interactions. The membrane electrode assembly fabricated with this CCL achieves a peak power density of 0.81 W/cm2 and demonstrates exceptional durability, retaining 77% of its initial mass activity and 87.3% of its power density following aggressive square-wave potential cycling, meeting the 2025 U.S. Department of Energy benchmarks. Computational fluid dynamics simulation further reveal that the unique porous architecture facilitates efficient oxygen transport and rapid water removal, sustaining high catalytic utilization under operational conditions. This strategy establishes TiN NTs scaffolds as a generalizable solution for the next generation of carbon-free, high-stability catalyst layers, offering practical guidance for durable and efficient fuel cell design.
The stability of cathode catalyst layers (CCLs) in proton exchange membrane fuel cells (PEMFCs) is critically undermined by Pt dissolution and the loss of effective gas-water management associated with carbon support corrosion. In this work, we develop a porous TiN nanotube−supported Pt (i.e., Pt/TiN NTs) CCL that integrates robust Pt–Ti interfacial bonding with a highly accessible nanotube network to address these persistent challenges. The formation of abundant Pt–Ti bonds at the interface markedly strengthens Pt anchoring, resulting in a 2.3−fold reduction in Pt dissolution and minimal particle coarsening after accelerated durability testing compared to nanoflows-based controls dominated by Pt–N−Ti interactions. The membrane electrode assembly fabricated with this CCL achieves a peak power density of 0.81 W/cm2 and demonstrates exceptional durability, retaining 77% of its initial mass activity and 87.3% of its power density following aggressive square-wave potential cycling, meeting the 2025 U.S. Department of Energy benchmarks. Computational fluid dynamics simulation further reveal that the unique porous architecture facilitates efficient oxygen transport and rapid water removal, sustaining high catalytic utilization under operational conditions. This strategy establishes TiN NTs scaffolds as a generalizable solution for the next generation of carbon-free, high-stability catalyst layers, offering practical guidance for durable and efficient fuel cell design.
2026, 37(4): 111901
doi: 10.1016/j.cclet.2025.111901
摘要:
The management of breast cancer remains clinically intractable, driven by its highly invasive behavior and limited susceptibility to conventional treatments. In this study, we engineered an innovative cyclodextrin-porphyrin co-assembled nanoplatform (CT NPs) to enable multimodal breast cancer therapy. By successfully encapsulating camptothecin (CPT) within this nanocarrier, the system (CTC NPs) achieved synergistic chemo-phototherapeutic efficacy through dual-modality action. The highly biocompatible cyclodextrin carrier significantly improved the physicochemical characteristics of CPT. In vivo studies revealed that CTC NPs effectively evaded clearance by the reticuloendothelial system, overcame the defect of premature drug leakage, and exhibited superior tumor targeting and infiltration capabilities. Under near-infrared (NIR) laser irradiation, CTC NPs can simultaneously induce localized hyperthermia and produce reactive oxygen species (ROS), thereby achieving efficient tumor ablation. In 4T1 tumor-bearing mice, CTC NPs exhibited targeted, safe, and highly potent anti-tumor efficacy, significantly suppressing both primary tumor progression (tumor suppression rate > 95%) and metastatic dissemination. In summary, this integrated nanoplatform establishes a novel theranostic paradigm for synergistic chemo-phototherapy against triple-negative breast cancer (TNBC), achieving precise tumor ablation through NIR-triggered drug release and real-time imaging guidance.
The management of breast cancer remains clinically intractable, driven by its highly invasive behavior and limited susceptibility to conventional treatments. In this study, we engineered an innovative cyclodextrin-porphyrin co-assembled nanoplatform (CT NPs) to enable multimodal breast cancer therapy. By successfully encapsulating camptothecin (CPT) within this nanocarrier, the system (CTC NPs) achieved synergistic chemo-phototherapeutic efficacy through dual-modality action. The highly biocompatible cyclodextrin carrier significantly improved the physicochemical characteristics of CPT. In vivo studies revealed that CTC NPs effectively evaded clearance by the reticuloendothelial system, overcame the defect of premature drug leakage, and exhibited superior tumor targeting and infiltration capabilities. Under near-infrared (NIR) laser irradiation, CTC NPs can simultaneously induce localized hyperthermia and produce reactive oxygen species (ROS), thereby achieving efficient tumor ablation. In 4T1 tumor-bearing mice, CTC NPs exhibited targeted, safe, and highly potent anti-tumor efficacy, significantly suppressing both primary tumor progression (tumor suppression rate > 95%) and metastatic dissemination. In summary, this integrated nanoplatform establishes a novel theranostic paradigm for synergistic chemo-phototherapy against triple-negative breast cancer (TNBC), achieving precise tumor ablation through NIR-triggered drug release and real-time imaging guidance.
2026, 37(4): 111938
doi: 10.1016/j.cclet.2025.111938
摘要:
Two pairs of potent analgesic alkaloid enantiomers with unprecedented chemical architectures, named pyrethalkalines A (1) and B (2), were isolated from the roots of Anacyclus pyrethrum. Pyrethalkaline A (1) is an unprecedented 6/6/6/6/5-fused pentacyclic triamino alkaloid featuring a unique 8,15-diaza-pentacyclo[12.3.1.11,9.05,19.010,14]nonadecane core, and pyrethalkaline B (2) is a novel 6/6/6/6/5/6-fused hexacyclic triamino alkaloid possessing an unprecedented 8,13,19-triazahexacyclo[16.3.1.11,9.05,23.010,18.011,16]tricosane motif. Their structures were elucidated by comprehensive spectroscopic data analysis, quantum 13C nuclear magnetic resonance (NMR) DP4+ and electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction analysis, and their plausible biosynthetic pathways were proposed. Alkaloids (±)-1 and (−)-1 at three lower doses of 1, 0.2, and 0.04 mg/kg, and (+)-2 at two lower doses of 1 and 0.2 mg/kg showed more potent analgesic activity than the positive control morphine. Further investigation revealed that (+)-1 and (−)-1 are dual transient receptor potential melastatin 8 (TRPM8) (half-maximal inhibitory concentration (IC50) = 1.90 ± 0.09 and 1.40 ± 0.17 µmol/L, respectively) and Kv1.2 inhibitors. Molecular dockings of 1 provide a novel structural model to develop potent analgesics dual targeting TRPM8 and Kv1.2 ion channels, and (±)-1 have the potential for the development of a non-opioid potent analgesic to treat neurogenic pains.
Two pairs of potent analgesic alkaloid enantiomers with unprecedented chemical architectures, named pyrethalkalines A (1) and B (2), were isolated from the roots of Anacyclus pyrethrum. Pyrethalkaline A (1) is an unprecedented 6/6/6/6/5-fused pentacyclic triamino alkaloid featuring a unique 8,15-diaza-pentacyclo[12.3.1.11,9.05,19.010,14]nonadecane core, and pyrethalkaline B (2) is a novel 6/6/6/6/5/6-fused hexacyclic triamino alkaloid possessing an unprecedented 8,13,19-triazahexacyclo[16.3.1.11,9.05,23.010,18.011,16]tricosane motif. Their structures were elucidated by comprehensive spectroscopic data analysis, quantum 13C nuclear magnetic resonance (NMR) DP4+ and electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction analysis, and their plausible biosynthetic pathways were proposed. Alkaloids (±)-1 and (−)-1 at three lower doses of 1, 0.2, and 0.04 mg/kg, and (+)-2 at two lower doses of 1 and 0.2 mg/kg showed more potent analgesic activity than the positive control morphine. Further investigation revealed that (+)-1 and (−)-1 are dual transient receptor potential melastatin 8 (TRPM8) (half-maximal inhibitory concentration (IC50) = 1.90 ± 0.09 and 1.40 ± 0.17 µmol/L, respectively) and Kv1.2 inhibitors. Molecular dockings of 1 provide a novel structural model to develop potent analgesics dual targeting TRPM8 and Kv1.2 ion channels, and (±)-1 have the potential for the development of a non-opioid potent analgesic to treat neurogenic pains.
2026, 37(4): 112002
doi: 10.1016/j.cclet.2025.112002
摘要:
Organic fluorescence-phosphorescence dual-emitting materials based on tunable single chromophores have attracted much attention for their broad application prospects in information technology, display media and other fields due to their high luminescence stability, simple preparation process and excellent reproducibility. Herein, we constructed a novel LP-activated fluorescence-phosphorescence dual-light-harvesting (FPRET) supramolecular assembly based on LP with orthogonal charges, the phosphorescent molecule G and the NIR dye NIB through a supramolecular non-covalent strategy. The energy transfer efficiency of fluorescence is 54.68% when the molar ratio of G/LP to NIB is 10:1, while the energy transfer efficiency and antenna effect of phosphorescence are 48.75% and 241.43 respectively when the molar ratio of G/LP to NIB is 50:1. In addition, by co-assembling with carbon dots (CDs) and adjusting the ratio of donor to acceptor components, the full-color spectral regulation including white light (CIE chromaticity coordinates x, y = 0.31, 0.33) was realized. Utilizing this LP to promote the supramolecular full-color FPRET assembly of single fluorophore G and showing the multi-level anti-counterfeiting of intelligent logic gates through pattern, time, and color editing, it provides a new insight and direction for the development of a new generation of high-performance optical functional materials.
Organic fluorescence-phosphorescence dual-emitting materials based on tunable single chromophores have attracted much attention for their broad application prospects in information technology, display media and other fields due to their high luminescence stability, simple preparation process and excellent reproducibility. Herein, we constructed a novel LP-activated fluorescence-phosphorescence dual-light-harvesting (FPRET) supramolecular assembly based on LP with orthogonal charges, the phosphorescent molecule G and the NIR dye NIB through a supramolecular non-covalent strategy. The energy transfer efficiency of fluorescence is 54.68% when the molar ratio of G/LP to NIB is 10:1, while the energy transfer efficiency and antenna effect of phosphorescence are 48.75% and 241.43 respectively when the molar ratio of G/LP to NIB is 50:1. In addition, by co-assembling with carbon dots (CDs) and adjusting the ratio of donor to acceptor components, the full-color spectral regulation including white light (CIE chromaticity coordinates x, y = 0.31, 0.33) was realized. Utilizing this LP to promote the supramolecular full-color FPRET assembly of single fluorophore G and showing the multi-level anti-counterfeiting of intelligent logic gates through pattern, time, and color editing, it provides a new insight and direction for the development of a new generation of high-performance optical functional materials.
2026, 37(4): 112096
doi: 10.1016/j.cclet.2025.112096
摘要:
The development of efficient and cost-effective non-precious-metal single-atom catalysts (SACs) is crucial for advancing the practical application of electrocatalytic CO2 reduction (CO2RR). However, identifying highly active metal atoms and designing catalysts with uniform active center structures remain significant challenges. To address this, we developed a generic pyrolysis method to synthesize a series of transition metal-based SACs with atomically dispersed metal anchored on carbon nitride support (M-C3N4, M = Fe, Ni, Cu). Benefiting from the unique electronic structure of the Fe-N4 sites supported on C3N4, the Fe-C3N4 catalyst demonstrated exceptional performance, achieving a CO Faradaic efficiency of 99.6% and maintaining excellent stability. Theoretical calculations indicate that the Fe site exhibits a relatively stronger interaction with the *COOH intermediate, thereby helping to lower the energy barrier of the CO2 protonation process. This study provides valuable theoretical insights and practical synthesis strategies for designing high-performance non-precious-metal SACs for CO2RR.
The development of efficient and cost-effective non-precious-metal single-atom catalysts (SACs) is crucial for advancing the practical application of electrocatalytic CO2 reduction (CO2RR). However, identifying highly active metal atoms and designing catalysts with uniform active center structures remain significant challenges. To address this, we developed a generic pyrolysis method to synthesize a series of transition metal-based SACs with atomically dispersed metal anchored on carbon nitride support (M-C3N4, M = Fe, Ni, Cu). Benefiting from the unique electronic structure of the Fe-N4 sites supported on C3N4, the Fe-C3N4 catalyst demonstrated exceptional performance, achieving a CO Faradaic efficiency of 99.6% and maintaining excellent stability. Theoretical calculations indicate that the Fe site exhibits a relatively stronger interaction with the *COOH intermediate, thereby helping to lower the energy barrier of the CO2 protonation process. This study provides valuable theoretical insights and practical synthesis strategies for designing high-performance non-precious-metal SACs for CO2RR.
2026, 37(4): 112324
doi: 10.1016/j.cclet.2025.112324
摘要:
Cancer persists as a major global health challenge, marked by high recurrence rates in aggressive malignancies such as melanoma. While immunotherapy has emerged as a promising approach, its clinical benefits are often limited by tumor immune escape mechanisms and an immunosuppressive tumor microenvironment (TME). These hurdles have driven the exploration of integrated approaches, with photothermal-immunotherapy gaining significant traction. In this study, we developed a multifunctional nanoadjuvant (MICN@PI) engineered with an acid-responsive calcium carbonate core, a hypoxia-alleviating MnO2 component, a polydopamine shell for photothermal ablation, and co-loaded immunomodulators (imiquimod and indoximod). The MnO2 in the nanoadjuvant catalytically converted the overexpressed H2O2 in the TME into O2. Concurrently, the combined action of imiquimod and indoximod orchestrated a potent adaptive immune response. Upon near-infrared laser irradiation, MICN@PI achieved significant tumor ablation, inhibited recurrence, and prolonged survival in a murine melanoma model, offering a safe and effective synergistic photothermal-immunotherapy strategy for cancer treatment.
Cancer persists as a major global health challenge, marked by high recurrence rates in aggressive malignancies such as melanoma. While immunotherapy has emerged as a promising approach, its clinical benefits are often limited by tumor immune escape mechanisms and an immunosuppressive tumor microenvironment (TME). These hurdles have driven the exploration of integrated approaches, with photothermal-immunotherapy gaining significant traction. In this study, we developed a multifunctional nanoadjuvant (MICN@PI) engineered with an acid-responsive calcium carbonate core, a hypoxia-alleviating MnO2 component, a polydopamine shell for photothermal ablation, and co-loaded immunomodulators (imiquimod and indoximod). The MnO2 in the nanoadjuvant catalytically converted the overexpressed H2O2 in the TME into O2. Concurrently, the combined action of imiquimod and indoximod orchestrated a potent adaptive immune response. Upon near-infrared laser irradiation, MICN@PI achieved significant tumor ablation, inhibited recurrence, and prolonged survival in a murine melanoma model, offering a safe and effective synergistic photothermal-immunotherapy strategy for cancer treatment.
2026, 37(4): 111845
doi: 10.1016/j.cclet.2025.111845
摘要:
2026, 37(4): 112163
doi: 10.1016/j.cclet.2025.112163
摘要:
2026, 37(1): 110064
doi: 10.1016/j.cclet.2024.110064
摘要:
This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.
This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.
2026, 37(1): 110071
doi: 10.1016/j.cclet.2024.110071
摘要:
Regulation of apoptosis represents a key parameter in all living organisms. In this paper, an input-induced logic-gated modular nanocalculator is designed to regulate cancer cell apoptosis by programmatically combining and connecting logic gate modules with different functions. Via rational design of the various logic gate modules of the nanocalculator, different apoptosis related operations including cancer cell targeting, apoptosis induction, and apoptosis monitoring could be performed. Importantly, each of these logic gate modules could independently perform apoptosis related YES logic operations when ran separately. After combining each YES logic gate module into a logic circuit and connecting it to the GO scaffold to construct a logic-gated nanocalculator, the input-induced logic-gated modular nanocalculator could selectively enter cancer cells and control the drug release to logically apoptosis (output), by performing AND logic gate operations when inputs (nucleolin and H+) were included at the same time. Moreover, evidence suggests that these efficient logical calculations proceed in cancer cell apoptosis regulation without the general limiations of lithography in nanotechnology. As such, this work provides a new vision for the construction of a logic-gated modular nanocalculator with logical calculation proficiency potentially useful in cancer therapy and the regulation of life.
Regulation of apoptosis represents a key parameter in all living organisms. In this paper, an input-induced logic-gated modular nanocalculator is designed to regulate cancer cell apoptosis by programmatically combining and connecting logic gate modules with different functions. Via rational design of the various logic gate modules of the nanocalculator, different apoptosis related operations including cancer cell targeting, apoptosis induction, and apoptosis monitoring could be performed. Importantly, each of these logic gate modules could independently perform apoptosis related YES logic operations when ran separately. After combining each YES logic gate module into a logic circuit and connecting it to the GO scaffold to construct a logic-gated nanocalculator, the input-induced logic-gated modular nanocalculator could selectively enter cancer cells and control the drug release to logically apoptosis (output), by performing AND logic gate operations when inputs (nucleolin and H+) were included at the same time. Moreover, evidence suggests that these efficient logical calculations proceed in cancer cell apoptosis regulation without the general limiations of lithography in nanotechnology. As such, this work provides a new vision for the construction of a logic-gated modular nanocalculator with logical calculation proficiency potentially useful in cancer therapy and the regulation of life.
2026, 37(1): 110414
doi: 10.1016/j.cclet.2024.110414
摘要:
Magnesium hydride (MgH2) demonstrates immense potential as a solid-state hydrogen storage material, while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics. Herein, a MOF derived multi-phase FeNi3-S catalyst was specially designed for efficient hydrogen storage in MgH2. Experiments confirmed that the incorporation of FeNi3-S into MgH2 significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption. The initial dehydrogenation temperature of the MgH2 + 10 wt% FeNi3-S composite was 202 °C, which was 123 °C lower than that of pure MgH2. At 325 °C, the MgH2 + 10 wt% FeNi3-S composite released 6.57 wt% H2 (fully dehydrogenated) within 1000 s. Remarkably, MgH2 + 10 wt% FeNi3-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H2 within 30 min at 100 °C. Moreover, 6.3 wt% H2 was still retained after 20 cycles at 300 °C, demonstrating the superior cycling performance of the MgH2 + 10 wt% FeNi3-S composite. The activation energy fitting calculations further evidenced the addition of FeNi3-S enhanced the de/resorption kinetics of MgH2 (Ea = 98.6 kJ/mol and 43.3 kJ/mol, respectively). Through phase and microstructural analysis, it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg2Ni + Fe/MgS and MgH2/Mg2NiH4 + Fe/MgS hydrogen storage systems. Further mechanistic analysis revealed that Mg2Ni/Mg2NiH4 served as “hydrogen pump” and Fe/MgS served as “hydrogen diffusion channel”, thus accelerating the dissociation and recombination of hydrogen molecules. In conclusion, this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH2, which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
Magnesium hydride (MgH2) demonstrates immense potential as a solid-state hydrogen storage material, while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics. Herein, a MOF derived multi-phase FeNi3-S catalyst was specially designed for efficient hydrogen storage in MgH2. Experiments confirmed that the incorporation of FeNi3-S into MgH2 significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption. The initial dehydrogenation temperature of the MgH2 + 10 wt% FeNi3-S composite was 202 °C, which was 123 °C lower than that of pure MgH2. At 325 °C, the MgH2 + 10 wt% FeNi3-S composite released 6.57 wt% H2 (fully dehydrogenated) within 1000 s. Remarkably, MgH2 + 10 wt% FeNi3-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H2 within 30 min at 100 °C. Moreover, 6.3 wt% H2 was still retained after 20 cycles at 300 °C, demonstrating the superior cycling performance of the MgH2 + 10 wt% FeNi3-S composite. The activation energy fitting calculations further evidenced the addition of FeNi3-S enhanced the de/resorption kinetics of MgH2 (Ea = 98.6 kJ/mol and 43.3 kJ/mol, respectively). Through phase and microstructural analysis, it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg2Ni + Fe/MgS and MgH2/Mg2NiH4 + Fe/MgS hydrogen storage systems. Further mechanistic analysis revealed that Mg2Ni/Mg2NiH4 served as “hydrogen pump” and Fe/MgS served as “hydrogen diffusion channel”, thus accelerating the dissociation and recombination of hydrogen molecules. In conclusion, this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH2, which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
2026, 37(1): 110572
doi: 10.1016/j.cclet.2024.110572
摘要:
The rate-limited activation of NN triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation. Here, polymeric carbon nitride with frustrated Lewis pairs (FLPs) was constructed by inserting electron-deficient magnesium into g-C3N4 (CN). The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen (N2) fixation by carbon nitride.
The rate-limited activation of NN triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation. Here, polymeric carbon nitride with frustrated Lewis pairs (FLPs) was constructed by inserting electron-deficient magnesium into g-C3N4 (CN). The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen (N2) fixation by carbon nitride.
2026, 37(1): 110576
doi: 10.1016/j.cclet.2024.110576
摘要:
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion. However, their applications are challenged by the sluggish oxygen reducton reaction (ORR) kinetics at cathodes owning to the low O2 solubility and diffusion rate. Herein, we proposed a photo-biocatalytic fuel cell (PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase (ZIF-8/CDs/BOD@algae). Microalgae absorbed CO2 and provided O2 in situ for BOD catalysts. Due to effective absorption of O2 by imidazole and confinement of hydrophobic porous ZIF-8, oxygen diffusion has been accelerated in MOF/enzyme systems. Importantly, the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD. Thus, the biocathode exhibited a high current density of 1767 µA/cm2, a 2.26-fold increase compared with that of CDs/BOD/algae biocathode. Also, it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation. When coupled with Mo: BiVO4 photoanodes, the PBFC exhibited a remarkable power output of 131.8 µW/cm2 using tetracycline hydrochloride (TCH) as a fuel and an increased degradation rate of TCH. Therefore, this work not only establishs an effective confinement strategy for enzyme to enrich oxygen, but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion. However, their applications are challenged by the sluggish oxygen reducton reaction (ORR) kinetics at cathodes owning to the low O2 solubility and diffusion rate. Herein, we proposed a photo-biocatalytic fuel cell (PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase (ZIF-8/CDs/BOD@algae). Microalgae absorbed CO2 and provided O2 in situ for BOD catalysts. Due to effective absorption of O2 by imidazole and confinement of hydrophobic porous ZIF-8, oxygen diffusion has been accelerated in MOF/enzyme systems. Importantly, the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD. Thus, the biocathode exhibited a high current density of 1767 µA/cm2, a 2.26-fold increase compared with that of CDs/BOD/algae biocathode. Also, it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation. When coupled with Mo: BiVO4 photoanodes, the PBFC exhibited a remarkable power output of 131.8 µW/cm2 using tetracycline hydrochloride (TCH) as a fuel and an increased degradation rate of TCH. Therefore, this work not only establishs an effective confinement strategy for enzyme to enrich oxygen, but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
2026, 37(1): 110752
doi: 10.1016/j.cclet.2024.110752
摘要:
Converting CO2 into methanol (CH3OH), a high-value-added liquid-phase product, through efficient and highly selective photocatalysis remains a significant challenge. Herein, we present a straightforward cation exchange strategy for the in-situ growth of BiVO4 on an InVO4 substrate to generate a Z-scheme heterojunction of InVO4/BiVO4. This in-situ partial transformation approach endows the InVO4/BiVO4 heterojunction with a tightly connected interface, resulting in a significant improvement in charge separation efficiency between InVO4 and BiVO4. Moreover, the construction of the heterojunction reduces the formation energy barrier of the *COOH intermediate during the photoreduction of CO2 and increases the desorption energy barrier of the *CO intermediate, facilitating the deep reduction of *CO. Consequently, the InVO4/BiVO4 heterojunction is capable of photocatalytic CO2 reduction to CH3OH with high efficiency and selectivity. Under conditions where water serves as the electron source and a light intensity of 100 mW/cm2, the yield of CH3OH reaches 130.5 µmol g−1 h−1 with a selectivity of 92 %, outperforming photocatalysts reported under similar conditions.
Converting CO2 into methanol (CH3OH), a high-value-added liquid-phase product, through efficient and highly selective photocatalysis remains a significant challenge. Herein, we present a straightforward cation exchange strategy for the in-situ growth of BiVO4 on an InVO4 substrate to generate a Z-scheme heterojunction of InVO4/BiVO4. This in-situ partial transformation approach endows the InVO4/BiVO4 heterojunction with a tightly connected interface, resulting in a significant improvement in charge separation efficiency between InVO4 and BiVO4. Moreover, the construction of the heterojunction reduces the formation energy barrier of the *COOH intermediate during the photoreduction of CO2 and increases the desorption energy barrier of the *CO intermediate, facilitating the deep reduction of *CO. Consequently, the InVO4/BiVO4 heterojunction is capable of photocatalytic CO2 reduction to CH3OH with high efficiency and selectivity. Under conditions where water serves as the electron source and a light intensity of 100 mW/cm2, the yield of CH3OH reaches 130.5 µmol g−1 h−1 with a selectivity of 92 %, outperforming photocatalysts reported under similar conditions.
2026, 37(1): 110903
doi: 10.1016/j.cclet.2025.110903
摘要:
Many labdane-related diterpenoids (LRDs) exhibit high values in drug development. Their diversity in structure and bioactivity, to a large extent, arise from oxidative modifications which are mainly catalyzed by cytochrome P450s (CYPs). The medicinal plant Euphorbia fischeriana Steud. is rich in LRDs with distinct scaffolds. Herein, we characterized three cytochrome P450s involved in LRD biosynthesis from this plant. Notably, CYP71D450 and CYP701A148 are two substrate-promiscuity CYPs. The former is the first example of CYPs which can oxidize C-3 of ent–atisane skeleton and ent–isopimara-7(8),15-diene, and the latter is the first example of CYPs which can oxidize C-19 of ent–abietane and ent–pimarane skeletons. This study expands the toolkit for bioproduction of diverse LRDs.
Many labdane-related diterpenoids (LRDs) exhibit high values in drug development. Their diversity in structure and bioactivity, to a large extent, arise from oxidative modifications which are mainly catalyzed by cytochrome P450s (CYPs). The medicinal plant Euphorbia fischeriana Steud. is rich in LRDs with distinct scaffolds. Herein, we characterized three cytochrome P450s involved in LRD biosynthesis from this plant. Notably, CYP71D450 and CYP701A148 are two substrate-promiscuity CYPs. The former is the first example of CYPs which can oxidize C-3 of ent–atisane skeleton and ent–isopimara-7(8),15-diene, and the latter is the first example of CYPs which can oxidize C-19 of ent–abietane and ent–pimarane skeletons. This study expands the toolkit for bioproduction of diverse LRDs.
2026, 37(1): 110919
doi: 10.1016/j.cclet.2025.110919
摘要:
Owing to their intricate molecular frameworks and copious chiral centers, the structural identification and configurational assignment of natural products are challenging tasks. Comprehensive spectral data analysis is crucial for the confirmation of absolute configurations. Ignoring critical parameters will lead to false structure, which may confuse the total synthesis and drug development. Herein, the configurations of seven heterogeneous Pallavicinia diterpenoids (PDs) isolated from Pallavicinia liverworts are revised using a combination of single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. Meanwhile, identification of five unprecedented PD heterodimers PD-dimers A–E (18–22) along with eleven previously undescribed PDs (5–9, 13–17, 23) obtained by the reinvestigation of the Chinese liverwort Pallavicinia subciliata have resulted in corrections and support the revised conclusions.
Owing to their intricate molecular frameworks and copious chiral centers, the structural identification and configurational assignment of natural products are challenging tasks. Comprehensive spectral data analysis is crucial for the confirmation of absolute configurations. Ignoring critical parameters will lead to false structure, which may confuse the total synthesis and drug development. Herein, the configurations of seven heterogeneous Pallavicinia diterpenoids (PDs) isolated from Pallavicinia liverworts are revised using a combination of single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. Meanwhile, identification of five unprecedented PD heterodimers PD-dimers A–E (18–22) along with eleven previously undescribed PDs (5–9, 13–17, 23) obtained by the reinvestigation of the Chinese liverwort Pallavicinia subciliata have resulted in corrections and support the revised conclusions.
2026, 37(1): 110956
doi: 10.1016/j.cclet.2025.110956
摘要:
Overproduction of reactive oxygen species (ROS) following ischemic injury triggers an inflammatory response, significantly impeding neurological functional recovery. Nanozymes with potent antioxidative and anti-inflammatory effects thus offer great potential for ischemic stroke treatment. In this study, we developed an ischemia-homing nanozyme by combining melatonin (MT)-loaded honeycomb manganese dioxide (MnO2) nanoflowers with M2-type microglia membranes to rescue the ischemic penumbra. The surface-engineered M2-type microglia membranes provided intrinsic ischemia-homing and blood-brain barrier (BBB)-crossing properties to the biomimetic nanozymes. This nanozyme can not only transforms harmfulsuperoxide anion radicals (•O2–) and hydrogen peroxide (H2O2) into harmless water and oxygen but also scavenges highly toxic hydroxyl radicals (•OH), dramatically lowering intracellular ROS levels. More importantly, the biomimetic nanoparticles reduce cerebral infarct areas and provide significant neuroprotection against ischemic stroke by lowering oxidative stress, inhibiting cell apoptosis, and decreasing inflammation. This study may offer a viable approach for the use of nanozymes in treating ischemic stroke.
Overproduction of reactive oxygen species (ROS) following ischemic injury triggers an inflammatory response, significantly impeding neurological functional recovery. Nanozymes with potent antioxidative and anti-inflammatory effects thus offer great potential for ischemic stroke treatment. In this study, we developed an ischemia-homing nanozyme by combining melatonin (MT)-loaded honeycomb manganese dioxide (MnO2) nanoflowers with M2-type microglia membranes to rescue the ischemic penumbra. The surface-engineered M2-type microglia membranes provided intrinsic ischemia-homing and blood-brain barrier (BBB)-crossing properties to the biomimetic nanozymes. This nanozyme can not only transforms harmfulsuperoxide anion radicals (•O2–) and hydrogen peroxide (H2O2) into harmless water and oxygen but also scavenges highly toxic hydroxyl radicals (•OH), dramatically lowering intracellular ROS levels. More importantly, the biomimetic nanoparticles reduce cerebral infarct areas and provide significant neuroprotection against ischemic stroke by lowering oxidative stress, inhibiting cell apoptosis, and decreasing inflammation. This study may offer a viable approach for the use of nanozymes in treating ischemic stroke.
2026, 37(1): 110959
doi: 10.1016/j.cclet.2025.110959
摘要:
Metal ion homeostasis plays a pivotal role in maintaining cellular functions, and its disruption can initiate regulated cell death pathways. Despite its therapeutic potential, metal ion therapy for breast cancer has been hampered by inefficient ion delivery and the intrinsic resistance mechanisms of cancer cells. In this work, a cuproptosis amplifier of copper-telaglenastat coordinate (denoted as Cu-CB) is developed to trigger cell ferroptosis for synergistic breast cancer treatment. Telaglenastat (CB-839), a glutaminase inhibitor, is identified as an effective copper ionophore that facilitates the formation of Cu-CB. Specially, Cu-CB can promote the aggregation of lipoylated proteins to initiate cuproptosis, while also inhibiting glutathione (GSH) synthesis and downregulating glutathione peroxidase 4 (GPX4) to trigger ferroptosis. The interplay between these cuproptosis and apoptosis pathways, mediated by Cu-CB, significantly amplifies reactive oxygen species (ROS) production and lipid peroxidation, culminating in the synergistic suppression of breast cancer. Both in vitro and in vivo studies validate the superior antitumor effects of Cu-CB through the induction of cuproptosis and ferroptosis, which may provide a new insight for metal ion delivery systems and metal ion-based tumor therapies.
Metal ion homeostasis plays a pivotal role in maintaining cellular functions, and its disruption can initiate regulated cell death pathways. Despite its therapeutic potential, metal ion therapy for breast cancer has been hampered by inefficient ion delivery and the intrinsic resistance mechanisms of cancer cells. In this work, a cuproptosis amplifier of copper-telaglenastat coordinate (denoted as Cu-CB) is developed to trigger cell ferroptosis for synergistic breast cancer treatment. Telaglenastat (CB-839), a glutaminase inhibitor, is identified as an effective copper ionophore that facilitates the formation of Cu-CB. Specially, Cu-CB can promote the aggregation of lipoylated proteins to initiate cuproptosis, while also inhibiting glutathione (GSH) synthesis and downregulating glutathione peroxidase 4 (GPX4) to trigger ferroptosis. The interplay between these cuproptosis and apoptosis pathways, mediated by Cu-CB, significantly amplifies reactive oxygen species (ROS) production and lipid peroxidation, culminating in the synergistic suppression of breast cancer. Both in vitro and in vivo studies validate the superior antitumor effects of Cu-CB through the induction of cuproptosis and ferroptosis, which may provide a new insight for metal ion delivery systems and metal ion-based tumor therapies.
2026, 37(1): 110964
doi: 10.1016/j.cclet.2025.110964
摘要:
Alzheimer’s disease (AD) is a common neurodegenerative disorder among the elderly population. There are currently no effective therapeutic drugs available, the multi-target-directed ligands (MTDLs) strategy has been considered as the promising approach. Given the structural diversity of natural products, Rivastigmine’s pharmacophore was integrated with diverse natural product scaffolds to construct a combinatorial compound library. This library was subsequently screened and optimized to identify a novel butyrylcholinesterase (BuChE) inhibitor, compound 3c. The results showed that compound 3c exhibited favorable BuChE inhibitory activity (half-maximal inhibitory concentration (IC50) = 0.43 µmol/L), potential anti-inflammatory potency, good Aβ1–42 aggregation inhibitory capacity and remarkable neuroprotective effects. The in vivo study exhibited that 3c significantly ameliorated AlCl3-induced zebrafish AD model and scopolamine-induced memory impairment. Collectively, compound 3c was the artificial intelligence (AI)-driven promising multifunctional agent with BuChE inhibition for the treatment of AD.
Alzheimer’s disease (AD) is a common neurodegenerative disorder among the elderly population. There are currently no effective therapeutic drugs available, the multi-target-directed ligands (MTDLs) strategy has been considered as the promising approach. Given the structural diversity of natural products, Rivastigmine’s pharmacophore was integrated with diverse natural product scaffolds to construct a combinatorial compound library. This library was subsequently screened and optimized to identify a novel butyrylcholinesterase (BuChE) inhibitor, compound 3c. The results showed that compound 3c exhibited favorable BuChE inhibitory activity (half-maximal inhibitory concentration (IC50) = 0.43 µmol/L), potential anti-inflammatory potency, good Aβ1–42 aggregation inhibitory capacity and remarkable neuroprotective effects. The in vivo study exhibited that 3c significantly ameliorated AlCl3-induced zebrafish AD model and scopolamine-induced memory impairment. Collectively, compound 3c was the artificial intelligence (AI)-driven promising multifunctional agent with BuChE inhibition for the treatment of AD.
2026, 37(1): 110966
doi: 10.1016/j.cclet.2025.110966
摘要:
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms, therapeutic agents and functional tools. Herein, we present a novel nanoplatform activated by near-infrared (NIR) light for triple-modal proteins study, which enabling target protein labeling, enrichment and visualization. Azido-naphthalimide-coated upconversion nanoparticles (UCNPs) serve as NIR light-responsive nanoplatforms, showing promising applications in studying interactions between various bioactive molecules and proteins in living systems. Under NIR light irradiation, azido-naphthalimides are activated by ultraviolet (UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance. We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments, achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria. Furthermore, in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform. This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms, therapeutic agents and functional tools. Herein, we present a novel nanoplatform activated by near-infrared (NIR) light for triple-modal proteins study, which enabling target protein labeling, enrichment and visualization. Azido-naphthalimide-coated upconversion nanoparticles (UCNPs) serve as NIR light-responsive nanoplatforms, showing promising applications in studying interactions between various bioactive molecules and proteins in living systems. Under NIR light irradiation, azido-naphthalimides are activated by ultraviolet (UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance. We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments, achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria. Furthermore, in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform. This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
2026, 37(1): 110970
doi: 10.1016/j.cclet.2025.110970
摘要:
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death (ICD)-enhanced cancer therapy, which holds immense promise for the efficient treatment of cancer. However, precise delivery of ICD inducer is severely hindered by complex biological barriers. How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge. Herein, this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage (Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ) (DACHPt) as ICD inducer. After actively targeting the CD44 on the surface of 4T1 tumor cell, this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment, resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation. By integration of internal and external stimuli intelligently, this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death (ICD)-enhanced cancer therapy, which holds immense promise for the efficient treatment of cancer. However, precise delivery of ICD inducer is severely hindered by complex biological barriers. How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge. Herein, this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage (Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ) (DACHPt) as ICD inducer. After actively targeting the CD44 on the surface of 4T1 tumor cell, this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment, resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation. By integration of internal and external stimuli intelligently, this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
2026, 37(1): 110971
doi: 10.1016/j.cclet.2025.110971
摘要:
Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH2) compared to the para-amino substituted one (p-NH2). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH2 vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH2) compared to the para-amino substituted one (p-NH2). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH2 vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
2026, 37(1): 110979
doi: 10.1016/j.cclet.2025.110979
摘要:
Sulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
Sulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
2026, 37(1): 110981
doi: 10.1016/j.cclet.2025.110981
摘要:
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
2026, 37(1): 111042
doi: 10.1016/j.cclet.2025.111042
摘要:
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
2026, 37(1): 111072
doi: 10.1016/j.cclet.2025.111072
摘要:
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
2026, 37(1): 111082
doi: 10.1016/j.cclet.2025.111082
摘要:
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
2026, 37(1): 111085
doi: 10.1016/j.cclet.2025.111085
摘要:
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
2026, 37(1): 111095
doi: 10.1016/j.cclet.2025.111095
摘要:
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
2026, 37(1): 111116
doi: 10.1016/j.cclet.2025.111116
摘要:
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
2026, 37(1): 111131
doi: 10.1016/j.cclet.2025.111131
摘要:
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
2026, 37(1): 111132
doi: 10.1016/j.cclet.2025.111132
摘要:
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
2026, 37(1): 111134
doi: 10.1016/j.cclet.2025.111134
摘要:
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
2026, 37(1): 111142
doi: 10.1016/j.cclet.2025.111142
摘要:
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
2026, 37(1): 111146
doi: 10.1016/j.cclet.2025.111146
摘要:
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
2026, 37(1): 111147
doi: 10.1016/j.cclet.2025.111147
摘要:
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
2026, 37(1): 111153
doi: 10.1016/j.cclet.2025.111153
摘要:
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
2026, 37(1): 111154
doi: 10.1016/j.cclet.2025.111154
摘要:
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
2026, 37(1): 111165
doi: 10.1016/j.cclet.2025.111165
摘要:
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
2026, 37(1): 111168
doi: 10.1016/j.cclet.2025.111168
摘要:
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
2026, 37(1): 111177
doi: 10.1016/j.cclet.2025.111177
摘要:
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
2026, 37(1): 111184
doi: 10.1016/j.cclet.2025.111184
摘要:
DNA methylation is an important promising biomarker for cancer diagnosis and monitoring. Therefore, the assessment of DNA methylation levels is helpful for the prognosis and diagnosis of cancer. However, it is still a huge challenge to sensitively and accurately quantify the levels of DNA methylation in clinical sample. In this work, we proposed a protospacer adjacent motif (PAM)-free mediated CRISPR-Cas12a ultra-sensitive and quantitative DNA methylation detection method. Through recognizing the dsDNA with toehold region, CRISPR-Cas12a not only got rid of the limitation of PAM, but also improved its distinction ability for single CpG site methylation, nearly 5-fold that of conventional PAM-containing dsDNA. We further introduced assist-strand and design an artificial mismatch to greatly improve the ability to distinguish single CpG methylation site. Our results showed that the discrimination factor was > 200. Then, we constructed toe-dsDNA by using "heating and freezing", which made our method universally applicable and feasible. In addition, we greatly simplified the difficulty of primer design. Our method detected four highly methylated genes acyl carrier protein (ACP), CLV3/ESR-related (CLE), Disabled (DAB) and Homeobox (HOX) with a detection limit of 0.01% and excellent linearity in DNA methylation standards. Then, we verified the clinical utility of this method in 29 hepatocellular carcinomas, 11 ovarian cancers and 4 health people. In conclusion, we have successfully constructed a PAM-free CRISPR-Cas12a DNA methylation quantification method, which achieves high congruence in sensitivity, specificity and universality, fully demonstrating its significant clinical application value.
DNA methylation is an important promising biomarker for cancer diagnosis and monitoring. Therefore, the assessment of DNA methylation levels is helpful for the prognosis and diagnosis of cancer. However, it is still a huge challenge to sensitively and accurately quantify the levels of DNA methylation in clinical sample. In this work, we proposed a protospacer adjacent motif (PAM)-free mediated CRISPR-Cas12a ultra-sensitive and quantitative DNA methylation detection method. Through recognizing the dsDNA with toehold region, CRISPR-Cas12a not only got rid of the limitation of PAM, but also improved its distinction ability for single CpG site methylation, nearly 5-fold that of conventional PAM-containing dsDNA. We further introduced assist-strand and design an artificial mismatch to greatly improve the ability to distinguish single CpG methylation site. Our results showed that the discrimination factor was > 200. Then, we constructed toe-dsDNA by using "heating and freezing", which made our method universally applicable and feasible. In addition, we greatly simplified the difficulty of primer design. Our method detected four highly methylated genes acyl carrier protein (ACP), CLV3/ESR-related (CLE), Disabled (DAB) and Homeobox (HOX) with a detection limit of 0.01% and excellent linearity in DNA methylation standards. Then, we verified the clinical utility of this method in 29 hepatocellular carcinomas, 11 ovarian cancers and 4 health people. In conclusion, we have successfully constructed a PAM-free CRISPR-Cas12a DNA methylation quantification method, which achieves high congruence in sensitivity, specificity and universality, fully demonstrating its significant clinical application value.
2026, 37(1): 111186
doi: 10.1016/j.cclet.2025.111186
摘要:
Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO2, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO2 stationary phase. Firstly, COF@SiO2 was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO2. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO2 can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO2 is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO2, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO2 stationary phase. Firstly, COF@SiO2 was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO2. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO2 can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO2 is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
2026, 37(1): 111187
doi: 10.1016/j.cclet.2025.111187
摘要:
Cuprous oxide (Cu2O) is one of the most promising catalysts for electrochemical conversion of CO2 into value-added C2 products. The efficiency of CO2-to-C2 conversion is highly dependent on the Cu2O crystal plane orientation and the corresponding adsorbed *CO species. Herein, we constructed high-index crystal planes (311) in Cu2O (CO–Cu2O) via a facile self-selective CO-induced strategy under a CO atmosphere, which was verified by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) results. By exploiting the high surface energy of the high index crystal planes, *CO species are stabilized in CO–Cu2O during CO2RR, resulting in exceptional catalytic performance for CO2-to-C2 products. In situ infrared spectroscopy revealed that both atop-type (*COatop) and hollow-type (*COhollow) adsorption of *CO species occurred on the CO–Cu2O. The asymmetric C–C coupling energy barrier between *COatop and *COhollow in (311) crystal plane decreases by 47.8% compared to the symmetric coupling of *COatop in conventional (100) crystal planes. Consequently, the Faradaic efficiency of C2 products generated with CO–Cu2O was increased by as high as 100% compared to that with pristine Cu2O.
Cuprous oxide (Cu2O) is one of the most promising catalysts for electrochemical conversion of CO2 into value-added C2 products. The efficiency of CO2-to-C2 conversion is highly dependent on the Cu2O crystal plane orientation and the corresponding adsorbed *CO species. Herein, we constructed high-index crystal planes (311) in Cu2O (CO–Cu2O) via a facile self-selective CO-induced strategy under a CO atmosphere, which was verified by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) results. By exploiting the high surface energy of the high index crystal planes, *CO species are stabilized in CO–Cu2O during CO2RR, resulting in exceptional catalytic performance for CO2-to-C2 products. In situ infrared spectroscopy revealed that both atop-type (*COatop) and hollow-type (*COhollow) adsorption of *CO species occurred on the CO–Cu2O. The asymmetric C–C coupling energy barrier between *COatop and *COhollow in (311) crystal plane decreases by 47.8% compared to the symmetric coupling of *COatop in conventional (100) crystal planes. Consequently, the Faradaic efficiency of C2 products generated with CO–Cu2O was increased by as high as 100% compared to that with pristine Cu2O.
2026, 37(1): 111197
doi: 10.1016/j.cclet.2025.111197
摘要:
The direct transformation of dinitrogen (N2) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N2 to N-methylimides. Initially, the N2-bridging end-on dititanium side-on dipotassium complex [{(TrenTMS)Ti}2(μ-η1:η1:η2:η2-N2K2)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(NMe, TMSNN2TMS)Ti}(μ-NMe)]2 with complete cleavage of the N≡N bond. The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N-methylimides. Moreover, nitrogen-15 (15N) labeled experiments provided a novel approach to synthesizing 15N-labeled methylimides.
The direct transformation of dinitrogen (N2) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N2 to N-methylimides. Initially, the N2-bridging end-on dititanium side-on dipotassium complex [{(TrenTMS)Ti}2(μ-η1:η1:η2:η2-N2K2)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(NMe, TMSNN2TMS)Ti}(μ-NMe)]2 with complete cleavage of the N≡N bond. The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N-methylimides. Moreover, nitrogen-15 (15N) labeled experiments provided a novel approach to synthesizing 15N-labeled methylimides.
2026, 37(1): 111207
doi: 10.1016/j.cclet.2025.111207
摘要:
The excessive use of pesticides has exacerbated environmental pollution due to herbicide residues, while their persistent toxicity poses serious challenges to global ecological security. A magnetically recyclable CoFe2O4/BiOBr S-scheme heterojunctions was prepared by microwave-assisted co-precipitation method for photocatalytic degradation of Diuron (DUR) in water. The formation of S-scheme heterojunction enhances electron transfer and charge separation, which was demonstrated by free radical trapping, electrochemical experiments, and DFT calculations. The magnetic CoFe2O4/BiOBr catalysts can achieve 99.9% removal of diuron in 50 min under visible light irradiation. Furthermore, the system maintains stable performance across a broad pH range (3–9), enabling adaptation to diverse water environments, effective elimination of multiple pollutants, and strong resistance to ionic interference. Using magnetic recovery, CoFe2O4/BiOBr exhibits a high removal rate of 99% and a markedly low ion leaching rate (< 20 µg/L) after six cycles photocatalytic process, confirming its excellent stability and durability. According to HPLC-QTOF-MS and DFT calculation, the main ways of DUR degradation include dechlorinated hydroxylation, dealkylation and hydroxylation of aromatic ring and side chain. Toxicity analysis showed that the toxicity of the intermediates generated during degradation was generally lower than that of DUR. The magnetic CoFe2O4/BiOBr S-scheme heterojunction developed in this study exhibits excellent photocatalytic performance, high applicability, good stability, and durability, providing an effective magnetic for the removal of refractory pollutants.
The excessive use of pesticides has exacerbated environmental pollution due to herbicide residues, while their persistent toxicity poses serious challenges to global ecological security. A magnetically recyclable CoFe2O4/BiOBr S-scheme heterojunctions was prepared by microwave-assisted co-precipitation method for photocatalytic degradation of Diuron (DUR) in water. The formation of S-scheme heterojunction enhances electron transfer and charge separation, which was demonstrated by free radical trapping, electrochemical experiments, and DFT calculations. The magnetic CoFe2O4/BiOBr catalysts can achieve 99.9% removal of diuron in 50 min under visible light irradiation. Furthermore, the system maintains stable performance across a broad pH range (3–9), enabling adaptation to diverse water environments, effective elimination of multiple pollutants, and strong resistance to ionic interference. Using magnetic recovery, CoFe2O4/BiOBr exhibits a high removal rate of 99% and a markedly low ion leaching rate (< 20 µg/L) after six cycles photocatalytic process, confirming its excellent stability and durability. According to HPLC-QTOF-MS and DFT calculation, the main ways of DUR degradation include dechlorinated hydroxylation, dealkylation and hydroxylation of aromatic ring and side chain. Toxicity analysis showed that the toxicity of the intermediates generated during degradation was generally lower than that of DUR. The magnetic CoFe2O4/BiOBr S-scheme heterojunction developed in this study exhibits excellent photocatalytic performance, high applicability, good stability, and durability, providing an effective magnetic for the removal of refractory pollutants.
2026, 37(1): 111219
doi: 10.1016/j.cclet.2025.111219
摘要:
Albeit notable endeavors in the construction of organophosphorodithioates, the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge. Herein, an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine. This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields (up to 98% yield) with high stereoselectivities (up to 97% ee and >99:1 E/Z).
Albeit notable endeavors in the construction of organophosphorodithioates, the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge. Herein, an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine. This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields (up to 98% yield) with high stereoselectivities (up to 97% ee and >99:1 E/Z).
2026, 37(1): 111222
doi: 10.1016/j.cclet.2025.111222
摘要:
T-cell acute lymphoblastic leukemia (T-ALL) is a common yet severe pediatric cancer treated with L-asparaginase (ASP). To boost the treatment's effectiveness and lessen its toxicity, enzyme@MOF nanoparticles were engineered with a hyaluronic acid (HA)-targeted polyethylene glycol (PEG) surface. These nanoparticles, termed ASP@MOF/PEG-HA, showed efficient uptake by drug-resistant T-ALL cells. The pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) based metal-organic framework (MOF) nanoparticles allowed the encapsulated ASP to significantly increase cytotoxicity against T-ALL cells. Furthermore, HA's ability to bind to T-ALL cells with elevated CD44 expression further induced apoptosis in CD44+ T-ALL cells with poor prognosis. In animal models, the nanoparticles improved survival rates and reduced the burden of leukemia, demonstrating substantial anti-leukemia effects. Thus, these nanoparticles offer an effective treatment approach for drug-resistant T-ALL cells characterized by increased CD44 expression.
T-cell acute lymphoblastic leukemia (T-ALL) is a common yet severe pediatric cancer treated with L-asparaginase (ASP). To boost the treatment's effectiveness and lessen its toxicity, enzyme@MOF nanoparticles were engineered with a hyaluronic acid (HA)-targeted polyethylene glycol (PEG) surface. These nanoparticles, termed ASP@MOF/PEG-HA, showed efficient uptake by drug-resistant T-ALL cells. The pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) based metal-organic framework (MOF) nanoparticles allowed the encapsulated ASP to significantly increase cytotoxicity against T-ALL cells. Furthermore, HA's ability to bind to T-ALL cells with elevated CD44 expression further induced apoptosis in CD44+ T-ALL cells with poor prognosis. In animal models, the nanoparticles improved survival rates and reduced the burden of leukemia, demonstrating substantial anti-leukemia effects. Thus, these nanoparticles offer an effective treatment approach for drug-resistant T-ALL cells characterized by increased CD44 expression.
2026, 37(1): 111237
doi: 10.1016/j.cclet.2025.111237
摘要:
Hepatic fibrosis is regulated by the synergistic actions of various cells and cytokines, with the activation and proliferation of hepatic stellate cells (HSCs) being considered the central event in this process. To achieve specific targeting of activated hepatic stellate cells (aHSCs) and precise treatment of hepatic fibrosis, this study developed a dual-functional drug delivery system (SIL/cRGD-PEG-PPS PMs) with both targeting and responsive release capabilities. It aims to target the αvβ3 receptor specifically expressed on the surface of aHSCs using the cyclic peptide c(RGDyk), and to exploit the high reactive oxygen species (ROS) level in the cellular microenvironment to achieve concentrated burst release of drugs at the pathological sites of hepatic fibrosis. Based on multiple assessments, SIL/cRGD-PEG-PPS PMs specifically enhanced the targeted delivery of silybin (SIL) to aHSCs, inhibited the proliferation and migration of aHSCs, and exhibited good biosafety. Additionally, it demonstrated excellent anti-fibrotic activity in fibrotic mice. In summary, this study shows great potential in targeted treatment of hepatic fibrosis and provides a multifunctional tool for advancing the research and therapeutic strategies of hepatic fibrosis.
Hepatic fibrosis is regulated by the synergistic actions of various cells and cytokines, with the activation and proliferation of hepatic stellate cells (HSCs) being considered the central event in this process. To achieve specific targeting of activated hepatic stellate cells (aHSCs) and precise treatment of hepatic fibrosis, this study developed a dual-functional drug delivery system (SIL/cRGD-PEG-PPS PMs) with both targeting and responsive release capabilities. It aims to target the αvβ3 receptor specifically expressed on the surface of aHSCs using the cyclic peptide c(RGDyk), and to exploit the high reactive oxygen species (ROS) level in the cellular microenvironment to achieve concentrated burst release of drugs at the pathological sites of hepatic fibrosis. Based on multiple assessments, SIL/cRGD-PEG-PPS PMs specifically enhanced the targeted delivery of silybin (SIL) to aHSCs, inhibited the proliferation and migration of aHSCs, and exhibited good biosafety. Additionally, it demonstrated excellent anti-fibrotic activity in fibrotic mice. In summary, this study shows great potential in targeted treatment of hepatic fibrosis and provides a multifunctional tool for advancing the research and therapeutic strategies of hepatic fibrosis.
2026, 37(1): 111251
doi: 10.1016/j.cclet.2025.111251
摘要:
Nanofiltration (NF) technology, with its capacity for nanoscale filtration and controllable selectivity, holds significant promise in diverse applications. However, the current upper bound of permeance and selectivity of NF membranes is intrinsically constrained by the morphology and structure of the polyamide (PA) selective layer. This issue arises because NF membranes typically exhibit relatively smooth nodular structures, which theoretically impede efficient water transport. In this study, we enhanced the formation of nanobubbles by synergistically regulating with surfactant and low temperatures, resulting in the fabrication of PA NF membranes with a crumpled morphology. We observed that lower temperatures promote enhanced gas solubility in the aqueous phase, facilitating increased nanobubble formation through the foaming effect of surfactant sodium dodecylbenzene sulfonate (SDBS). Consequently, this resulted in the creation of PA NF membranes with more crumpled structures and superior performance, with pure water permeance reaching 36.25 ± 0.42 L m-2 h-1 bar-1, representing an improvement of 14.47 L m-2 h-1 bar-1 compared to the control group. Additionally, it maintains a high Na2SO4 rejection rate of 97.00% ± 0.58%. The PA NF membranes produced by eliminating nanobubbles and free interfaces exhibited a smooth structure, whereas introducing nanobubbles (through NaHCO3 addition, N2 pressurization, and ultrasonication) resulted in the formation of crumpled membranes. This emphasized that the large amount of nanobubbles generated by SDBS and low temperature in the interfacial process played a critical role in shaping crumpled PA NF membranes and enhancing membrane performance. This approach has the potential to provide valuable insights into customizing the structural design of TFC PA NF membranes, contributing to further advancements in this field.
Nanofiltration (NF) technology, with its capacity for nanoscale filtration and controllable selectivity, holds significant promise in diverse applications. However, the current upper bound of permeance and selectivity of NF membranes is intrinsically constrained by the morphology and structure of the polyamide (PA) selective layer. This issue arises because NF membranes typically exhibit relatively smooth nodular structures, which theoretically impede efficient water transport. In this study, we enhanced the formation of nanobubbles by synergistically regulating with surfactant and low temperatures, resulting in the fabrication of PA NF membranes with a crumpled morphology. We observed that lower temperatures promote enhanced gas solubility in the aqueous phase, facilitating increased nanobubble formation through the foaming effect of surfactant sodium dodecylbenzene sulfonate (SDBS). Consequently, this resulted in the creation of PA NF membranes with more crumpled structures and superior performance, with pure water permeance reaching 36.25 ± 0.42 L m-2 h-1 bar-1, representing an improvement of 14.47 L m-2 h-1 bar-1 compared to the control group. Additionally, it maintains a high Na2SO4 rejection rate of 97.00% ± 0.58%. The PA NF membranes produced by eliminating nanobubbles and free interfaces exhibited a smooth structure, whereas introducing nanobubbles (through NaHCO3 addition, N2 pressurization, and ultrasonication) resulted in the formation of crumpled membranes. This emphasized that the large amount of nanobubbles generated by SDBS and low temperature in the interfacial process played a critical role in shaping crumpled PA NF membranes and enhancing membrane performance. This approach has the potential to provide valuable insights into customizing the structural design of TFC PA NF membranes, contributing to further advancements in this field.
2026, 37(1): 111252
doi: 10.1016/j.cclet.2025.111252
摘要:
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms, the laborious syntheses of unsymmetrical 1, 10-phenanthroline-derived diamide ligands (DAPhen) have hindered its extensive study. In this work, we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps (vs. previous 12 steps). A variety of DAPhen ligands are readily available, especially unsymmetrical ones, which give us a platform to systematically study the substituent effect on f-block elements extraction performance. The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO22+ as the representative f-block element. This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen, which paves way for the investigations on their coordination properties with metal ions and other applications.
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms, the laborious syntheses of unsymmetrical 1, 10-phenanthroline-derived diamide ligands (DAPhen) have hindered its extensive study. In this work, we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps (vs. previous 12 steps). A variety of DAPhen ligands are readily available, especially unsymmetrical ones, which give us a platform to systematically study the substituent effect on f-block elements extraction performance. The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO22+ as the representative f-block element. This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen, which paves way for the investigations on their coordination properties with metal ions and other applications.
2026, 37(1): 111253
doi: 10.1016/j.cclet.2025.111253
摘要:
Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO2 reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH2-IS-Co molecular cages for CO2 photoreduction. Experimental results demonstrate that ZrT-1-NH2-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g-1 h-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO2 reduction process. Furthermore, the successful synthesis of ZrT-1-NH2-IS-Ni and ZrT-1-NH2-IS-Mn show the universality of the modification strategies, with their CO2 catalytic activity surpassing that of ZrT-1-NH2.
Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO2 reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH2-IS-Co molecular cages for CO2 photoreduction. Experimental results demonstrate that ZrT-1-NH2-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g-1 h-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO2 reduction process. Furthermore, the successful synthesis of ZrT-1-NH2-IS-Ni and ZrT-1-NH2-IS-Mn show the universality of the modification strategies, with their CO2 catalytic activity surpassing that of ZrT-1-NH2.
2026, 37(1): 111260
doi: 10.1016/j.cclet.2025.111260
摘要:
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species (RSSs) in the thiol-dependent redox systems are crucial in ferroptosis. This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy. However, the traditional techniques, including fluorescent (FL) imaging and electrospray ionization-based mass spectrometry (MS) detection, cannot achieve the discrimination of different RSSs. Herein, simultaneous MS detection of multiple RSSs, including cysteine (Cys), homocysteine (Hcy), glutathione (GSH) and hydrogen sulfide (H2S), was obtained upon enhancing ionization efficiency by a fluorescent probe (NBD-O-1). Based on the interaction between NBD-O-1 and RSSs, the complex of RSSs with a fragment of NBD-O-1 can be generated, which can be easily ionized for MS detection in the negative mode. Therefore, the intracellular RSSs can be well detected upon the incubation of HeLa cells with the probe of NBD-O-1, exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection. Furthermore, the RSSs during ferroptosis in HeLa cells have been evaluated using the present strategy, demonstrating the potential for ferroptosis examinations. This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS, providing significant molecular information for addressing the ferroptosis mechanism.
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species (RSSs) in the thiol-dependent redox systems are crucial in ferroptosis. This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy. However, the traditional techniques, including fluorescent (FL) imaging and electrospray ionization-based mass spectrometry (MS) detection, cannot achieve the discrimination of different RSSs. Herein, simultaneous MS detection of multiple RSSs, including cysteine (Cys), homocysteine (Hcy), glutathione (GSH) and hydrogen sulfide (H2S), was obtained upon enhancing ionization efficiency by a fluorescent probe (NBD-O-1). Based on the interaction between NBD-O-1 and RSSs, the complex of RSSs with a fragment of NBD-O-1 can be generated, which can be easily ionized for MS detection in the negative mode. Therefore, the intracellular RSSs can be well detected upon the incubation of HeLa cells with the probe of NBD-O-1, exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection. Furthermore, the RSSs during ferroptosis in HeLa cells have been evaluated using the present strategy, demonstrating the potential for ferroptosis examinations. This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS, providing significant molecular information for addressing the ferroptosis mechanism.
Beyond superhalogen assembly: Field-driven hyperhalogen design via dual-external-field cooperativity
2026, 37(1): 111265
doi: 10.1016/j.cclet.2025.111265
摘要:
Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Agn− model systems but also in the experimentally synthesized Ag25 nanocluster. Using the 3D Ag19− structure as a model, we further reveal the DEF's pivotal role in O2 activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Agn− model systems but also in the experimentally synthesized Ag25 nanocluster. Using the 3D Ag19− structure as a model, we further reveal the DEF's pivotal role in O2 activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
2026, 37(1): 111270
doi: 10.1016/j.cclet.2025.111270
摘要:
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum (PMS) and Smilax glabra (SGS). The starches were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, high-performance anion-exchange chromatography, and differential scanning calorimetry. Significant differences were observed in their morphological, physicochemical, and functional properties. PMS had a smaller particle size (13.68 µm), irregular polygonal shape, A-type, lower water absorption (62.67%), and higher oil absorption (51.17%). In contrast, SGS exhibited larger particles (31.75 µm), a nearly spherical shape, B-type, higher crystallinity (50.66%), and greater amylose content (21.54%), with superior thermal stability, shear resistance, and gelatinization enthalpy. SGS also contained higher resistant starch (83.28%) and longer average chain length (20.58%), but showed lower solubility, swelling power, light transmittance, and freeze-thaw stability. The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation. These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum (PMS) and Smilax glabra (SGS). The starches were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, high-performance anion-exchange chromatography, and differential scanning calorimetry. Significant differences were observed in their morphological, physicochemical, and functional properties. PMS had a smaller particle size (13.68 µm), irregular polygonal shape, A-type, lower water absorption (62.67%), and higher oil absorption (51.17%). In contrast, SGS exhibited larger particles (31.75 µm), a nearly spherical shape, B-type, higher crystallinity (50.66%), and greater amylose content (21.54%), with superior thermal stability, shear resistance, and gelatinization enthalpy. SGS also contained higher resistant starch (83.28%) and longer average chain length (20.58%), but showed lower solubility, swelling power, light transmittance, and freeze-thaw stability. The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation. These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
2026, 37(1): 111283
doi: 10.1016/j.cclet.2025.111283
摘要:
To enhance the anti-resistance efficacy of our previously disclosed naphthyl-triazine 5, structure-based drug design strategy was rationally conducted to design a series of novel biphenyl-piperidine-triazine-containing non-nucleoside reverse transcriptase inhibitors. Remarkably, several of these compounds demonstrated single-digit nanomolar antiviral potency against both wild-type (WT) human immunodeficiency virus-1 (HIV-1) and five clinically relevant mutant strains. Among these, compound 11s emerged as the most potent inhibitor, showing remarkable efficacy against WT HIV-1 (50% effective concentration (EC50) = 2 nmol/L) and five mutant strains (EC50 = 0.003–0.073 µmol/L), which was significantly superior to that of compound 5. This optimized derivative demonstrated substantially improved pharmacological properties compared to existing drugs etravirine (ETR) and rilpivirine (RPV), showing a 4-fold reduction in cytotoxicity alongside 6-fold enhancement in selectivity index (50% cytotoxic concentration (CC50) = 19.69 µmol/L, selectivity index (SI) = 7438). The compound’s metabolic profile revealed exceptional stability, with an elimination half-life (t1/2 = 41.4 min) more than double that of RPV (t1/2 = 16.03 min). Comprehensive safety evaluation indicated minimal cytochrome P450 (CYP) enzymes interference, low cardiac ion channel activity, and no observable acute toxicity, collectively suggesting a reduced risk profile for therapeutic applications. These promising characteristics significantly advance the development potential of biphenyl-piperidine-triazine derivatives as next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs), offering enhanced efficacy, improved safety, and favorable pharmacokinetic properties for antiretroviral therapy.
To enhance the anti-resistance efficacy of our previously disclosed naphthyl-triazine 5, structure-based drug design strategy was rationally conducted to design a series of novel biphenyl-piperidine-triazine-containing non-nucleoside reverse transcriptase inhibitors. Remarkably, several of these compounds demonstrated single-digit nanomolar antiviral potency against both wild-type (WT) human immunodeficiency virus-1 (HIV-1) and five clinically relevant mutant strains. Among these, compound 11s emerged as the most potent inhibitor, showing remarkable efficacy against WT HIV-1 (50% effective concentration (EC50) = 2 nmol/L) and five mutant strains (EC50 = 0.003–0.073 µmol/L), which was significantly superior to that of compound 5. This optimized derivative demonstrated substantially improved pharmacological properties compared to existing drugs etravirine (ETR) and rilpivirine (RPV), showing a 4-fold reduction in cytotoxicity alongside 6-fold enhancement in selectivity index (50% cytotoxic concentration (CC50) = 19.69 µmol/L, selectivity index (SI) = 7438). The compound’s metabolic profile revealed exceptional stability, with an elimination half-life (t1/2 = 41.4 min) more than double that of RPV (t1/2 = 16.03 min). Comprehensive safety evaluation indicated minimal cytochrome P450 (CYP) enzymes interference, low cardiac ion channel activity, and no observable acute toxicity, collectively suggesting a reduced risk profile for therapeutic applications. These promising characteristics significantly advance the development potential of biphenyl-piperidine-triazine derivatives as next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs), offering enhanced efficacy, improved safety, and favorable pharmacokinetic properties for antiretroviral therapy.
2026, 37(1): 111307
doi: 10.1016/j.cclet.2025.111307
摘要:
Electrochemical CO2 reduction reaction (CO2RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO2 reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO2 on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H2O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO2. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h−1 cm−2 at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h−1 cm−2). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H2O and supply sufficient protons to promote the protonation of CO2 to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
Electrochemical CO2 reduction reaction (CO2RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO2 reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO2 on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H2O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO2. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h−1 cm−2 at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h−1 cm−2). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H2O and supply sufficient protons to promote the protonation of CO2 to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
2026, 37(1): 111308
doi: 10.1016/j.cclet.2025.111308
摘要:
The hydrogen evolution reaction (HER) is a key process in electrocatalytic water splitting for hydrogen production, yet it is often limited by sluggish H*-OH adsorption and H* binding kinetics. We obtained Ru-modified NiO nanoparticles (Ru-NiO/NF) with enhanced HER properties by substituting ruthenium (Ru) for Ni atoms in the NiO (200) crystalline facets on nickel foam by a one-step electrodeposition technique. This novel catalyst exhibits a significantly reduced H*-OH adsorption energy and improved kinetics, with an overpotential of only 60 mV at 10 mA/cm2 and a Tafel slope of 26.19 mV/dec. The Ru-NiO/NF maintains its activity for over 115 h, outperforming NiO/NF by reducing the overpotential by 177 mV. DFT calculations confirm that the addition of Ru to NiO enhances the HER kinetics by modifying the electronic structure, optimizing the surface chemistry, stabilizing the intermediates, lowering the energy barriers, and facilitating efficient charge transfer through a robust three-dimensional structure, resulting in a change in the rate-limiting step and a significant reduction in the Gibbs free energy. This study presents a highly efficient HER catalyst and offers insights into designing advanced NiO-based electrocatalysts by reducing reaction energy barriers.
The hydrogen evolution reaction (HER) is a key process in electrocatalytic water splitting for hydrogen production, yet it is often limited by sluggish H*-OH adsorption and H* binding kinetics. We obtained Ru-modified NiO nanoparticles (Ru-NiO/NF) with enhanced HER properties by substituting ruthenium (Ru) for Ni atoms in the NiO (200) crystalline facets on nickel foam by a one-step electrodeposition technique. This novel catalyst exhibits a significantly reduced H*-OH adsorption energy and improved kinetics, with an overpotential of only 60 mV at 10 mA/cm2 and a Tafel slope of 26.19 mV/dec. The Ru-NiO/NF maintains its activity for over 115 h, outperforming NiO/NF by reducing the overpotential by 177 mV. DFT calculations confirm that the addition of Ru to NiO enhances the HER kinetics by modifying the electronic structure, optimizing the surface chemistry, stabilizing the intermediates, lowering the energy barriers, and facilitating efficient charge transfer through a robust three-dimensional structure, resulting in a change in the rate-limiting step and a significant reduction in the Gibbs free energy. This study presents a highly efficient HER catalyst and offers insights into designing advanced NiO-based electrocatalysts by reducing reaction energy barriers.
2026, 37(1): 111321
doi: 10.1016/j.cclet.2025.111321
摘要:
The first hemiterpene-quassinoid adducts, bruquass A and B (1 and 2), were rapidly isolated and identified from Brucea javanica using an integrated analytical strategy. They possessed unusual carbon skeletons formed by the coupling of quassinoids with hemiterpene units via vinylogous aldol reactions. Their structural configurations were determined through comprehensive spectroscopic analysis and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 were proposed, and guided by these biogenetic insights, the biomimetic synthesis of compound 1 was successfully achieved. Furthermore, compounds 1 and 2 exhibited significant antifeedant activity against Plutella xylostella. The bioactivity assessment results open up the prospects of 1 and 2 as a promising new class of botanical insecticide.
The first hemiterpene-quassinoid adducts, bruquass A and B (1 and 2), were rapidly isolated and identified from Brucea javanica using an integrated analytical strategy. They possessed unusual carbon skeletons formed by the coupling of quassinoids with hemiterpene units via vinylogous aldol reactions. Their structural configurations were determined through comprehensive spectroscopic analysis and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 were proposed, and guided by these biogenetic insights, the biomimetic synthesis of compound 1 was successfully achieved. Furthermore, compounds 1 and 2 exhibited significant antifeedant activity against Plutella xylostella. The bioactivity assessment results open up the prospects of 1 and 2 as a promising new class of botanical insecticide.
2026, 37(1): 111353
doi: 10.1016/j.cclet.2025.111353
摘要:
Two supramolecular organic frameworks (SOFs) have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water. Dynamic light scattering and 1H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature. One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice, which improves by 40% compared with the highest value of the reported SOFs. In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrug-resistant MDR A549/ADR tumor cells to realize intracellular delivery, leading to enhanced antitumor efficacy. Moreover, it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism. As the first examples that undergo room-temperature reversible assembly and disassembly, the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
Two supramolecular organic frameworks (SOFs) have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water. Dynamic light scattering and 1H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature. One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice, which improves by 40% compared with the highest value of the reported SOFs. In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrug-resistant MDR A549/ADR tumor cells to realize intracellular delivery, leading to enhanced antitumor efficacy. Moreover, it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism. As the first examples that undergo room-temperature reversible assembly and disassembly, the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
2026, 37(1): 111385
doi: 10.1016/j.cclet.2025.111385
摘要:
Achieving non-centrosymmetric (NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn2+/Pb2+), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6H11N2PbCl3 exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
Achieving non-centrosymmetric (NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn2+/Pb2+), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6H11N2PbCl3 exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
2026, 37(1): 111415
doi: 10.1016/j.cclet.2025.111415
摘要:
Aqueous zinc-ion batteries (AZIBs) have advantages including low economic cost and high safety. Nevertheless, the serious hydrogen evolution reactions (HER) and rampant growth of Zn dendrite hinder their further development. Herein, potassium acetate (KAc) additive with cation/anion synergy effect is added into the ZnSO4 electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions. According to density functional theory calculation and experimental results, CH3COO− (Ac−) anions are capable of forming stronger hydrogen bonds with H2O molecules, leading to an expanded electrochemical stability window, reduced the reactivity of H2O, and hence suppressing HER. Meanwhile, Ac− anions can also preferentially adsorb onto the Zn anode, promoting dense deposition towards the (100) crystal plane. Besides, dissociated K+ ions serve as electrostatic shielding cations, which significantly promote uniform Zn deposition and prevent dendrite formation. Thus, the ZnZn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 mA/cm2. Furthermore, the ZnMnO2 full battery exhibits superior stability with a capacity retention of 86.95% at 2.0 A/g after 4000 cycles. Therefore, the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
Aqueous zinc-ion batteries (AZIBs) have advantages including low economic cost and high safety. Nevertheless, the serious hydrogen evolution reactions (HER) and rampant growth of Zn dendrite hinder their further development. Herein, potassium acetate (KAc) additive with cation/anion synergy effect is added into the ZnSO4 electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions. According to density functional theory calculation and experimental results, CH3COO− (Ac−) anions are capable of forming stronger hydrogen bonds with H2O molecules, leading to an expanded electrochemical stability window, reduced the reactivity of H2O, and hence suppressing HER. Meanwhile, Ac− anions can also preferentially adsorb onto the Zn anode, promoting dense deposition towards the (100) crystal plane. Besides, dissociated K+ ions serve as electrostatic shielding cations, which significantly promote uniform Zn deposition and prevent dendrite formation. Thus, the ZnZn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 mA/cm2. Furthermore, the ZnMnO2 full battery exhibits superior stability with a capacity retention of 86.95% at 2.0 A/g after 4000 cycles. Therefore, the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
2026, 37(1): 111425
doi: 10.1016/j.cclet.2025.111425
摘要:
Effective treatment of subcutaneous tumors remains a focal point in cancer therapy. Photothermal therapy, a novel therapeutic approach, has emerged as a promising alternative, offering a less invasive option for the treatment of subcutaneous tumors. This study reports the exploration of novel supramolecular halogen-bonded organic frameworks (XOFs) based on [N···Br+···N] halogen bonds through the ligand exchange strategy and their application in photothermal therapy. Through ligand exchange, XOF(Br)-TPy was successfully prepared, and its structure and properties were thoroughly characterized using NMR, XPS, FT-IR, and XRD techniques. Due to their cationic characteristics, these XOFs serve as effective carriers for the photothermal agent IR820. In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation, effectively inducing tumor cell ablation. Furthermore, in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model. This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br) and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
Effective treatment of subcutaneous tumors remains a focal point in cancer therapy. Photothermal therapy, a novel therapeutic approach, has emerged as a promising alternative, offering a less invasive option for the treatment of subcutaneous tumors. This study reports the exploration of novel supramolecular halogen-bonded organic frameworks (XOFs) based on [N···Br+···N] halogen bonds through the ligand exchange strategy and their application in photothermal therapy. Through ligand exchange, XOF(Br)-TPy was successfully prepared, and its structure and properties were thoroughly characterized using NMR, XPS, FT-IR, and XRD techniques. Due to their cationic characteristics, these XOFs serve as effective carriers for the photothermal agent IR820. In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation, effectively inducing tumor cell ablation. Furthermore, in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model. This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br) and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
2026, 37(1): 111450
doi: 10.1016/j.cclet.2025.111450
摘要:
Cisplatin (CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma (NPC). However, serious toxic side effects of CDDP limit patient tolerance and treatment compliance, which urgently needs to be addressed in clinical application. Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility, low toxicity and passive targeting ability. Nevertheless, CDDP's poor water/lipid solubility usually results in a low liposome drug-lipid ratio, limiting tumor delivery ability. Herein, a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously. The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances (gallic acid, epigallocatechin gallate and tannic acid), followed by encapsulation of complex in liposomes to improve tumor targeting. Notably, the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay. In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome (CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency, favorable stability, pH-sensitive release, enhanced cellular uptake and apoptosis effect. In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time, inhibited the growth of tumors, and significantly reduced the toxic side effects compared to CDDP monotherapy. This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
Cisplatin (CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma (NPC). However, serious toxic side effects of CDDP limit patient tolerance and treatment compliance, which urgently needs to be addressed in clinical application. Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility, low toxicity and passive targeting ability. Nevertheless, CDDP's poor water/lipid solubility usually results in a low liposome drug-lipid ratio, limiting tumor delivery ability. Herein, a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously. The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances (gallic acid, epigallocatechin gallate and tannic acid), followed by encapsulation of complex in liposomes to improve tumor targeting. Notably, the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay. In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome (CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency, favorable stability, pH-sensitive release, enhanced cellular uptake and apoptosis effect. In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time, inhibited the growth of tumors, and significantly reduced the toxic side effects compared to CDDP monotherapy. This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
2026, 37(1): 111458
doi: 10.1016/j.cclet.2025.111458
摘要:
Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm2, 0.2 mAh/cm2. Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72% during 500 cycles. Moreover, the full cell Hemin@Zn//NH4V4O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm2, 0.2 mAh/cm2. Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72% during 500 cycles. Moreover, the full cell Hemin@Zn//NH4V4O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
2026, 37(1): 111476
doi: 10.1016/j.cclet.2025.111476
摘要:
Schizophrenia (SCZ) is a severe mental disorder with an unclear pathogenesis. Increasing evidence suggests that oxidative stress (OS) may contribute to the neuropathological processes underlying SCZ. Biothiols, key endogenous antioxidants, have been proposed as potential biomarkers for the disease. However, due to the presence of the blood-brain barrier (BBB), fluorescent probes are rarely used to image biothiols in the brain of SCZ models. In this study, a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties, and carboxylic esters as recognition units. A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes. By introducing trifluoromethyl and benzothiazole groups into the fluorophore, the emission wavelength was successfully shifted into the near-infrared region. Additionally, various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters, thereby improving the probes' reactivity and lipophilicity. Systematic evaluation of the physicochemical characteristics, and optical performance led to the identification of DCI-BT-11 as the most promising candidate. DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo. Notably, DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine (NAC) in the brains of SCZ mouse models, offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
Schizophrenia (SCZ) is a severe mental disorder with an unclear pathogenesis. Increasing evidence suggests that oxidative stress (OS) may contribute to the neuropathological processes underlying SCZ. Biothiols, key endogenous antioxidants, have been proposed as potential biomarkers for the disease. However, due to the presence of the blood-brain barrier (BBB), fluorescent probes are rarely used to image biothiols in the brain of SCZ models. In this study, a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties, and carboxylic esters as recognition units. A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes. By introducing trifluoromethyl and benzothiazole groups into the fluorophore, the emission wavelength was successfully shifted into the near-infrared region. Additionally, various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters, thereby improving the probes' reactivity and lipophilicity. Systematic evaluation of the physicochemical characteristics, and optical performance led to the identification of DCI-BT-11 as the most promising candidate. DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo. Notably, DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine (NAC) in the brains of SCZ mouse models, offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
2026, 37(1): 111486
doi: 10.1016/j.cclet.2025.111486
摘要:
By using carbohydrates as the biomass carbon sources, Se/C materials could be easily prepared. The materials could catalyze the oxidative deoximation reactions, which are significant transformations in both pharmaceutical industry and fine chemical production. Compared with the reported organoselenium-catalyzed ionic reactions, the Se/C-catalyzed deoximation reactions occurred via unique free radical mechanisms, endowing the Se species high catalytic reactivity. The Se/C catalysts were recyclable and their turnover numbers (TONs) were high (>104), making the reactions practical for industrial grade preparation. The unique free radical mechanisms of the reaction and green and practical features of the catalysts are the characteristics and advantages of the work.
By using carbohydrates as the biomass carbon sources, Se/C materials could be easily prepared. The materials could catalyze the oxidative deoximation reactions, which are significant transformations in both pharmaceutical industry and fine chemical production. Compared with the reported organoselenium-catalyzed ionic reactions, the Se/C-catalyzed deoximation reactions occurred via unique free radical mechanisms, endowing the Se species high catalytic reactivity. The Se/C catalysts were recyclable and their turnover numbers (TONs) were high (>104), making the reactions practical for industrial grade preparation. The unique free radical mechanisms of the reaction and green and practical features of the catalysts are the characteristics and advantages of the work.
2026, 37(1): 111500
doi: 10.1016/j.cclet.2025.111500
摘要:
The detection of amino acid enantiomers holds significant importance in biomedical, chemical, food, and other fields. Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes, which can compromise accuracy and repeatability. In this study, we report a novel fluorescent probe (R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths (> 60 nm). This water-soluble probe (R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers, enabling reliable chiral detection of 14 natural amino acids. It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color. Additionally, a logic operation with two inputs and three outputs was constructed based on these optical properties. Notably, amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels. This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
The detection of amino acid enantiomers holds significant importance in biomedical, chemical, food, and other fields. Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes, which can compromise accuracy and repeatability. In this study, we report a novel fluorescent probe (R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths (> 60 nm). This water-soluble probe (R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers, enabling reliable chiral detection of 14 natural amino acids. It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color. Additionally, a logic operation with two inputs and three outputs was constructed based on these optical properties. Notably, amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels. This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
2026, 37(1): 111520
doi: 10.1016/j.cclet.2025.111520
摘要:
Metal-support interaction (MSI) is crucial for fine-tuning the active-site structure of supported catalysts and enhancing performance. Here, we present an ammonia-directed reactive gas-metal-support interaction (RGMSI), in which NH3 reduces ZnO and assembles an anti-perovskite Ni3ZnN structure with interstitial nitrogen, significantly boosting hydrogenation efficiency. Nitrogen incorporation expands the lattice parameter, increasing the (111) lattice spacing from 2.04 Å in Ni to 2.18 Å in Ni3ZnN, with an extended Ni-Ni interatomic distance from 2.49 Å to 2.65 Å. Additionally, Ni-N coordination shifts the d-band center downward and induces electron deficiency in Ni via charge transfer. These modifications optimize reactant adsorption on the tailored Ni3ZnN structure compared to Ni, leading to a remarkable increase in 1,3-butadiene hydrogenation selectivity from 30.0% to 92.9%, along with an enhanced TOF from 0.067 s−1 to 0.079 s−1. These findings highlight RGMSI as a versatile and effective strategy for designing supported metal catalysts, offering new insights into selective hydrogenation catalysis.
Metal-support interaction (MSI) is crucial for fine-tuning the active-site structure of supported catalysts and enhancing performance. Here, we present an ammonia-directed reactive gas-metal-support interaction (RGMSI), in which NH3 reduces ZnO and assembles an anti-perovskite Ni3ZnN structure with interstitial nitrogen, significantly boosting hydrogenation efficiency. Nitrogen incorporation expands the lattice parameter, increasing the (111) lattice spacing from 2.04 Å in Ni to 2.18 Å in Ni3ZnN, with an extended Ni-Ni interatomic distance from 2.49 Å to 2.65 Å. Additionally, Ni-N coordination shifts the d-band center downward and induces electron deficiency in Ni via charge transfer. These modifications optimize reactant adsorption on the tailored Ni3ZnN structure compared to Ni, leading to a remarkable increase in 1,3-butadiene hydrogenation selectivity from 30.0% to 92.9%, along with an enhanced TOF from 0.067 s−1 to 0.079 s−1. These findings highlight RGMSI as a versatile and effective strategy for designing supported metal catalysts, offering new insights into selective hydrogenation catalysis.
2026, 37(1): 111551
doi: 10.1016/j.cclet.2025.111551
摘要:
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes (PLEDs). Herein, we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors (PG and PDG) via metal-free CN coupling polymerization for the fabrication of deep-blue PLEDs. The steric, rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state. Due to the different length of electron-deficient diphenyl sulfone monomers, PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films. Interestingly, similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation. Finally, PLEDs based on PG are fabricated with a stable deep-blue emission of CIE (0.15, 0.10), and corresponding EL spectral profile is also completely identical to PL ones of diluted solution, revealed the intrachain emission without obvious interchain excited state, confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes (PLEDs). Herein, we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors (PG and PDG) via metal-free CN coupling polymerization for the fabrication of deep-blue PLEDs. The steric, rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state. Due to the different length of electron-deficient diphenyl sulfone monomers, PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films. Interestingly, similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation. Finally, PLEDs based on PG are fabricated with a stable deep-blue emission of CIE (0.15, 0.10), and corresponding EL spectral profile is also completely identical to PL ones of diluted solution, revealed the intrachain emission without obvious interchain excited state, confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
2026, 37(1): 111582
doi: 10.1016/j.cclet.2025.111582
摘要:
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
2026, 37(1): 111609
doi: 10.1016/j.cclet.2025.111609
摘要:
Despite demonstrating significant anti-tumor potential as an artemisinin derivative, artesunate faces delivery efficiency challenges due to low water solubility and insufficient targeting specificity. To improve the delivery efficiency, we engineered three artesunate (ART) derivatives, AC15-L (linear), AC15-B (branched), and AC15-C (cyclic) with distinct aliphatic chain architectures. Unexpectedly, we observed that AC15-C exhibited superior cytotoxicity against 4T1 breast cancer cells, and had the highest binding affinity for Lon protease 1 (LONP1) (−72.6 kcal/mol). Subsequently, disulfide bond-containing lipid-PEG (DSPE-SS-PEG2K) modified chain architecture-engineered ART derivatives nanoassemblies (NAs) were developed to mitigate solubility-related limitations while enhancing targeting precision. Molecular docking and experimental validation demonstrated that ART derivatives inhibited LONP1 through hydrophobic interactions while preserved Fe2+-mediated Fenton-like reaction activity. In vitro and in vivo evaluations demonstrated that AC15-C NAs outperformed free ART and other NAs, suppressing 4T1 tumor growth via dual action: LONP1-directed mitochondrial proteostasis collapse and reactive oxygen species (ROS) amplification through Fe2+-ART interactions. This study elucidated a novel anti-tumor mechanism of ART through the rational design of derivatives with spatially configured aliphatic chains, and developed reduction-responsive NAs to provide an advanced delivery strategy.
Despite demonstrating significant anti-tumor potential as an artemisinin derivative, artesunate faces delivery efficiency challenges due to low water solubility and insufficient targeting specificity. To improve the delivery efficiency, we engineered three artesunate (ART) derivatives, AC15-L (linear), AC15-B (branched), and AC15-C (cyclic) with distinct aliphatic chain architectures. Unexpectedly, we observed that AC15-C exhibited superior cytotoxicity against 4T1 breast cancer cells, and had the highest binding affinity for Lon protease 1 (LONP1) (−72.6 kcal/mol). Subsequently, disulfide bond-containing lipid-PEG (DSPE-SS-PEG2K) modified chain architecture-engineered ART derivatives nanoassemblies (NAs) were developed to mitigate solubility-related limitations while enhancing targeting precision. Molecular docking and experimental validation demonstrated that ART derivatives inhibited LONP1 through hydrophobic interactions while preserved Fe2+-mediated Fenton-like reaction activity. In vitro and in vivo evaluations demonstrated that AC15-C NAs outperformed free ART and other NAs, suppressing 4T1 tumor growth via dual action: LONP1-directed mitochondrial proteostasis collapse and reactive oxygen species (ROS) amplification through Fe2+-ART interactions. This study elucidated a novel anti-tumor mechanism of ART through the rational design of derivatives with spatially configured aliphatic chains, and developed reduction-responsive NAs to provide an advanced delivery strategy.
2026, 37(1): 111622
doi: 10.1016/j.cclet.2025.111622
摘要:
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells (OSCs) based on non-fused ring electron acceptors (NFREAs). However, research on the impact of fluorination positions at side chains on NFREAs device performance remains scant. In this study, we introduce two isomeric NFREAs, designated as GA-2F-E and GA-2F, distinguished by their fluorination positions at the side chains. Both NFREAs share a thiophene[3,2-b]thiophene core, but their side chains differ: GA-2F-E features two (4-butylphenyl)-N-(4-fluorophenyl) amino groups, whereas GA-2F’s side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core. To delve into the influence of fluorination positions on the optoelectronic properties, aggregation behavior, and overall efficiency of the acceptor molecules, a comprehensive investigation was conducted. The findings reveal that, despite similar photophysical properties and comparable absorption bandwidths, GA-2F-E, with fluorine atoms positioned on both sides of the molecular framework, demonstrates more compact π-π stacking, reduced bimolecular recombination, superior exciton transport, and a more balanced, higher mobility. As a result of these advantages, OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency (PCE) of 16.45%, surpassing the 15.83% PCE of devices utilizing D18:GA-2F. This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance, paving the way for the development of more efficient NFREAs.
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells (OSCs) based on non-fused ring electron acceptors (NFREAs). However, research on the impact of fluorination positions at side chains on NFREAs device performance remains scant. In this study, we introduce two isomeric NFREAs, designated as GA-2F-E and GA-2F, distinguished by their fluorination positions at the side chains. Both NFREAs share a thiophene[3,2-b]thiophene core, but their side chains differ: GA-2F-E features two (4-butylphenyl)-N-(4-fluorophenyl) amino groups, whereas GA-2F’s side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core. To delve into the influence of fluorination positions on the optoelectronic properties, aggregation behavior, and overall efficiency of the acceptor molecules, a comprehensive investigation was conducted. The findings reveal that, despite similar photophysical properties and comparable absorption bandwidths, GA-2F-E, with fluorine atoms positioned on both sides of the molecular framework, demonstrates more compact π-π stacking, reduced bimolecular recombination, superior exciton transport, and a more balanced, higher mobility. As a result of these advantages, OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency (PCE) of 16.45%, surpassing the 15.83% PCE of devices utilizing D18:GA-2F. This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance, paving the way for the development of more efficient NFREAs.
2026, 37(1): 111623
doi: 10.1016/j.cclet.2025.111623
摘要:
Field-effect nanofluidic transistors (FENTs), biomimicking the structure and functionality of neuron, act as biological transistors with the ability to gate switching responses to external stimuli. The switching ratio has been verified to evaluate the performance of FENTs, but until recently, the response time, another crucial indicator, has been ignored. Employing finite-element method, we investigated the relationship among gate charge, switching ratio and response time by divisionally manipulating gate charge, including entrance surface and the surface of confinement space, for ion transport to optimize switching capability. The dual-split gate charge on FENTs exhibits synergistic effect on switching response. Based on the two regional gate charge on FENTs, multivalence ions in lower concentration, high aspect ratio and single channel show higher switching ratio but longer response time compared to monovalent ions. The findings highlight the necessity of balancing these two signals in FENTs and offer insights for optimizing their design and expanding applications to dual-signal-detection iontronics.
Field-effect nanofluidic transistors (FENTs), biomimicking the structure and functionality of neuron, act as biological transistors with the ability to gate switching responses to external stimuli. The switching ratio has been verified to evaluate the performance of FENTs, but until recently, the response time, another crucial indicator, has been ignored. Employing finite-element method, we investigated the relationship among gate charge, switching ratio and response time by divisionally manipulating gate charge, including entrance surface and the surface of confinement space, for ion transport to optimize switching capability. The dual-split gate charge on FENTs exhibits synergistic effect on switching response. Based on the two regional gate charge on FENTs, multivalence ions in lower concentration, high aspect ratio and single channel show higher switching ratio but longer response time compared to monovalent ions. The findings highlight the necessity of balancing these two signals in FENTs and offer insights for optimizing their design and expanding applications to dual-signal-detection iontronics.
2026, 37(1): 111659
doi: 10.1016/j.cclet.2025.111659
摘要:
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction (OER). However, the correlation among catalyst structure, magnetic property, and magnetic field enhanced-electrochemical activity remains to be fully elucidated. Herein, single-domain CoFe2O4 catalysts with tunable oxygen vacancies (CFO-VO) were synthesized to probe how VO mediates magnetism and OER activity under magnetic field. The introduction of VO can simultaneously modulate saturation magnetization (Ms) and coercivity (Hc), where the increased Ms dominates the magnetic field-enhanced OER activity. Under a 14,000 G magnetic field, the optimized CFO-VO exhibits up to 16.1% reduction in overpotential and 365% enhancement in magnetocurrent (MC). Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction, magnetohydrodynamic effect, and spin charge transfer effect. Importantly, the magnetic field promotes additional Co3+ generation to compensate for charge imbalance caused by VO filling, maintaining dynamic equilibrium of VO and effective reactant adsorption-conversion processes. This work unveils the synergistic mechanism of VO and magnetic parameters for enhancing OER performance under the magnetic field, providing new insights into the design of high-efficiency spin-regulated OER catalysts.
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction (OER). However, the correlation among catalyst structure, magnetic property, and magnetic field enhanced-electrochemical activity remains to be fully elucidated. Herein, single-domain CoFe2O4 catalysts with tunable oxygen vacancies (CFO-VO) were synthesized to probe how VO mediates magnetism and OER activity under magnetic field. The introduction of VO can simultaneously modulate saturation magnetization (Ms) and coercivity (Hc), where the increased Ms dominates the magnetic field-enhanced OER activity. Under a 14,000 G magnetic field, the optimized CFO-VO exhibits up to 16.1% reduction in overpotential and 365% enhancement in magnetocurrent (MC). Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction, magnetohydrodynamic effect, and spin charge transfer effect. Importantly, the magnetic field promotes additional Co3+ generation to compensate for charge imbalance caused by VO filling, maintaining dynamic equilibrium of VO and effective reactant adsorption-conversion processes. This work unveils the synergistic mechanism of VO and magnetic parameters for enhancing OER performance under the magnetic field, providing new insights into the design of high-efficiency spin-regulated OER catalysts.
2026, 37(1): 111660
doi: 10.1016/j.cclet.2025.111660
摘要:
Structural instability and sluggish lithium-ion (Li+) kinetics of spinel NiCo2O4 anodes severely hinder their applications in high-energy-density lithium-ion batteries. Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics. However, their controlled synthesis mechanisms remain elusive. Herein, a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo2O4 nanorods. Remarkably, mesocrystalline NiCo2O4 exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g, attributed to its porous structure facilitating Li+ transport kinetics and unique stress-buffering effect validated by ex-situ TEM. Theoretical calculations and interfacial chemical analysis reveal that substrate-crystal surface engineering regulates the nucleation-growth pathways: Acid-treated nickel foam enables epitaxial growth via lattice matching, acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization. In contrast, carbon cloth requires high-temperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy. This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis. The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
Structural instability and sluggish lithium-ion (Li+) kinetics of spinel NiCo2O4 anodes severely hinder their applications in high-energy-density lithium-ion batteries. Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics. However, their controlled synthesis mechanisms remain elusive. Herein, a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo2O4 nanorods. Remarkably, mesocrystalline NiCo2O4 exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g, attributed to its porous structure facilitating Li+ transport kinetics and unique stress-buffering effect validated by ex-situ TEM. Theoretical calculations and interfacial chemical analysis reveal that substrate-crystal surface engineering regulates the nucleation-growth pathways: Acid-treated nickel foam enables epitaxial growth via lattice matching, acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization. In contrast, carbon cloth requires high-temperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy. This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis. The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
2026, 37(1): 111679
doi: 10.1016/j.cclet.2025.111679
摘要:
In this study, electrochemical C-H carboxylation of benzylamines with CO2 was reported. This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids (α-AAs) under mild conditions. Various substituted benzylamines containing diverse functional groups and even highly reactive moieties, such as cyano, amide and alkene groups could be successfully transformed to the carboxylated products. Notably, this method proved to be applicable to the late-stage modification of biorelevant compounds, highlighting its potential for synthetic chemistry. Mechanistic studies such as radical trapping experiments, kinetic isotope effect (KIE) tests and cyclic voltammetry (CV) studies provided useful insight into this transformation.
In this study, electrochemical C-H carboxylation of benzylamines with CO2 was reported. This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids (α-AAs) under mild conditions. Various substituted benzylamines containing diverse functional groups and even highly reactive moieties, such as cyano, amide and alkene groups could be successfully transformed to the carboxylated products. Notably, this method proved to be applicable to the late-stage modification of biorelevant compounds, highlighting its potential for synthetic chemistry. Mechanistic studies such as radical trapping experiments, kinetic isotope effect (KIE) tests and cyclic voltammetry (CV) studies provided useful insight into this transformation.
2026, 37(1): 111721
doi: 10.1016/j.cclet.2025.111721
摘要:
Thermally activated delayed fluorescence (TADF) emitters show great potential in photodynamic therapy (PDT) and bioimaging, leveraging their structural adaptability, efficient reverse intersystem crossing (RISC), robust photosensitizing capability, and high photoluminescence quantum yields (PLQYs). Herein, we developed a new class of donor–acceptor–donor (D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine, phenothiazine and 9,9-dimethyl-9,10-dihydroacridine. These materials exhibit enhanced TADF properties, aggregation-induced emission (AIE), alongside high reactive oxygen species (ROS) generation efficiency, effectively mitigating aggregation-caused quenching observed in traditional fluorophores. Among them, IDP-p-PXZ, incorporating the phenoxazine donor, stands out with the smallest singlet–triplet splitting energy (ΔEST) and the highest spin-orbit coupling matrix elements (SOCMEs). Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) nanoparticles (NPs), IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air, an exceptionally fast intersystem crossing (ISC) rate constant (kISC) of 3.4 × 107 s−1, and a radiative rate constant (kr) of 5.05 × 106 s−1. These NPs exhibit superior biocompatibility, efficient cellular internalization, and potent ROS production, enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
Thermally activated delayed fluorescence (TADF) emitters show great potential in photodynamic therapy (PDT) and bioimaging, leveraging their structural adaptability, efficient reverse intersystem crossing (RISC), robust photosensitizing capability, and high photoluminescence quantum yields (PLQYs). Herein, we developed a new class of donor–acceptor–donor (D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine, phenothiazine and 9,9-dimethyl-9,10-dihydroacridine. These materials exhibit enhanced TADF properties, aggregation-induced emission (AIE), alongside high reactive oxygen species (ROS) generation efficiency, effectively mitigating aggregation-caused quenching observed in traditional fluorophores. Among them, IDP-p-PXZ, incorporating the phenoxazine donor, stands out with the smallest singlet–triplet splitting energy (ΔEST) and the highest spin-orbit coupling matrix elements (SOCMEs). Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) nanoparticles (NPs), IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air, an exceptionally fast intersystem crossing (ISC) rate constant (kISC) of 3.4 × 107 s−1, and a radiative rate constant (kr) of 5.05 × 106 s−1. These NPs exhibit superior biocompatibility, efficient cellular internalization, and potent ROS production, enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
2026, 37(1): 111724
doi: 10.1016/j.cclet.2025.111724
摘要:
Herein, we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires (NWs), including PdPt NWs, PdAu NWs, PdIr NWs, and PdRu NWs, which exhibits high mass activity and turnover frequency (TOF) for HER, surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes, respectively. It also demonstrates high stability in alkaline electrolyte at a current density of 220 mA/cm2 for 280 h, highlighting its potential for practical applications under industrial current conditions. PdPt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects, significantly increasing the density of active sites and precisely tuning the electronic structure, which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance. This study highlights the potential of PdPt NWs as highly efficient catalysts, offering outstanding catalytic performance and stability for practical applications.
Herein, we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires (NWs), including PdPt NWs, PdAu NWs, PdIr NWs, and PdRu NWs, which exhibits high mass activity and turnover frequency (TOF) for HER, surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes, respectively. It also demonstrates high stability in alkaline electrolyte at a current density of 220 mA/cm2 for 280 h, highlighting its potential for practical applications under industrial current conditions. PdPt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects, significantly increasing the density of active sites and precisely tuning the electronic structure, which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance. This study highlights the potential of PdPt NWs as highly efficient catalysts, offering outstanding catalytic performance and stability for practical applications.
2026, 37(1): 111736
doi: 10.1016/j.cclet.2025.111736
摘要:
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like arene-perfluoroarene (AP) interactions offers an effective approach for fabricating chiral functional materials. Herein, chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene (OFN) through AP interaction were systemically studied. The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism (CD) and circularly polarized luminescence (CPL) signals. Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved. Besides, no significant CPL signal was observed in the self-assembly of L/D-PF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction. Notably, a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN, indicating that that minor structural changes of molecules could cause large changes in assembly. In addition, a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN. This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer, chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like arene-perfluoroarene (AP) interactions offers an effective approach for fabricating chiral functional materials. Herein, chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene (OFN) through AP interaction were systemically studied. The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism (CD) and circularly polarized luminescence (CPL) signals. Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved. Besides, no significant CPL signal was observed in the self-assembly of L/D-PF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction. Notably, a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN, indicating that that minor structural changes of molecules could cause large changes in assembly. In addition, a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN. This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer, chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
2026, 37(1): 111740
doi: 10.1016/j.cclet.2025.111740
摘要:
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones, the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner. In addition, the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones, the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner. In addition, the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
2026, 37(1): 111741
doi: 10.1016/j.cclet.2025.111741
摘要:
The photocatalytic oxidation of methane (CH4) to valuable chemicals like low alcohols (CH3OH and C2H5OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g−1 h−1 and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
The photocatalytic oxidation of methane (CH4) to valuable chemicals like low alcohols (CH3OH and C2H5OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g−1 h−1 and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
2026, 37(1): 111756
doi: 10.1016/j.cclet.2025.111756
摘要:
The three-dimensional (3D) Pd-based nanoflower structures, assembled from two-dimensional (2D) nanosheets, are characterized by their stable and ordered configurations. These structures have been extensively designed as anode materials for fuel cells. However, the exploration of trimetallic nanoflowers with porous architectures remains limited. In this study, we present a straightforward one-step solvothermal method for the synthesis of trimetallic PdCuNi porous nanoflowers (PNFs). Leveraging several unique advantages, such as an open superstructure, high porosity, and enhanced electronic interactions among the trimetals, the resulting PdCuNi PNFs demonstrate significantly improved electrochemical performance, with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR), respectively. Furthermore, the PdCuNi PNFs exhibit optimized d-band centers and the most negative onset oxidation potential, indicating enhanced antitoxicity and stability. This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
The three-dimensional (3D) Pd-based nanoflower structures, assembled from two-dimensional (2D) nanosheets, are characterized by their stable and ordered configurations. These structures have been extensively designed as anode materials for fuel cells. However, the exploration of trimetallic nanoflowers with porous architectures remains limited. In this study, we present a straightforward one-step solvothermal method for the synthesis of trimetallic PdCuNi porous nanoflowers (PNFs). Leveraging several unique advantages, such as an open superstructure, high porosity, and enhanced electronic interactions among the trimetals, the resulting PdCuNi PNFs demonstrate significantly improved electrochemical performance, with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR), respectively. Furthermore, the PdCuNi PNFs exhibit optimized d-band centers and the most negative onset oxidation potential, indicating enhanced antitoxicity and stability. This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
2026, 37(1): 111779
doi: 10.1016/j.cclet.2025.111779
摘要:
α-Chiral amides are common in pharmaceuticals, agrochemicals, natural products, and peptides, prompting the need for new synthetic methods. Here, we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesize α-chiral amides from benzyl ammonium salts and isocyanates. The key to success is using a chiral 2,2′-bipyridine ligand (-)-Ph-SBpy, enabling high yield (up to 95%) and enantiomeric ratio (up to 98:2 er) under mild conditions. Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate, enhancing selectivity and efficiency. The synthetic utility is showcased through transformations of the enantioenriched amides, and the mechanism and enantioselectivity are supported by experimental and computational studies.
α-Chiral amides are common in pharmaceuticals, agrochemicals, natural products, and peptides, prompting the need for new synthetic methods. Here, we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesize α-chiral amides from benzyl ammonium salts and isocyanates. The key to success is using a chiral 2,2′-bipyridine ligand (-)-Ph-SBpy, enabling high yield (up to 95%) and enantiomeric ratio (up to 98:2 er) under mild conditions. Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate, enhancing selectivity and efficiency. The synthetic utility is showcased through transformations of the enantioenriched amides, and the mechanism and enantioselectivity are supported by experimental and computational studies.
2026, 37(1): 111787
doi: 10.1016/j.cclet.2025.111787
摘要:
In the field of organic solar cells (OSCs), side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors (SMAs), which could adjust the material solubility and modulate the intermolecular stacking properties, profoundly impacting the film morphology and thus acting on the final power conversion efficiency (PCE) of the materials. In this study, two asymmetric acceptor molecules, Qx-PhBr-BO and Qx-PhBr-X, were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site. The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior, giving rise to redshifted absorption and tight π-π stacking. Morphology analysis shows that the Qx-PhBr-X-based devices have smoother surfaces and a phase-separated structure, which is more favorable for charge transport and extraction. The Qx-PhBr-X-based devices exhibit balanced hole-electron mobility, efficient exciton dissociation, and low charge recombination. As a result, Qx-PhBr-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16%, which is significantly higher than that of Qx-PhBr-BO at 16.28%. These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
In the field of organic solar cells (OSCs), side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors (SMAs), which could adjust the material solubility and modulate the intermolecular stacking properties, profoundly impacting the film morphology and thus acting on the final power conversion efficiency (PCE) of the materials. In this study, two asymmetric acceptor molecules, Qx-PhBr-BO and Qx-PhBr-X, were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site. The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior, giving rise to redshifted absorption and tight π-π stacking. Morphology analysis shows that the Qx-PhBr-X-based devices have smoother surfaces and a phase-separated structure, which is more favorable for charge transport and extraction. The Qx-PhBr-X-based devices exhibit balanced hole-electron mobility, efficient exciton dissociation, and low charge recombination. As a result, Qx-PhBr-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16%, which is significantly higher than that of Qx-PhBr-BO at 16.28%. These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
2026, 37(1): 111804
doi: 10.1016/j.cclet.2025.111804
摘要:
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
2026, 37(1): 111806
doi: 10.1016/j.cclet.2025.111806
摘要:
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
2026, 37(1): 111826
doi: 10.1016/j.cclet.2025.111826
摘要:
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
2026, 37(1): 111926
doi: 10.1016/j.cclet.2025.111926
摘要:
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
2026, 37(1): 111930
doi: 10.1016/j.cclet.2025.111930
摘要:
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
2026, 37(1): 110967
doi: 10.1016/j.cclet.2025.110967
摘要:
Detecting biomarkers in body fluids by optical lateral flow immune assay (LFIA) technology provides rapid access to disease information for early diagnosis. LFIA is based on an antigen-antibody reaction and is rapidly becoming the preferred choice of physicians and patients for point-of-care testing due to its simplicity, cost-effectiveness, and rapid detection. Observing the optical signal change from the colloidal gold of the traditional LFIA strip has been widely applied for various biomarkers detection in body fluids. Despite the significant progress, rapid real-time detection of color changes in the colloidal gold by the naked eye still faces many limitations, such as large errors and the inability to quantify and accurately detect. New optical LFIA strip technology has emerged in recent years to extend its application scenarios for achieving quantitative detection such as fluorescence, afterglow, and chemiluminescence. Herein, we summarized the development of optical LFIA technology from single to hyphenated optical signals for biomarkers detection in body fluids from invasive and non-invasive sources. Moreover, the challenge and outlook of optical LFIA strip technology are highlighted to inspire the designing of next-generation diagnostic platforms.
Detecting biomarkers in body fluids by optical lateral flow immune assay (LFIA) technology provides rapid access to disease information for early diagnosis. LFIA is based on an antigen-antibody reaction and is rapidly becoming the preferred choice of physicians and patients for point-of-care testing due to its simplicity, cost-effectiveness, and rapid detection. Observing the optical signal change from the colloidal gold of the traditional LFIA strip has been widely applied for various biomarkers detection in body fluids. Despite the significant progress, rapid real-time detection of color changes in the colloidal gold by the naked eye still faces many limitations, such as large errors and the inability to quantify and accurately detect. New optical LFIA strip technology has emerged in recent years to extend its application scenarios for achieving quantitative detection such as fluorescence, afterglow, and chemiluminescence. Herein, we summarized the development of optical LFIA technology from single to hyphenated optical signals for biomarkers detection in body fluids from invasive and non-invasive sources. Moreover, the challenge and outlook of optical LFIA strip technology are highlighted to inspire the designing of next-generation diagnostic platforms.
2026, 37(1): 111120
doi: 10.1016/j.cclet.2025.111120
摘要:
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
2026, 37(1): 111183
doi: 10.1016/j.cclet.2025.111183
摘要:
Antibiotic resistance genes (ARGs) are recognized as a primary threat to the sustainability of environment and human health in the 21st century. Nanomaterials (NMs) have attracted substantial attention due to their unique dimensions and structures. Unfortunately, emerging evidence suggests that NMs may facilitate the transmission of ARGs. It is crucial to elucidate how NMs affect the evolution and dissemination of ARGs. The current review comprehensively examines the role of NMs in the widespread transmission of ARGs in aquatic environments and the underlying mechanisms involved in the process. It aims to clarify the effects and mechanisms of NMs on the horizontal gene transfer processes that are associated with ARGs, including the enhancement of cell membrane permeability, the formation of nanopores on membranes, promotion of mutagenesis, and the generation of reactive oxygen species (ROSs). Furthermore, the trade-off between the removal of ARGs and horizontal transfer has been elucidated. The review aspires to guide future research directions, advance knowledge on the implications of NMs in the field of ARGs' transmission, and provide a theoretical foundation for the development of safer and more effective applications of NMs.
Antibiotic resistance genes (ARGs) are recognized as a primary threat to the sustainability of environment and human health in the 21st century. Nanomaterials (NMs) have attracted substantial attention due to their unique dimensions and structures. Unfortunately, emerging evidence suggests that NMs may facilitate the transmission of ARGs. It is crucial to elucidate how NMs affect the evolution and dissemination of ARGs. The current review comprehensively examines the role of NMs in the widespread transmission of ARGs in aquatic environments and the underlying mechanisms involved in the process. It aims to clarify the effects and mechanisms of NMs on the horizontal gene transfer processes that are associated with ARGs, including the enhancement of cell membrane permeability, the formation of nanopores on membranes, promotion of mutagenesis, and the generation of reactive oxygen species (ROSs). Furthermore, the trade-off between the removal of ARGs and horizontal transfer has been elucidated. The review aspires to guide future research directions, advance knowledge on the implications of NMs in the field of ARGs' transmission, and provide a theoretical foundation for the development of safer and more effective applications of NMs.
2026, 37(1): 111232
doi: 10.1016/j.cclet.2025.111232
摘要:
The development of highly effective therapeutics is a priority in addressing the escalating threat that cancer poses to human health. Cyclodextrins (CDs) with exceptional biocompatibility and devisable structural hierarchy are emerging as versatile building blocks for engineered drug delivery systems, showing a promising prospect in cancer therapy. CDs enable precise synthesis of functionalized polymers with tailored architectures, endowing their excellent stability and large surface area to prolong drug circulation, enhance solubility, and increase targeting efficiency. Recently, CD-based nanotherapeutics has shown transformative potential in chemotherapy, phototherapy, immunotherapy, gene therapy and other co-delivery systems of combination therapy. This review will introduce the types of CD-based nanotherapeutics, systematically summarize their design methods and anticancer application, and further discuss the prospects and challenges, providing a roadmap for advancing CD nanotechnology toward cancer therapeutics.
The development of highly effective therapeutics is a priority in addressing the escalating threat that cancer poses to human health. Cyclodextrins (CDs) with exceptional biocompatibility and devisable structural hierarchy are emerging as versatile building blocks for engineered drug delivery systems, showing a promising prospect in cancer therapy. CDs enable precise synthesis of functionalized polymers with tailored architectures, endowing their excellent stability and large surface area to prolong drug circulation, enhance solubility, and increase targeting efficiency. Recently, CD-based nanotherapeutics has shown transformative potential in chemotherapy, phototherapy, immunotherapy, gene therapy and other co-delivery systems of combination therapy. This review will introduce the types of CD-based nanotherapeutics, systematically summarize their design methods and anticancer application, and further discuss the prospects and challenges, providing a roadmap for advancing CD nanotechnology toward cancer therapeutics.
2026, 37(1): 111249
doi: 10.1016/j.cclet.2025.111249
摘要:
The escalating global issues of water scarcity and pollution emphasize the critical need for the rapid development of efficient and eco-friendly water treatment technologies. Photoelectrocatalytic technology has emerged as a promising solution for effectively degrading refractory organic pollutants in water under light conditions. This review delves into the advancements made in the field, focusing on strategies to enhance the generation of active species by modulating the micro-interface of the photoanode. Strategies, such as morphological control, element doping, introduction of surface oxygen vacancies, and construction of heterostructures, significantly improve the separation efficiency of photogenerated charges and the generation of active species, thereby boosting the efficiency of photoelectrocatalytic performance. Furthermore, the review explores the potential applications of photoelectrocatalytic technology in organic pollutant degradation in solutions. It also outlines the current challenges and future development directions. Despite its remarkable laboratory success, practical implementation of photoelectrocatalytic technology encounters obstacles related to stability, cost-effectiveness, and operational efficiency. Future investigations need to focus on optimizing the performance of photoelectrocatalytic materials and exploring strategies for upscaling their application in real water treatment scenarios.
The escalating global issues of water scarcity and pollution emphasize the critical need for the rapid development of efficient and eco-friendly water treatment technologies. Photoelectrocatalytic technology has emerged as a promising solution for effectively degrading refractory organic pollutants in water under light conditions. This review delves into the advancements made in the field, focusing on strategies to enhance the generation of active species by modulating the micro-interface of the photoanode. Strategies, such as morphological control, element doping, introduction of surface oxygen vacancies, and construction of heterostructures, significantly improve the separation efficiency of photogenerated charges and the generation of active species, thereby boosting the efficiency of photoelectrocatalytic performance. Furthermore, the review explores the potential applications of photoelectrocatalytic technology in organic pollutant degradation in solutions. It also outlines the current challenges and future development directions. Despite its remarkable laboratory success, practical implementation of photoelectrocatalytic technology encounters obstacles related to stability, cost-effectiveness, and operational efficiency. Future investigations need to focus on optimizing the performance of photoelectrocatalytic materials and exploring strategies for upscaling their application in real water treatment scenarios.
2026, 37(1): 111273
doi: 10.1016/j.cclet.2025.111273
摘要:
Chitosan (CS), a natural polymer derived from chitin found in the exoskeletons of crustaceans, has garnered significant interest in the pharmaceutical field due to its unique properties, including biocompatibility and biodegradability. In recent years, various studies have reported that CS can affect drug bioavailability, and interestingly, it works as an oral absorption enhancer and inhibitor. This review offers an in-depth analysis of the mechanisms underlying such a phenomenon and supports its application as a pharmaceutical excipient. CS enhances oral drug absorption through various mechanisms, such as interaction with the intestinal mucosa, tight junction modulation, inhibition of efflux transporters, enzyme inhibition, solubility and stability enhancement, and complexation. On the other side, CS exhibits the ability to inhibit the absorption of certain drugs by adsorbing to lipids and sterols, modulating bile acids and gut microbiota, altering drug-cell interaction at the polar interface, and mucus-mediated entrapment and interference. Future potential pharmaceutical research in this field includes elucidating the underneath absorption relevant mechanisms, rational use in formulations as excipient, exploring functional CS derivatives, and developing CS-based drug delivery systems. This comprehensive review highlights CS’s versatile and significant role in enhancing and inhibiting oral drug absorption, providing insights into the complexities of drug delivery and the potential of CS to improve therapeutic outcomes.
Chitosan (CS), a natural polymer derived from chitin found in the exoskeletons of crustaceans, has garnered significant interest in the pharmaceutical field due to its unique properties, including biocompatibility and biodegradability. In recent years, various studies have reported that CS can affect drug bioavailability, and interestingly, it works as an oral absorption enhancer and inhibitor. This review offers an in-depth analysis of the mechanisms underlying such a phenomenon and supports its application as a pharmaceutical excipient. CS enhances oral drug absorption through various mechanisms, such as interaction with the intestinal mucosa, tight junction modulation, inhibition of efflux transporters, enzyme inhibition, solubility and stability enhancement, and complexation. On the other side, CS exhibits the ability to inhibit the absorption of certain drugs by adsorbing to lipids and sterols, modulating bile acids and gut microbiota, altering drug-cell interaction at the polar interface, and mucus-mediated entrapment and interference. Future potential pharmaceutical research in this field includes elucidating the underneath absorption relevant mechanisms, rational use in formulations as excipient, exploring functional CS derivatives, and developing CS-based drug delivery systems. This comprehensive review highlights CS’s versatile and significant role in enhancing and inhibiting oral drug absorption, providing insights into the complexities of drug delivery and the potential of CS to improve therapeutic outcomes.
2026, 37(1): 111512
doi: 10.1016/j.cclet.2025.111512
摘要:
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents, including suboptimal sensitivity, off-target biodistribution, and inherent cytotoxicity. These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents, which was engineered to dynamically respond to endogenous biochemical cues (e.g., pH gradients, redox potential, enzyme activity, hypoxia environment) or exogenous physical triggers (e.g., photoirradiation, thermal gradients, ultrasound (US)/magnetic stimuli). Through spatiotemporally controlled structural transformations, stimuli-responsive block copolymers enable precise contrast targeting, activatable signal amplification, and theranostic integration, thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity. Hence, this mini-review systematically examines molecular engineering principles for designing pH-, redox-, enzyme-, light-, thermo-, and US/magnetic-responsive polymers, with emphasis on structure-property relationships governing imaging performance modulation. Furthermore, we critically analyze emerging strategies for optical imaging, US synergies, and magnetic resonance imaging (MRI). Multimodal bioimaging has also been elaborated, which could overcome the inherent trade-offs between resolution, penetration depth, and functional specificity in single-modal approaches. By elucidating mechanistic insights and translational challenges, this mini-review aims to establish a design framework of stimuli-responsive block copolymers-based for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents, including suboptimal sensitivity, off-target biodistribution, and inherent cytotoxicity. These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents, which was engineered to dynamically respond to endogenous biochemical cues (e.g., pH gradients, redox potential, enzyme activity, hypoxia environment) or exogenous physical triggers (e.g., photoirradiation, thermal gradients, ultrasound (US)/magnetic stimuli). Through spatiotemporally controlled structural transformations, stimuli-responsive block copolymers enable precise contrast targeting, activatable signal amplification, and theranostic integration, thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity. Hence, this mini-review systematically examines molecular engineering principles for designing pH-, redox-, enzyme-, light-, thermo-, and US/magnetic-responsive polymers, with emphasis on structure-property relationships governing imaging performance modulation. Furthermore, we critically analyze emerging strategies for optical imaging, US synergies, and magnetic resonance imaging (MRI). Multimodal bioimaging has also been elaborated, which could overcome the inherent trade-offs between resolution, penetration depth, and functional specificity in single-modal approaches. By elucidating mechanistic insights and translational challenges, this mini-review aims to establish a design framework of stimuli-responsive block copolymers-based for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
2026, 37(1): 111513
doi: 10.1016/j.cclet.2025.111513
摘要:
Malignant pleural effusion (MPE) is a serious disease caused by malignant tumors with high morbidity and mortality. Chemotherapy, immunotherapy, and antiangiogenic therapy are common treatments for MPE at present. However, traditional chemotherapeutic drugs have many side effects and can easily lead to drug resistance in patients. The complex tumor microenvironment (TME) of MPE directly reduces the antitumor efficacy of immunotherapy. Fortunately, drug delivery systems (DDSs) based on biomaterials have the ability to overcome some of the drawbacks of conventional treatments by improving drug stability, increasing the accuracy of tumor cell targeting, reducing toxic side effects, and remodeling TME, ultimately improving drug efficacy. Therefore, the purpose of this review is to provide an overview and discussion of the latest progress in biomaterial-based DDSs for the treatment of MPE. We discuss the application of biomaterials in the treatment of MPE from multiple perspectives, including chemotherapy, immunotherapy, combination therapy, and pleurodesis, where microspheres, cell membrane-derived microparticles (MPs), micelles, nanoparticles, and liposomes, are involved. The application of these biomaterials has been proven to have great potential in the treatment of MPE, providing a new idea for follow-up research.
Malignant pleural effusion (MPE) is a serious disease caused by malignant tumors with high morbidity and mortality. Chemotherapy, immunotherapy, and antiangiogenic therapy are common treatments for MPE at present. However, traditional chemotherapeutic drugs have many side effects and can easily lead to drug resistance in patients. The complex tumor microenvironment (TME) of MPE directly reduces the antitumor efficacy of immunotherapy. Fortunately, drug delivery systems (DDSs) based on biomaterials have the ability to overcome some of the drawbacks of conventional treatments by improving drug stability, increasing the accuracy of tumor cell targeting, reducing toxic side effects, and remodeling TME, ultimately improving drug efficacy. Therefore, the purpose of this review is to provide an overview and discussion of the latest progress in biomaterial-based DDSs for the treatment of MPE. We discuss the application of biomaterials in the treatment of MPE from multiple perspectives, including chemotherapy, immunotherapy, combination therapy, and pleurodesis, where microspheres, cell membrane-derived microparticles (MPs), micelles, nanoparticles, and liposomes, are involved. The application of these biomaterials has been proven to have great potential in the treatment of MPE, providing a new idea for follow-up research.
2026, 37(1): 111524
doi: 10.1016/j.cclet.2025.111524
摘要:
In recent years, development of strategies to treat central nervous system (CNS) diseases has attracted extensive attention. A major obstacle in this field is the blood-brain barrier (BBB), which significantly limits the efficient delivery of therapeutic agents to the brain and hinders the treatment of CNS diseases. Overcoming the restrictive nature of the BBB has thus emerged as a key objective in CNS drug development. Nanomaterials have garnered growing interest due to their unique physicochemical properties and potential to traverse the BBB, enabling targeted drug delivery to brain tissue and improving therapeutic efficacy. In this review, we present current insights into the structure and function of the BBB and highlight a range of nanomaterial-based strategies for BBB penetration, including receptor-mediated transport (RMT), adsorptive-mediated transcytosis, reversible BBB disruption, and intranasal administration. Finally, we summarize recent advances in enhancing BBB permeability for CNS therapeutics and discuss persisting challenges, offering perspectives for future research in this field.
In recent years, development of strategies to treat central nervous system (CNS) diseases has attracted extensive attention. A major obstacle in this field is the blood-brain barrier (BBB), which significantly limits the efficient delivery of therapeutic agents to the brain and hinders the treatment of CNS diseases. Overcoming the restrictive nature of the BBB has thus emerged as a key objective in CNS drug development. Nanomaterials have garnered growing interest due to their unique physicochemical properties and potential to traverse the BBB, enabling targeted drug delivery to brain tissue and improving therapeutic efficacy. In this review, we present current insights into the structure and function of the BBB and highlight a range of nanomaterial-based strategies for BBB penetration, including receptor-mediated transport (RMT), adsorptive-mediated transcytosis, reversible BBB disruption, and intranasal administration. Finally, we summarize recent advances in enhancing BBB permeability for CNS therapeutics and discuss persisting challenges, offering perspectives for future research in this field.
2026, 37(1): 111543
doi: 10.1016/j.cclet.2025.111543
摘要:
Plant bacterial diseases cause significant harm to agricultural production because of their frequent, intermittent and regional outbreaks. Currently, chemical control is still a more effective method for bacterial disease. To develop new, efficient and safe antibacterial agrochemicals, we summarize the research progress of compounds with antibacterial activities in the past ten years, classify them according to their active skeletons, and discuss their structure-activity relationships and mechanisms of action. Finally, the development trend of antibacterial agrochemicals was prospected. This review provides valuable information for the development of antibacterial agrochemicals.
Plant bacterial diseases cause significant harm to agricultural production because of their frequent, intermittent and regional outbreaks. Currently, chemical control is still a more effective method for bacterial disease. To develop new, efficient and safe antibacterial agrochemicals, we summarize the research progress of compounds with antibacterial activities in the past ten years, classify them according to their active skeletons, and discuss their structure-activity relationships and mechanisms of action. Finally, the development trend of antibacterial agrochemicals was prospected. This review provides valuable information for the development of antibacterial agrochemicals.
2026, 37(1): 111545
doi: 10.1016/j.cclet.2025.111545
摘要:
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry, significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold. Catalyzed direct Csp2–H functionalization provides an effective and cost-efficient approach to synthesizing carbazoles from simple and readily available starting materials, ensuring a promising path characterized by excellent atom and step economy. This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp2–H functionalization techniques for synthesizing carbazoles.
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry, significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold. Catalyzed direct Csp2–H functionalization provides an effective and cost-efficient approach to synthesizing carbazoles from simple and readily available starting materials, ensuring a promising path characterized by excellent atom and step economy. This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp2–H functionalization techniques for synthesizing carbazoles.
2026, 37(1): 111596
doi: 10.1016/j.cclet.2025.111596
摘要:
In recent years, different drugs therapies for treatment pulmonary fibrosis (PF) have gained much attention due to development of drug delivery technology and urgent clinical needs. PF treatment existed a variety of currently clinical problem but PF could be treated with different drugs potentially though drug delivery technology. This review systematically expounds its basic theory, various drug delivery technologies, and future development directions. In the introduction, the relationship between the pathological mechanism of PF and drug delivery, the basic principles of the drug delivery system and the biological barriers faced by pulmonary drug delivery are analyzed. This review details delivery of small molecule drug, macromolecular drug and cells, including chemical synthesis and natural small molecule drug delivery, as well as RNA and cell-based delivery. Finally, the challenges and perspectives of these drugs to treat PF delivery technologies are discussed and key aspects in the development of PF drugs are considered. We hoped that this review can provide comprehensive and in-depth theoretical reference and technical support for the drug treatment of PF.
In recent years, different drugs therapies for treatment pulmonary fibrosis (PF) have gained much attention due to development of drug delivery technology and urgent clinical needs. PF treatment existed a variety of currently clinical problem but PF could be treated with different drugs potentially though drug delivery technology. This review systematically expounds its basic theory, various drug delivery technologies, and future development directions. In the introduction, the relationship between the pathological mechanism of PF and drug delivery, the basic principles of the drug delivery system and the biological barriers faced by pulmonary drug delivery are analyzed. This review details delivery of small molecule drug, macromolecular drug and cells, including chemical synthesis and natural small molecule drug delivery, as well as RNA and cell-based delivery. Finally, the challenges and perspectives of these drugs to treat PF delivery technologies are discussed and key aspects in the development of PF drugs are considered. We hoped that this review can provide comprehensive and in-depth theoretical reference and technical support for the drug treatment of PF.
2026, 37(1): 111604
doi: 10.1016/j.cclet.2025.111604
摘要:
Hydrogen peroxide (H2O2) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection, metal etching, textile printing and dyeing, chemical synthesis and food processing. However, over 90% of industrial H2O2 is currently produced through the multi-step anthraquinone oxidation process, which suffers from a process with some drawbacks such as complex, high-energy consumption, and toxic byproducts emissions. Compared to the traditional anthraquinone method, artificial photosynthesis of H2O2 using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O2 as the clean reactants and sole energy as the driving force. In recent years, metal-free photocatalysts mainly including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and carbon nitrile (g-C3N4) have garnered significant interest due to their superior thermal and chemical stability, diverse synthesis methods, tunable functionality, light weight nature and non-toxicity. These materials also exhibit adjustable band structure and unique photoelectric properties. Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H2O2, however, a comprehensive summary of current research status on metal-free-based photocatalytic overall H2O2 production remain scarce. This review outlines recent process in overall H2O2 photosynthesis based on metal-free photocatalysts. First, we introduced the fundamental concepts of photocatalytic overall H2O2 production. Then, we analyze representative studies on photocatalytic overall H2O2 synthesis using metal-free materials. Finally, we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H2O2 generation.
Hydrogen peroxide (H2O2) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection, metal etching, textile printing and dyeing, chemical synthesis and food processing. However, over 90% of industrial H2O2 is currently produced through the multi-step anthraquinone oxidation process, which suffers from a process with some drawbacks such as complex, high-energy consumption, and toxic byproducts emissions. Compared to the traditional anthraquinone method, artificial photosynthesis of H2O2 using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O2 as the clean reactants and sole energy as the driving force. In recent years, metal-free photocatalysts mainly including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and carbon nitrile (g-C3N4) have garnered significant interest due to their superior thermal and chemical stability, diverse synthesis methods, tunable functionality, light weight nature and non-toxicity. These materials also exhibit adjustable band structure and unique photoelectric properties. Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H2O2, however, a comprehensive summary of current research status on metal-free-based photocatalytic overall H2O2 production remain scarce. This review outlines recent process in overall H2O2 photosynthesis based on metal-free photocatalysts. First, we introduced the fundamental concepts of photocatalytic overall H2O2 production. Then, we analyze representative studies on photocatalytic overall H2O2 synthesis using metal-free materials. Finally, we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H2O2 generation.
2026, 37(1): 111661
doi: 10.1016/j.cclet.2025.111661
摘要:
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused, and has obtained huge attention. In this field, great progress has been achieved during the past five years. Followed by the roadmap (Chinese Chemical Letters, 2019, 30, 2089–2109) written by us before five years, we think that it should be updated to give more insights in this field. Thus, we write the present roadmap based on the fast changed background. In this roadmap, oxygen and carbon dioxide reduction reactions (including at high temperature), photocatalytic hydrogen generation and carbon dioxide reduction reactions, (photo)electrocatalytic reduction of O2 to H2O2 and NH3 generated from N2 are discussed. The progress and challenges in above catalytic processes are given. We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused, and has obtained huge attention. In this field, great progress has been achieved during the past five years. Followed by the roadmap (Chinese Chemical Letters, 2019, 30, 2089–2109) written by us before five years, we think that it should be updated to give more insights in this field. Thus, we write the present roadmap based on the fast changed background. In this roadmap, oxygen and carbon dioxide reduction reactions (including at high temperature), photocatalytic hydrogen generation and carbon dioxide reduction reactions, (photo)electrocatalytic reduction of O2 to H2O2 and NH3 generated from N2 are discussed. The progress and challenges in above catalytic processes are given. We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
2026, 37(1): 111673
doi: 10.1016/j.cclet.2025.111673
摘要:
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals, where electron transfer at the electrode produces catalysts with more valence states. Among these transition metal catalysts, electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention. This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates, which can be broadly classified into the functionalization of C = C bonds, C−H bond activation, C−C and C−X bond activation, and so on.
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals, where electron transfer at the electrode produces catalysts with more valence states. Among these transition metal catalysts, electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention. This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates, which can be broadly classified into the functionalization of C = C bonds, C−H bond activation, C−C and C−X bond activation, and so on.
2026, 37(1): 111886
doi: 10.1016/j.cclet.2025.111886
摘要:
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
2026, 37(1): 111894
doi: 10.1016/j.cclet.2025.111894
摘要:
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
2026, 37(1): 111638
doi: 10.1016/j.cclet.2025.111638
摘要:
2026, 37(1): 111796
doi: 10.1016/j.cclet.2025.111796
摘要:
