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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: 9.4
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2025, 36(10): 110369
doi: 10.1016/j.cclet.2024.110369
摘要:
Owing to the advantages of high energy density, low cost, abundant sulfur reserves and environmentally friendly nature, lithium-sulfur batteries (LSBs) were considered as one of the potential candidates of energy storage devices for the next generation. However, the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li2S product and the capacity degradation triggered by the severe shuttle effect of polysulfides. It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides (LiPSs). In this work, we report a straightforward method for fabrication of the phosphorus doped porous CeO2 (P-CeO2) as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs. Through coin batteries tests, P-CeO2 modified PP separator (P-CeO2//PP) exhibits remarkable electrochemical performance. It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C, surpassing the performance of the bare CeO2//PP separator. Furthermore, the P-CeO2//PP separator demonstrates enhanced cycling stability, with a low-capacity fading rate of only 0.048% per cycle over 1000 cycles at 2 C. In compared with bare CeO2//PP, P-CeO2//PP exhibits high redox peak current, enhanced adsorption property of Li2S6 and early Li2S precipitation. These results highlight the superior performance of the P-CeO2//PP separator compared to the bare CeO2//PP separator. Hence, this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.
Owing to the advantages of high energy density, low cost, abundant sulfur reserves and environmentally friendly nature, lithium-sulfur batteries (LSBs) were considered as one of the potential candidates of energy storage devices for the next generation. However, the significant challenges in this area stem from the sluggish reaction kinetics of the insoluble Li2S product and the capacity degradation triggered by the severe shuttle effect of polysulfides. It has been firmly established through numerous studies that modifying separators is an effective approach to enhance the properties of LSBs by facilitating the catalytic kinetic conversion and chemical adsorption of lithium polysulfides (LiPSs). In this work, we report a straightforward method for fabrication of the phosphorus doped porous CeO2 (P-CeO2) as separator modifier to accelerate the catalytic kinetic conversion of polysulfides and effectively inhibit the shuttle effect in LSBs. Through coin batteries tests, P-CeO2 modified PP separator (P-CeO2//PP) exhibits remarkable electrochemical performance. It demonstrates a high initial capacity of 1180 mAh/g at 0.5 C, surpassing the performance of the bare CeO2//PP separator. Furthermore, the P-CeO2//PP separator demonstrates enhanced cycling stability, with a low-capacity fading rate of only 0.048% per cycle over 1000 cycles at 2 C. In compared with bare CeO2//PP, P-CeO2//PP exhibits high redox peak current, enhanced adsorption property of Li2S6 and early Li2S precipitation. These results highlight the superior performance of the P-CeO2//PP separator compared to the bare CeO2//PP separator. Hence, this research presents a successful strategy for the modification of LIBs separator with improved electrochemical performance and cycle stability.
2025, 36(10): 110372
doi: 10.1016/j.cclet.2024.110372
摘要:
Lithium-sulfur batteries (LSBs) are promising energy storage systems due to their low cost and high energy density. However, sluggish reaction kinetics and the "shuttle effect" of lithium polysulfides (LiPSs) from sulfur cathode hinder the practical application of LSBs. In this work, a separator loaded with the Eu2O3−δ nanoparticles/carbon nanotube interlayer is designed to immobilize LiPSs and catalyze their conversion reaction. The oxygen-deficient Eu2O3−δ nanoparticles, with abundant catalytic sites, promote LiPSs conversion kinetics even at high current densities. Moreover, the unique 4f electronic structure of Eu2O3−δ effectively mitigates undesired sulfur cathode crossover, significantly enhancing the cycling performance of LSBs. Specifically, a high capacity of 620.7 mAh/g at a rate of 5 C is achieved, maintaining at 545 mAh/g after 300 cycles at 1 C. This work demonstrates the potential application of rare earth catalysts in LSBs, offering new research avenues for promoting dynamic conversion design in electrocatalysts.
Lithium-sulfur batteries (LSBs) are promising energy storage systems due to their low cost and high energy density. However, sluggish reaction kinetics and the "shuttle effect" of lithium polysulfides (LiPSs) from sulfur cathode hinder the practical application of LSBs. In this work, a separator loaded with the Eu2O3−δ nanoparticles/carbon nanotube interlayer is designed to immobilize LiPSs and catalyze their conversion reaction. The oxygen-deficient Eu2O3−δ nanoparticles, with abundant catalytic sites, promote LiPSs conversion kinetics even at high current densities. Moreover, the unique 4f electronic structure of Eu2O3−δ effectively mitigates undesired sulfur cathode crossover, significantly enhancing the cycling performance of LSBs. Specifically, a high capacity of 620.7 mAh/g at a rate of 5 C is achieved, maintaining at 545 mAh/g after 300 cycles at 1 C. This work demonstrates the potential application of rare earth catalysts in LSBs, offering new research avenues for promoting dynamic conversion design in electrocatalysts.
2025, 36(10): 110373
doi: 10.1016/j.cclet.2024.110373
摘要:
Sluggish sulfur conversion kinetics pose an ongoing challenge in lithium-sulfur batteries (LSBs). Here, we present a solution through far-reaching long-range electronic regulation (LRER) on single-atom active sites. N-doped carbons (Co-NC) are implanted with densely-distributed Co single atoms, and supported on Ti3C2Tx MXene substrates to assemble 3D Co-NC/MXene catalyst. MXene effectively mediates interlayer charge transfer (~0.70 |e|) contrasted with popular carbon materials (~0.06 |e|) to produce LRER through surrounding carbon atoms. The synergy of LRER with near-range electronic regulation (NRER) tunes electronic structures, and enhances heterostructural stability, thus provoking desirous catalytic kinetics of Co single atoms in sulfur reduction. Thereby, the Co-NC/MXene/S cathodes exhibit impressive rate performance and excellent cycling stability (only 0.015% capacity decay per cycle over 600 cycles at 4 C) in LSBs, surpassing state-of-the-art sulfur cathodes. This work reveals the importance of LRER for improved catalysis, and provides new guidance to tailor heterostructures to achieve high-efficient catalysts in various process.
Sluggish sulfur conversion kinetics pose an ongoing challenge in lithium-sulfur batteries (LSBs). Here, we present a solution through far-reaching long-range electronic regulation (LRER) on single-atom active sites. N-doped carbons (Co-NC) are implanted with densely-distributed Co single atoms, and supported on Ti3C2Tx MXene substrates to assemble 3D Co-NC/MXene catalyst. MXene effectively mediates interlayer charge transfer (~0.70 |e|) contrasted with popular carbon materials (~0.06 |e|) to produce LRER through surrounding carbon atoms. The synergy of LRER with near-range electronic regulation (NRER) tunes electronic structures, and enhances heterostructural stability, thus provoking desirous catalytic kinetics of Co single atoms in sulfur reduction. Thereby, the Co-NC/MXene/S cathodes exhibit impressive rate performance and excellent cycling stability (only 0.015% capacity decay per cycle over 600 cycles at 4 C) in LSBs, surpassing state-of-the-art sulfur cathodes. This work reveals the importance of LRER for improved catalysis, and provides new guidance to tailor heterostructures to achieve high-efficient catalysts in various process.
2025, 36(10): 110387
doi: 10.1016/j.cclet.2024.110387
摘要:
Direct conversion of methane into C1 oxygenates under mild condition with high selectivity is a desired goal in the field of energy and chemistry. But it still remains a great challenge due to the intrinsic inertness of methane originating from strong C-H bonds (104 kcal/mol), low solubility in the solvent, and poor selectivity. Herein, we present a direct single-step conversion of methane to formic acid (HCOOH) using molecular oxygen (O2) as the oxidant under gentle conditions on a decatungstate-doped porous cerium metal-organic framework (Ce-MOF), W10@Ce-bpdc. The HCOOH yield of W10@Ce-bpdc-2 was 155 µmol/gcat at room temperature in 12 h. The process and mechanism of conversion of methane to HCOOH was revealed by spectroscopic characteristics and controlled experiments. In the presence of light, O2 was converted to H2O2 by catalyst and then to ·OH radicals in solution, which interact with methane and undergo intermediates to produce HCOOH. Our experiment provides a new way to catalyze methane in combination with MOF and polyoxometalates (POMs).
Direct conversion of methane into C1 oxygenates under mild condition with high selectivity is a desired goal in the field of energy and chemistry. But it still remains a great challenge due to the intrinsic inertness of methane originating from strong C-H bonds (104 kcal/mol), low solubility in the solvent, and poor selectivity. Herein, we present a direct single-step conversion of methane to formic acid (HCOOH) using molecular oxygen (O2) as the oxidant under gentle conditions on a decatungstate-doped porous cerium metal-organic framework (Ce-MOF), W10@Ce-bpdc. The HCOOH yield of W10@Ce-bpdc-2 was 155 µmol/gcat at room temperature in 12 h. The process and mechanism of conversion of methane to HCOOH was revealed by spectroscopic characteristics and controlled experiments. In the presence of light, O2 was converted to H2O2 by catalyst and then to ·OH radicals in solution, which interact with methane and undergo intermediates to produce HCOOH. Our experiment provides a new way to catalyze methane in combination with MOF and polyoxometalates (POMs).
2025, 36(10): 110388
doi: 10.1016/j.cclet.2024.110388
摘要:
The development of high-performance cathode materials is critical to the practical application of sodium-ion batteries (SIBs). O3-type NaCrO2 (NCO) is one of the most competitive cathodes, but it suffers from rapid capacity decay caused by severe irreversible structural evolution. An Mg-Ti co-doped Na0.99Cr0.95Mg0.02Ti0.03O2 (NCO-MT) cathode material is designed and synthesized via a facile solid-state reaction to enhance the cyclability of NCO. A capacity retention of 71.6% after 2500 cycles with the capacity fade rate of 0.011% per cycle is achieved for NCO-MT at 5 C, which is attributed to the highly reversible crystal structure during cycling. Our findings offer a novel insight into the high-performance O3-type layered cathode materials for SIBs and are beneficial to promote the development of high-rate SIBs.
The development of high-performance cathode materials is critical to the practical application of sodium-ion batteries (SIBs). O3-type NaCrO2 (NCO) is one of the most competitive cathodes, but it suffers from rapid capacity decay caused by severe irreversible structural evolution. An Mg-Ti co-doped Na0.99Cr0.95Mg0.02Ti0.03O2 (NCO-MT) cathode material is designed and synthesized via a facile solid-state reaction to enhance the cyclability of NCO. A capacity retention of 71.6% after 2500 cycles with the capacity fade rate of 0.011% per cycle is achieved for NCO-MT at 5 C, which is attributed to the highly reversible crystal structure during cycling. Our findings offer a novel insight into the high-performance O3-type layered cathode materials for SIBs and are beneficial to promote the development of high-rate SIBs.
2025, 36(10): 110390
doi: 10.1016/j.cclet.2024.110390
摘要:
Mixed polyanion phosphate Na4Fe3(PO4)2P2O7 (NFPP) is regarded as the most promising cathode material for sodium-ion batteries (SIBs), due to its high structural stability and low-cost environmental friendliness. However, its intrinsic low conductivity and sluggish Na+ diffusion restricted the fast-charge and low-temperature sodium storage. Herein, an NFPP composite encapsulated by in-situ pyrolytic carbon and coupled with expanded graphite (NFPP@C/EG) was constructed via a sol-gel method followed by a ball-mill procedure. Due to the dual-carbon modified strategy, this NFPP@C/EG only enhanced the electronic conductivity, but also endowed more channels for Na+ diffusion. As cathode for SIBs, the optimized NFPP (M-NFPP@C/EG) delivers excellent rate capability (capacity of ~80.5 mAh/g at 50 C) and outstanding cycling stability (11000 cycles at 50 C with capacity retention of 89.85%). Additionally, cyclic voltammetry (CV) confirmed that its sodium storage behavior is pseudocapacitance-controlled, with in-situ electrochemical impedance spectroscopy (EIS) further elucidating improvements in electrode reaction kinetics. At lower temperatures (0 ℃), M-NFPP@C/EG demonstrated exceptional cycling performance (8800 cycles at 10 C with capacity retention of 95.81%). Moreover, pouch cells also exhibited excellent stability. This research demonstrates the feasibility of a dual carbon modification strategy in enhancing NFPP and proposes a low-cost, high-rate, and ultra-stable cathode material for SIBs.
Mixed polyanion phosphate Na4Fe3(PO4)2P2O7 (NFPP) is regarded as the most promising cathode material for sodium-ion batteries (SIBs), due to its high structural stability and low-cost environmental friendliness. However, its intrinsic low conductivity and sluggish Na+ diffusion restricted the fast-charge and low-temperature sodium storage. Herein, an NFPP composite encapsulated by in-situ pyrolytic carbon and coupled with expanded graphite (NFPP@C/EG) was constructed via a sol-gel method followed by a ball-mill procedure. Due to the dual-carbon modified strategy, this NFPP@C/EG only enhanced the electronic conductivity, but also endowed more channels for Na+ diffusion. As cathode for SIBs, the optimized NFPP (M-NFPP@C/EG) delivers excellent rate capability (capacity of ~80.5 mAh/g at 50 C) and outstanding cycling stability (11000 cycles at 50 C with capacity retention of 89.85%). Additionally, cyclic voltammetry (CV) confirmed that its sodium storage behavior is pseudocapacitance-controlled, with in-situ electrochemical impedance spectroscopy (EIS) further elucidating improvements in electrode reaction kinetics. At lower temperatures (0 ℃), M-NFPP@C/EG demonstrated exceptional cycling performance (8800 cycles at 10 C with capacity retention of 95.81%). Moreover, pouch cells also exhibited excellent stability. This research demonstrates the feasibility of a dual carbon modification strategy in enhancing NFPP and proposes a low-cost, high-rate, and ultra-stable cathode material for SIBs.
2025, 36(10): 110402
doi: 10.1016/j.cclet.2024.110402
摘要:
Although many racemic M4L6 cages have been synthesized, little attention has been paid to the resolution of M4L6 cages because resolution of these cages is very difficult. To explore the use of optically pure M4L6 cages in chiral applications, it is important to obtain a single enantiomer. In this work, the anionic ΔΔΔΔ-Zr4L6 and ΛΛΛΛ-Zr4L6 (L = embonate) cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN, respectively, and the active vertex of homochiral Zr4L6 cage traps π-conjugated coordination silver cations (such as [Ag2(DPPM)2]2+, chiral [Ag2(PPh3)2(DPEN)]2+ and [Ag(PPh3)(DPEN)]+), obtaining two pair of pure enantiomers (PTC-375(Δ/Λ) and PTC-376(Δ/Λ)). Interestingly, the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence (CPL) response, and PTC-376 enantiomers show a CPL output with glum values up to ~1.4 × 10−2. This work not only provides a new resolution strategy for metal-organic cages, but also expands their chiral application especially in CPL field.
Although many racemic M4L6 cages have been synthesized, little attention has been paid to the resolution of M4L6 cages because resolution of these cages is very difficult. To explore the use of optically pure M4L6 cages in chiral applications, it is important to obtain a single enantiomer. In this work, the anionic ΔΔΔΔ-Zr4L6 and ΛΛΛΛ-Zr4L6 (L = embonate) cages have been completely separated by introducing chiral organic ligands R/S-BINAP and 1S,2S/1R,2R-DPEN, respectively, and the active vertex of homochiral Zr4L6 cage traps π-conjugated coordination silver cations (such as [Ag2(DPPM)2]2+, chiral [Ag2(PPh3)2(DPEN)]2+ and [Ag(PPh3)(DPEN)]+), obtaining two pair of pure enantiomers (PTC-375(Δ/Λ) and PTC-376(Δ/Λ)). Interestingly, the chiral resolution and surface modification of such zirconium cage endow it with homochirality and significant circularly polarized luminescence (CPL) response, and PTC-376 enantiomers show a CPL output with glum values up to ~1.4 × 10−2. This work not only provides a new resolution strategy for metal-organic cages, but also expands their chiral application especially in CPL field.
2025, 36(10): 110403
doi: 10.1016/j.cclet.2024.110403
摘要:
Zn-air battery (ZAB) has garnered significant attention owing to its environmental friendliness and safety attributes. A critical challenge in advancing ZAB technology lies in the development of high-performance and cost-effective electrocatalysts for oxygen redox reactions (OER and ORR). Herein, we report Co/Fe carbon-supported composites as efficient bifunctional catalyst encapsulated in oxidative ammonolysis modified lignin-derived N-doped biochar (CoFe-CoxN@NOALC). It exhibited exceptional electrochemical performance in aqueous ZAB owing to their uniform dispersed and small particle size, with a peak power density of 154 mW/cm2 and a specific capacity of 770 mAh/g. Most notably, it exhibited a long cycle stability, surpassing 1500 h at a current density of 10 mA/cm2, with a mere 11.4% decrease in the charge-discharge efficiency of the battery. This study proposes a viable strategy for enhancing the performance and reducing the cost of Zn-air batteries through the utilization of biomass-derived materials.
Zn-air battery (ZAB) has garnered significant attention owing to its environmental friendliness and safety attributes. A critical challenge in advancing ZAB technology lies in the development of high-performance and cost-effective electrocatalysts for oxygen redox reactions (OER and ORR). Herein, we report Co/Fe carbon-supported composites as efficient bifunctional catalyst encapsulated in oxidative ammonolysis modified lignin-derived N-doped biochar (CoFe-CoxN@NOALC). It exhibited exceptional electrochemical performance in aqueous ZAB owing to their uniform dispersed and small particle size, with a peak power density of 154 mW/cm2 and a specific capacity of 770 mAh/g. Most notably, it exhibited a long cycle stability, surpassing 1500 h at a current density of 10 mA/cm2, with a mere 11.4% decrease in the charge-discharge efficiency of the battery. This study proposes a viable strategy for enhancing the performance and reducing the cost of Zn-air batteries through the utilization of biomass-derived materials.
2025, 36(10): 110404
doi: 10.1016/j.cclet.2024.110404
摘要:
Metal-organic frameworks (MOFs) containing face-to-face π-π interacting anthracene groups are promising photoresponsive materials because of their rich photophysical properties and their ability to undergo reversible [4 + 4] photocycloaddition reaction, but it is extremely challenging to obtain such materials. Herein, we propose a generalized method to accomplish photoresponsive MOFs by introducing anthracene pairs into the framework of the dianthracene-phosphonate-based MOFs by controlling the synthesis temperature. Compounds Dy2(ampH)2x(amp2H2)3-x(H2O)6·4H2O [x = 0.01, Dy-70; x = 0.02, Dy-80; x = 0.037, Dy-90; amp2H4 = pre-photodimerized 9-anthracenemethylphosphonic acid (ampH2)] were obtained by the reaction of DyCl3 and amp2H4 in water at 70, 80, and 90 ℃, respectively. They all show excimer emission of paired anthracenes at ca. 555 nm. Detailed studies of Dy-90 have shown that it undergoes a reversible photodimerization reaction under 365 nm and then 280 nm illumination, accompanied by luminescence changes. This property further enables Dy-90 to be used for optical anti-counterfeiting.
Metal-organic frameworks (MOFs) containing face-to-face π-π interacting anthracene groups are promising photoresponsive materials because of their rich photophysical properties and their ability to undergo reversible [4 + 4] photocycloaddition reaction, but it is extremely challenging to obtain such materials. Herein, we propose a generalized method to accomplish photoresponsive MOFs by introducing anthracene pairs into the framework of the dianthracene-phosphonate-based MOFs by controlling the synthesis temperature. Compounds Dy2(ampH)2x(amp2H2)3-x(H2O)6·4H2O [x = 0.01, Dy-70; x = 0.02, Dy-80; x = 0.037, Dy-90; amp2H4 = pre-photodimerized 9-anthracenemethylphosphonic acid (ampH2)] were obtained by the reaction of DyCl3 and amp2H4 in water at 70, 80, and 90 ℃, respectively. They all show excimer emission of paired anthracenes at ca. 555 nm. Detailed studies of Dy-90 have shown that it undergoes a reversible photodimerization reaction under 365 nm and then 280 nm illumination, accompanied by luminescence changes. This property further enables Dy-90 to be used for optical anti-counterfeiting.
2025, 36(10): 110405
doi: 10.1016/j.cclet.2024.110405
摘要:
Polar semiconductors, particularly the emerging polar two-dimensional (2D) halide perovskites, have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarization-generated photoelectric effects. However, the constraints on the organic cation's choice are still subject to limitations of polar 2D halide perovskites due to the size of the inorganic pocket between adjacent corner-sharing octahedra. Herein, a mixed spacer cation ordering strategy is employed to assemble a polar 2D halide perovskite NMAMAPbBr4 (NMPB, NMA is N-methylbenzene ammonium, MA is methylammonium) with alternating cation in the interlayer space. Driven by the incorporation of a second MA cation, the perovskite layer transformed from a 2D Pb7Br24 anionic network with corner- and face-sharing octahedra to a flat 2D PbBr4 perovskite networks only with corner-sharing octahedra. In the crystal structure of NMPB, the asymmetric hydrogen-bonding interactions between ordered mixed-spacer cations and 2D perovskite layers give rise to a second harmonic generation response and a large polarization of 1.3 µC/cm2. More intriguingly, the ordered 2D perovskite networks endow NMPB with excellent self-powered polarization-sensitive detection performance, showing a considerable polarization-related dichroism ratio up to 1.87. The reconstruction of an inorganic framework within a crystal through mixed cation ordering offers a new synthetic tool for templating perovskite lattices with controlled properties, overcoming limitations of conventional cation choice.
Polar semiconductors, particularly the emerging polar two-dimensional (2D) halide perovskites, have motivated immense interest in diverse photoelectronic devices due to their distinguishing polarization-generated photoelectric effects. However, the constraints on the organic cation's choice are still subject to limitations of polar 2D halide perovskites due to the size of the inorganic pocket between adjacent corner-sharing octahedra. Herein, a mixed spacer cation ordering strategy is employed to assemble a polar 2D halide perovskite NMAMAPbBr4 (NMPB, NMA is N-methylbenzene ammonium, MA is methylammonium) with alternating cation in the interlayer space. Driven by the incorporation of a second MA cation, the perovskite layer transformed from a 2D Pb7Br24 anionic network with corner- and face-sharing octahedra to a flat 2D PbBr4 perovskite networks only with corner-sharing octahedra. In the crystal structure of NMPB, the asymmetric hydrogen-bonding interactions between ordered mixed-spacer cations and 2D perovskite layers give rise to a second harmonic generation response and a large polarization of 1.3 µC/cm2. More intriguingly, the ordered 2D perovskite networks endow NMPB with excellent self-powered polarization-sensitive detection performance, showing a considerable polarization-related dichroism ratio up to 1.87. The reconstruction of an inorganic framework within a crystal through mixed cation ordering offers a new synthetic tool for templating perovskite lattices with controlled properties, overcoming limitations of conventional cation choice.
2025, 36(10): 110406
doi: 10.1016/j.cclet.2024.110406
摘要:
Na-Se batteries have caught tremendous attention because of natural abundant of element sodium and their high volumetric energy density (2530 Wh/L). However, the low utilization ratio of Se is the main obstacle for practical application. Herein, an advanced Se-based electrode is designed and prepared by using tea stem-derived micropore carbon matrix (TSC) as Se host and coating TSC/Se with cyclic polyacrylonitrile (cPAN). TSC/Se/cPAN electrode shows rate capacity of 318.3 mAh/g at 2 C (1 C=675 mA/g) and great discharge capacity of 420.6 mAh/g after 300 cycles at 0.2 C. The impressive electrochemical performance is mainly ascribed to the interface design of cPAN coating, resulting in the enhanced electronic conductivity of whole electrode and high ratio of robust inorganic salt NaCl in CEI film. The TSC/Se/cPANNVP full cell also exhibits great discharge capacity of 556.6 mAh/g after 55 cycles at 0.1 C.
Na-Se batteries have caught tremendous attention because of natural abundant of element sodium and their high volumetric energy density (2530 Wh/L). However, the low utilization ratio of Se is the main obstacle for practical application. Herein, an advanced Se-based electrode is designed and prepared by using tea stem-derived micropore carbon matrix (TSC) as Se host and coating TSC/Se with cyclic polyacrylonitrile (cPAN). TSC/Se/cPAN electrode shows rate capacity of 318.3 mAh/g at 2 C (1 C=675 mA/g) and great discharge capacity of 420.6 mAh/g after 300 cycles at 0.2 C. The impressive electrochemical performance is mainly ascribed to the interface design of cPAN coating, resulting in the enhanced electronic conductivity of whole electrode and high ratio of robust inorganic salt NaCl in CEI film. The TSC/Se/cPANNVP full cell also exhibits great discharge capacity of 556.6 mAh/g after 55 cycles at 0.1 C.
2025, 36(10): 110412
doi: 10.1016/j.cclet.2024.110412
摘要:
The in-depth study of the transport properties of the solid electrolyte interface (SEI) is crucial for the development of ultra-high-rate, and long lifespan sodium-ion batteries (SIBs). However, there remains a lack of theoretical investigation into the transport mechanisms of the main inorganic components of the SEI, namely NaF, Na2O, and Na2CO3. To address this research gap, we performed classical molecular dynamics simulations in this work to study the diffusion mechanisms of sodium ions in these inorganic components of the SEI, with special emphasis on the impact of the amorphous SEI environment on the diffusion behavior of sodium ions. The results have shown that amorphous SEI components significantly enhance the diffusion rate of sodium ions at room temperature compared to crystalline components. Within these amorphous SEI components, we reveal that the diffusion coefficients of sodium ions in amorphous Na2O and Na2CO3 are more than an order of magnitude higher than that of NaF, suggesting that amorphous Na2O and Na2CO3 are more effective in facilitating the Na ion diffusion. Analysis of the local atomic structure indicates that the amorphous local structures are dominant in Na2O and Na2CO3 at room temperature, maintaining a disordered amorphous phase. In contrast, amorphous NaF undergoes a spontaneously transformation into an ordered structure, exhibiting crystalline characteristics that restrict the diffusion of sodium ions. In summary, our work provides atomic insights into the impact of local amorphous environments on Na ion diffusion in SEI and suggests that amorphous SEI components play a critical role in improving battery performance.
The in-depth study of the transport properties of the solid electrolyte interface (SEI) is crucial for the development of ultra-high-rate, and long lifespan sodium-ion batteries (SIBs). However, there remains a lack of theoretical investigation into the transport mechanisms of the main inorganic components of the SEI, namely NaF, Na2O, and Na2CO3. To address this research gap, we performed classical molecular dynamics simulations in this work to study the diffusion mechanisms of sodium ions in these inorganic components of the SEI, with special emphasis on the impact of the amorphous SEI environment on the diffusion behavior of sodium ions. The results have shown that amorphous SEI components significantly enhance the diffusion rate of sodium ions at room temperature compared to crystalline components. Within these amorphous SEI components, we reveal that the diffusion coefficients of sodium ions in amorphous Na2O and Na2CO3 are more than an order of magnitude higher than that of NaF, suggesting that amorphous Na2O and Na2CO3 are more effective in facilitating the Na ion diffusion. Analysis of the local atomic structure indicates that the amorphous local structures are dominant in Na2O and Na2CO3 at room temperature, maintaining a disordered amorphous phase. In contrast, amorphous NaF undergoes a spontaneously transformation into an ordered structure, exhibiting crystalline characteristics that restrict the diffusion of sodium ions. In summary, our work provides atomic insights into the impact of local amorphous environments on Na ion diffusion in SEI and suggests that amorphous SEI components play a critical role in improving battery performance.
2025, 36(10): 110624
doi: 10.1016/j.cclet.2024.110624
摘要:
The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable. Here, we report a fluorinated N-heterocyclic carbene (NHC)–based pillarplex with a tunable quaternary structure, employed as an efficient building block for constructing hierarchical superstructures. Initially, multiple noncovalent interactions in the NHC-based pillarplex, particularly those between the fluorinated pillarplex and PF6- anions, induce the formation of a supramolecular gel at high concentrations. Additionally, this hierarchical self-assembled structure can be regulated by adjusting anion types, facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions. The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.
The precise control over the hierarchical self-assembly of sophisticated structures with comparable complexities and functions relying on the modulation of basic building blocks is elusive and highly desirable. Here, we report a fluorinated N-heterocyclic carbene (NHC)–based pillarplex with a tunable quaternary structure, employed as an efficient building block for constructing hierarchical superstructures. Initially, multiple noncovalent interactions in the NHC-based pillarplex, particularly those between the fluorinated pillarplex and PF6- anions, induce the formation of a supramolecular gel at high concentrations. Additionally, this hierarchical self-assembled structure can be regulated by adjusting anion types, facilitating the controlled transformation from a supramolecular gel into a supramolecular channel upon the introduction of four monocarboxylic acids as anions. The study provides insight into the construction and controlled regulation of superstructures based on NHC-based pillarplexes.
2025, 36(10): 110680
doi: 10.1016/j.cclet.2024.110680
摘要:
Recent advancements in nanotechnology have spotlighted the catalytic potential of nanozymes, particularly single-atom nanozymes (SANs), which are pivotal for innovations in biosensing and medical diagnostics. Among others, DNA stands out as an ideal biological regulator. Its inherent programmability and interaction capabilities allow it to significantly modulate nanozyme activity. This study delves into the dynamic interplay between DNA and molybdenum-zinc single-atom nanozymes (Mo-Zn SANs). Using molecular dynamics simulations, we uncover how DNA influences the peroxidase-like activities of Mo-Zn SANs, providing a foundational understanding that broadens the application scope of SANs in biosensing. With these insights as a foundation, we developed and demonstrated a model aptasensor for point-of-care testing (POCT), utilizing a label-free colorimetric approach that leverages DNA-nanozyme interactions to achieve high-sensitivity detection of lysozyme. Our work elucidates the nuanced control DNA exerts over nanozyme functionality and illustrates the application of this molecular mechanism through a smartphone-assisted biosensing platform. This study not only underscores the practical implications of DNA-regulated Mo-Zn SANs in enhancing biosensing platforms, but also highlights the potential of single-atom nanozyme technology to revolutionize diagnostic tools through its inherent versatility and sensitivity.
Recent advancements in nanotechnology have spotlighted the catalytic potential of nanozymes, particularly single-atom nanozymes (SANs), which are pivotal for innovations in biosensing and medical diagnostics. Among others, DNA stands out as an ideal biological regulator. Its inherent programmability and interaction capabilities allow it to significantly modulate nanozyme activity. This study delves into the dynamic interplay between DNA and molybdenum-zinc single-atom nanozymes (Mo-Zn SANs). Using molecular dynamics simulations, we uncover how DNA influences the peroxidase-like activities of Mo-Zn SANs, providing a foundational understanding that broadens the application scope of SANs in biosensing. With these insights as a foundation, we developed and demonstrated a model aptasensor for point-of-care testing (POCT), utilizing a label-free colorimetric approach that leverages DNA-nanozyme interactions to achieve high-sensitivity detection of lysozyme. Our work elucidates the nuanced control DNA exerts over nanozyme functionality and illustrates the application of this molecular mechanism through a smartphone-assisted biosensing platform. This study not only underscores the practical implications of DNA-regulated Mo-Zn SANs in enhancing biosensing platforms, but also highlights the potential of single-atom nanozyme technology to revolutionize diagnostic tools through its inherent versatility and sensitivity.
2025, 36(10): 110732
doi: 10.1016/j.cclet.2024.110732
摘要:
The efficient limitation of the "shuttle effect" of polysulfide from the rational construction of electrocatalysts to accelerate the redox kinetics of polysulfides is extremely important. In this work, the cobalt/Nickel bimetallic alloy polyhedrons decorated on layered TiO2 heterostructure (CoNi@TiO2/C) derived from MXene and bimetallic metal-organic framework have been prepared through liquid-phase deposition and high-temperature annealing processes. This heterostructure presents excellent electrical conductivity, which facilitates ion diffusion and electron transfer within the battery. Besides, the heterostructure from anchoring the CoNi bimetallic alloy on the layered TiO2 ensures the full exposure of active sites and accelerates polysulfide redox kinetics through chemisorption and catalytic conversion. Considering these advantages mentioned above, when applied as the lithium-sulfur batteries (LSBs) separator modifier, the cell assembled from the CoNi@TiO2/C modified separator demonstrates high specific capacity (1481.7 mAh/g at 0.5 C), superior rate capability (855.5 mAh/g at 3 C) and excellent cycling performance, which can maintain the high capacity of 856.09 mAh/g after 300 cycles with low capacity decay rate of 0.09% per cycle. Even under a high sulfur loading of 4.4 mg/cm2, the cell can still present excellent cycling stability. This study paves the way for the design of novel material for the construction of an outstanding functional separator layer and shines the light on the effective and feasible way for the inhibition of shuttle effect in lithium-sulfur batteries.
The efficient limitation of the "shuttle effect" of polysulfide from the rational construction of electrocatalysts to accelerate the redox kinetics of polysulfides is extremely important. In this work, the cobalt/Nickel bimetallic alloy polyhedrons decorated on layered TiO2 heterostructure (CoNi@TiO2/C) derived from MXene and bimetallic metal-organic framework have been prepared through liquid-phase deposition and high-temperature annealing processes. This heterostructure presents excellent electrical conductivity, which facilitates ion diffusion and electron transfer within the battery. Besides, the heterostructure from anchoring the CoNi bimetallic alloy on the layered TiO2 ensures the full exposure of active sites and accelerates polysulfide redox kinetics through chemisorption and catalytic conversion. Considering these advantages mentioned above, when applied as the lithium-sulfur batteries (LSBs) separator modifier, the cell assembled from the CoNi@TiO2/C modified separator demonstrates high specific capacity (1481.7 mAh/g at 0.5 C), superior rate capability (855.5 mAh/g at 3 C) and excellent cycling performance, which can maintain the high capacity of 856.09 mAh/g after 300 cycles with low capacity decay rate of 0.09% per cycle. Even under a high sulfur loading of 4.4 mg/cm2, the cell can still present excellent cycling stability. This study paves the way for the design of novel material for the construction of an outstanding functional separator layer and shines the light on the effective and feasible way for the inhibition of shuttle effect in lithium-sulfur batteries.
2025, 36(10): 110743
doi: 10.1016/j.cclet.2024.110743
摘要:
The generation of reactive intermediates is a pivotal step during photocatalytic redox elimination of organic micropollutants in water. The UV/S(Ⅳ)-based water treatment system has garnered significant attention as an efficient advanced reduction process for pollutant abatement. However, as a reductive system, the conventional UV/S(Ⅳ) approach exhibits limited efficacy in removing electron-rich micropollutants. Our study uncovered that meso-tetrakis(4-chlorophenyl)porphyrin-Fe(Ⅲ) chloride (TPPFe, a typical iron(Ⅲ) porphyrin) catalyzed the conversion of SO32− into SO3•− under UV365 irradiation without generating of eaq− and H•, leading to the formation of diverse oxidizing species. Additionally, the introduction of TPPFe induced an absorption redshift, broadening the range of applicable UV wavelengths. An in-depth photocatalytic cycle mechanism for TPPFeⅢCl−[TPPFeⅡCl]− was introduced and verified by density functional theory (DFT) calculations. Furthermore, quantum chemistry calculations via transition state were conducted to assess the oxidizing reactivity of the reactive species with micropollutants. Both •OH and SO4•− demonstrate a strong propensity to react with carbamazepine (CMZ, a model micropollutant). Meanwhile, 1O2 exhibits a distinct reaction mechanism with CMZ. Consequently, the radical- and 1O2-mediated distinct degradation pathways were elucidated. This study provides an experimental/theoretical exploration of reactive intermediate generation and their interactions with CMZ, shedding valuable insights into the mechanisms of electron-shuttling photosensitizers catalyzing the UV/S(Ⅳ) oxidation process.
The generation of reactive intermediates is a pivotal step during photocatalytic redox elimination of organic micropollutants in water. The UV/S(Ⅳ)-based water treatment system has garnered significant attention as an efficient advanced reduction process for pollutant abatement. However, as a reductive system, the conventional UV/S(Ⅳ) approach exhibits limited efficacy in removing electron-rich micropollutants. Our study uncovered that meso-tetrakis(4-chlorophenyl)porphyrin-Fe(Ⅲ) chloride (TPPFe, a typical iron(Ⅲ) porphyrin) catalyzed the conversion of SO32− into SO3•− under UV365 irradiation without generating of eaq− and H•, leading to the formation of diverse oxidizing species. Additionally, the introduction of TPPFe induced an absorption redshift, broadening the range of applicable UV wavelengths. An in-depth photocatalytic cycle mechanism for TPPFeⅢCl−[TPPFeⅡCl]− was introduced and verified by density functional theory (DFT) calculations. Furthermore, quantum chemistry calculations via transition state were conducted to assess the oxidizing reactivity of the reactive species with micropollutants. Both •OH and SO4•− demonstrate a strong propensity to react with carbamazepine (CMZ, a model micropollutant). Meanwhile, 1O2 exhibits a distinct reaction mechanism with CMZ. Consequently, the radical- and 1O2-mediated distinct degradation pathways were elucidated. This study provides an experimental/theoretical exploration of reactive intermediate generation and their interactions with CMZ, shedding valuable insights into the mechanisms of electron-shuttling photosensitizers catalyzing the UV/S(Ⅳ) oxidation process.
2025, 36(10): 110744
doi: 10.1016/j.cclet.2024.110744
摘要:
RNA offers distinct advantages for molecular self-assembly as a unique and programmable biomaterial. Recently, single-stranded RNA (ssRNA) origamis, capable of self-folding into defined nanostructures within a single-stranded RNA molecule, are considered a promising platform for immune recognition and therapy. Here, we utilize single-stranded rod RNA origami (Rod RNA-OG) as functional nucleic acid to synthesize valence-programmed RNA structures in a one-pot manner. We discover that the polyvalent RNA origamis are resistant to RNase degradation and can be efficiently internalized by macrophages for subsequent innate immune activation, even in the absence of any external protective agents such as lipids or polymers. The valence-programmed RNA origamis thus hold great promise as novel agonists for immunotherapy.
RNA offers distinct advantages for molecular self-assembly as a unique and programmable biomaterial. Recently, single-stranded RNA (ssRNA) origamis, capable of self-folding into defined nanostructures within a single-stranded RNA molecule, are considered a promising platform for immune recognition and therapy. Here, we utilize single-stranded rod RNA origami (Rod RNA-OG) as functional nucleic acid to synthesize valence-programmed RNA structures in a one-pot manner. We discover that the polyvalent RNA origamis are resistant to RNase degradation and can be efficiently internalized by macrophages for subsequent innate immune activation, even in the absence of any external protective agents such as lipids or polymers. The valence-programmed RNA origamis thus hold great promise as novel agonists for immunotherapy.
2025, 36(10): 110746
doi: 10.1016/j.cclet.2024.110746
摘要:
Polydopamine (PD) coating, one of the simplest and most versatile surface functionalization method faces challenges in terms of stability and reactivity. In this study, we propose an in situ dynamic reassembly approach to address these challenges. By immersing a pre-deposited PD coating in a strong alkaline solution containing poly(allylamine) hydrochloride (PAH), the dissociated PD oligomers undergo covalent crosslinking in situ, leading to the formation of a reconstructed PDPA coating enriched with stable amino groups through thorough crosslinking. The PDPA coating demonstrates superior chemical and mechanical stability compared to PD, while enhancing multifunctional properties and offering improved surface functional modification potential. The PDPA coating holds promise in materials science, biomedical engineering, and nanotechnology, enabling versatile surface modification and functionalization in extreme conditions.
Polydopamine (PD) coating, one of the simplest and most versatile surface functionalization method faces challenges in terms of stability and reactivity. In this study, we propose an in situ dynamic reassembly approach to address these challenges. By immersing a pre-deposited PD coating in a strong alkaline solution containing poly(allylamine) hydrochloride (PAH), the dissociated PD oligomers undergo covalent crosslinking in situ, leading to the formation of a reconstructed PDPA coating enriched with stable amino groups through thorough crosslinking. The PDPA coating demonstrates superior chemical and mechanical stability compared to PD, while enhancing multifunctional properties and offering improved surface functional modification potential. The PDPA coating holds promise in materials science, biomedical engineering, and nanotechnology, enabling versatile surface modification and functionalization in extreme conditions.
2025, 36(10): 110747
doi: 10.1016/j.cclet.2024.110747
摘要:
N6-methyladenine (6mA) is a prevalent DNA modification and is involved in a wide range of human diseases. Previous studies have indicated that 6mA is enriched in mitochondrial DNA (mtDNA) of mammals. By employing an evolved adenine deaminase, we developed a deaminase-mediated sequencing (DM-seq) method that could achieve genome-wide mapping of 6mA in mammalian mtDNA at single-base resolution. In this study, we used an engineered adenine deaminase, known as TadA8e protein, to map 6mA in mtDNA of hepatocellular carcinoma (HCC) by DM-seq. Through high-throughput sequencing, we identified sixteen 6mA sites in both HCC and adjacent normal tissue mtDNA. The results revealed an increased overall 6mA level in mtDNA associated with HCC. Furthermore, an elevation in 6mA level was observed alongside a decrease in the mRNA levels of the corresponding genes, indicating that increased 6mA level hindered transcription processes related to these genes. These findings demonstrate that 6mA in mtDNA is correlated with HCC and provide evidence supporting the inhibitory effect of elevated 6mA level on subsequent transcriptional activity. This research illuminates the intricate relationship between 6mA modification and transcriptional regulation in the context of HCC, offering valuable insights into the role of 6mA modification in HCC pathogenesis.
N6-methyladenine (6mA) is a prevalent DNA modification and is involved in a wide range of human diseases. Previous studies have indicated that 6mA is enriched in mitochondrial DNA (mtDNA) of mammals. By employing an evolved adenine deaminase, we developed a deaminase-mediated sequencing (DM-seq) method that could achieve genome-wide mapping of 6mA in mammalian mtDNA at single-base resolution. In this study, we used an engineered adenine deaminase, known as TadA8e protein, to map 6mA in mtDNA of hepatocellular carcinoma (HCC) by DM-seq. Through high-throughput sequencing, we identified sixteen 6mA sites in both HCC and adjacent normal tissue mtDNA. The results revealed an increased overall 6mA level in mtDNA associated with HCC. Furthermore, an elevation in 6mA level was observed alongside a decrease in the mRNA levels of the corresponding genes, indicating that increased 6mA level hindered transcription processes related to these genes. These findings demonstrate that 6mA in mtDNA is correlated with HCC and provide evidence supporting the inhibitory effect of elevated 6mA level on subsequent transcriptional activity. This research illuminates the intricate relationship between 6mA modification and transcriptional regulation in the context of HCC, offering valuable insights into the role of 6mA modification in HCC pathogenesis.
2025, 36(10): 110748
doi: 10.1016/j.cclet.2024.110748
摘要:
The performance and price of copper-based micro linear products are determined by the diameter uniformity. How to accurately detect the wire diameter of long-length copper based micro linear products without cutting or damage has always been a technical concern for production enterprises. Herein, a novel approach was developed for nondestructive detection of the average diameter at any given segment of a long copper wire by assessing the adsorption capacity of arginine on its surface. The amount of adsorbent on the surface of the copper wire exhibits a positive correlation with the area, which can be detected by extractive electrospray ionization mass spectrometry (EESI-MS) after online elution with ammonia. The experimental results demonstrated that the analysis can be completed within 15 min, with a good linear relationship between copper wires with different diameters and the adsorption capacity of arginine. The linear correlation coefficient R2 was 0.995, the relative standard deviation was 1.10%-2.81%, and the detection limit reached 2.5 µm (length of segment = 4 cm), showing potential applications for facile measurement of the average diameter of various metal wires.
The performance and price of copper-based micro linear products are determined by the diameter uniformity. How to accurately detect the wire diameter of long-length copper based micro linear products without cutting or damage has always been a technical concern for production enterprises. Herein, a novel approach was developed for nondestructive detection of the average diameter at any given segment of a long copper wire by assessing the adsorption capacity of arginine on its surface. The amount of adsorbent on the surface of the copper wire exhibits a positive correlation with the area, which can be detected by extractive electrospray ionization mass spectrometry (EESI-MS) after online elution with ammonia. The experimental results demonstrated that the analysis can be completed within 15 min, with a good linear relationship between copper wires with different diameters and the adsorption capacity of arginine. The linear correlation coefficient R2 was 0.995, the relative standard deviation was 1.10%-2.81%, and the detection limit reached 2.5 µm (length of segment = 4 cm), showing potential applications for facile measurement of the average diameter of various metal wires.
2025, 36(10): 110756
doi: 10.1016/j.cclet.2024.110756
摘要:
Reader proteins that bind specific methyllysine are important to biological functions of lysine methylation, but readers of many methyllysine sites are still unknown. Therefore, development of covalent probes is important to identify readers from cell samples so as to understand biological roles of lysine methylation. Generally, readers bind methyllysine via aromatic cages that contain tryptophan, tyrosine and phenylalanine, that offer a unique motif for selective crosslinking. We recently reported a site-selective tryptophan crosslinking strategy based on dimethylsulfonium that mimics dimethyllysine to crosslink tryptophan in aromatic cages of readers. Since tyrosine is a key residue for binding affinity to methyllysine, especially some readers that do not contain tryptophan residues in the binding pocket. Here we developed strategies of site-selective crosslinking to tyrosine. Ultraviolet (UV) source was applied to excite tyrosine at neutral pH or phenoxide at basic pH, and subsequent single-electron transfer (SET) from Tyr* to sulfonium inside the binding pocket enables selective crosslinking. In consequence, methyllysine readers with tyrosine-containing aromatic cages could be selectively crosslinked by site-specific sulfonium peptide probes. In addition, we expanded substrates from aromatic cages to tyrosine residues of proximate contact with sulfonium probes. The pair of LgBiT and SmBiT exhibited orthogonal crosslinking in complicated cell samples. As a result, we may expand sulfonium tools to target local tyrosine in future investigations.
Reader proteins that bind specific methyllysine are important to biological functions of lysine methylation, but readers of many methyllysine sites are still unknown. Therefore, development of covalent probes is important to identify readers from cell samples so as to understand biological roles of lysine methylation. Generally, readers bind methyllysine via aromatic cages that contain tryptophan, tyrosine and phenylalanine, that offer a unique motif for selective crosslinking. We recently reported a site-selective tryptophan crosslinking strategy based on dimethylsulfonium that mimics dimethyllysine to crosslink tryptophan in aromatic cages of readers. Since tyrosine is a key residue for binding affinity to methyllysine, especially some readers that do not contain tryptophan residues in the binding pocket. Here we developed strategies of site-selective crosslinking to tyrosine. Ultraviolet (UV) source was applied to excite tyrosine at neutral pH or phenoxide at basic pH, and subsequent single-electron transfer (SET) from Tyr* to sulfonium inside the binding pocket enables selective crosslinking. In consequence, methyllysine readers with tyrosine-containing aromatic cages could be selectively crosslinked by site-specific sulfonium peptide probes. In addition, we expanded substrates from aromatic cages to tyrosine residues of proximate contact with sulfonium probes. The pair of LgBiT and SmBiT exhibited orthogonal crosslinking in complicated cell samples. As a result, we may expand sulfonium tools to target local tyrosine in future investigations.
2025, 36(10): 110761
doi: 10.1016/j.cclet.2024.110761
摘要:
Covalent organic frameworks (COFs) have great potential as adsorbents due to their customizable functionality, low density and high porosity. However, COFs powder exists with poor processing and recycling performance. Moreover, due to the accumulation of COFs nanoparticles, it is not conducive to the full utilization of their surface functional groups. Currently, the strategy of COFs assembling into aerogel can be a good solution to this problem. Herein, we successfully synthesize composite aerogels (CSR) by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate. Sodium alginate in the composite improves the mechanical properties of the aerogel, and graphene provides a template for the in-situ growth of COFs. Impressively, CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs. The prepared CSR aerogels exhibit porous, low density, good processability and good mechanical properties. Among them, the density of CSR-N-1.6 is only 5 mg/cm3, which is the lowest density among the reported COF aerogels so far. Due to these remarkable properties, CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants (organic dyes and antibiotics) from polluted water. In addition, it is also possible to visually recognize the presence of antibiotics by fluorescence detection. This work not only provides a new strategy for synthesizing COF aerogels, but also accelerates the practical application of COF aerogels and contributes to environmental remediation.
Covalent organic frameworks (COFs) have great potential as adsorbents due to their customizable functionality, low density and high porosity. However, COFs powder exists with poor processing and recycling performance. Moreover, due to the accumulation of COFs nanoparticles, it is not conducive to the full utilization of their surface functional groups. Currently, the strategy of COFs assembling into aerogel can be a good solution to this problem. Herein, we successfully synthesize composite aerogels (CSR) by in-situ self-assembly of two-dimensional COFs and graphene based on crosslinking of sodium alginate. Sodium alginate in the composite improves the mechanical properties of the aerogel, and graphene provides a template for the in-situ growth of COFs. Impressively, CSR aerogels with different COFs and sizes can be prepared by changing the moiety of the ligand and modulating the addition amount of COFs. The prepared CSR aerogels exhibit porous, low density, good processability and good mechanical properties. Among them, the density of CSR-N-1.6 is only 5 mg/cm3, which is the lowest density among the reported COF aerogels so far. Due to these remarkable properties, CSR aerogels perform excellent adsorption and recycling properties for the efficient and rapid removal of organic pollutants (organic dyes and antibiotics) from polluted water. In addition, it is also possible to visually recognize the presence of antibiotics by fluorescence detection. This work not only provides a new strategy for synthesizing COF aerogels, but also accelerates the practical application of COF aerogels and contributes to environmental remediation.
2025, 36(10): 110766
doi: 10.1016/j.cclet.2024.110766
摘要:
Polarity, as a crucial environmental characteristic, plays a significant role in numerous cellular physiological processes. Abnormal changes in polarity are closely associated with various diseases. However, existing tools still have certain limitations that hinder accurate detection of polarity. Therefore, there is a pressing need to develop powerful tools for precisely monitoring changes in polarity. In this study, we developed two dual-emissive fluorogenic dyes by innovatively introducing 1,3-dithio-2-heteroarsenic cyclopentane and 1,2-diselenocyclopentane respectively into the near-infrared (NIR) coumarin-benzopyranium skeleton to enhance their cellular uptake capability. Additionally, we synthesized the polarity-sensitive dual-emissive fluorogenic probe CSFNS, which exhibits high cellular uptake rate, by modifying the spironolactone (Aldactone) structure of CBA into spirolactam. CSFNS not only demonstrates excellent polarity sensitivity in vitro but is also successfully applied to visually monitor the polarity changes in various types of living cells, including healthy cells, cancer cells and drug-induced senescent cells.
Polarity, as a crucial environmental characteristic, plays a significant role in numerous cellular physiological processes. Abnormal changes in polarity are closely associated with various diseases. However, existing tools still have certain limitations that hinder accurate detection of polarity. Therefore, there is a pressing need to develop powerful tools for precisely monitoring changes in polarity. In this study, we developed two dual-emissive fluorogenic dyes by innovatively introducing 1,3-dithio-2-heteroarsenic cyclopentane and 1,2-diselenocyclopentane respectively into the near-infrared (NIR) coumarin-benzopyranium skeleton to enhance their cellular uptake capability. Additionally, we synthesized the polarity-sensitive dual-emissive fluorogenic probe CSFNS, which exhibits high cellular uptake rate, by modifying the spironolactone (Aldactone) structure of CBA into spirolactam. CSFNS not only demonstrates excellent polarity sensitivity in vitro but is also successfully applied to visually monitor the polarity changes in various types of living cells, including healthy cells, cancer cells and drug-induced senescent cells.
2025, 36(10): 110769
doi: 10.1016/j.cclet.2024.110769
摘要:
Two unusual sesquiterpenoids, irpexlactones A (1) and B (2), were isolated from cultures of the basidiomycete Irpex lacteus. Their structures were established by means of spectroscopic methods, the single crystal X-ray diffraction, as well as electronic circular dichroism (ECD) calculations. They possess a novel carbon skeleton with a 5/6/3-fused ring system that may derive from tremulane type sesquiterpenoids with ring-rearrangement. Both compounds show significant inhibitory activities against nitric oxide production with half maximal inhibitory concentration (IC50) values of 2.2 and 1.4 µmol/L, respectively. Their anti-inflammatory effects were further evaluated by enzyme-linked immunosorbent assay (ELISA) and Western blot.
Two unusual sesquiterpenoids, irpexlactones A (1) and B (2), were isolated from cultures of the basidiomycete Irpex lacteus. Their structures were established by means of spectroscopic methods, the single crystal X-ray diffraction, as well as electronic circular dichroism (ECD) calculations. They possess a novel carbon skeleton with a 5/6/3-fused ring system that may derive from tremulane type sesquiterpenoids with ring-rearrangement. Both compounds show significant inhibitory activities against nitric oxide production with half maximal inhibitory concentration (IC50) values of 2.2 and 1.4 µmol/L, respectively. Their anti-inflammatory effects were further evaluated by enzyme-linked immunosorbent assay (ELISA) and Western blot.
2025, 36(10): 110770
doi: 10.1016/j.cclet.2024.110770
摘要:
Designing and synthesizing nanomedicines with multi-modal tumor therapeutic capabilities is the key to cancer treatment. Herein, we prepared MICG nanoparticles (NPs) by assembling glucose oxidase (GOx) and indocyanine green (ICG) with manganese carbonate (MnCO3) NPs for starvation therapy cascaded chemodynamic therapy, enhanced phototherapy and immune activation. In MICG NPs, the GOx consumes intratumoral glucose resulting in starvation therapy, and simultaneously produces H2O2 and decreases pH in tumor. The intensified acidic tumor environment promotes the decomposition of MnCO3 NPs to release Mn2+. The Mn2+ further catalyzes H2O2 to generate hydroxyl radical for chemodynamic therapy. While ICG can generate singlet oxygen (1O2) and heat to kill cancer cells through phototherapy mechanism. The hydroxyl radical and 1O2 will further accelerate the oxidative stress, intensify immunogenic cell death, induce dendritic cell maturation, and thus activate systemic immunity. This work provides a new therapeutic platform for combining therapy of tumor.
Designing and synthesizing nanomedicines with multi-modal tumor therapeutic capabilities is the key to cancer treatment. Herein, we prepared MICG nanoparticles (NPs) by assembling glucose oxidase (GOx) and indocyanine green (ICG) with manganese carbonate (MnCO3) NPs for starvation therapy cascaded chemodynamic therapy, enhanced phototherapy and immune activation. In MICG NPs, the GOx consumes intratumoral glucose resulting in starvation therapy, and simultaneously produces H2O2 and decreases pH in tumor. The intensified acidic tumor environment promotes the decomposition of MnCO3 NPs to release Mn2+. The Mn2+ further catalyzes H2O2 to generate hydroxyl radical for chemodynamic therapy. While ICG can generate singlet oxygen (1O2) and heat to kill cancer cells through phototherapy mechanism. The hydroxyl radical and 1O2 will further accelerate the oxidative stress, intensify immunogenic cell death, induce dendritic cell maturation, and thus activate systemic immunity. This work provides a new therapeutic platform for combining therapy of tumor.
2025, 36(10): 110772
doi: 10.1016/j.cclet.2024.110772
摘要:
The fluorophores Xan-OH and Xan-OH/FBS, based on xanthene structure, possess an effective near-infrared absorption, near-infrared Ⅱ (NIR-Ⅱ) fluorescent imaging ability, and excellent photothermal property. Xan-OH/FBS also has good viscosity-sensitivity, enabling the real-time in vivo visualization of acute liver injury induced by CCl4. Moreover, the photothermal conversion coefficient of Xan-OH and Xan-OH/FBS under 808 nm laser irradiation are significant (27.53% and 26.77%, respectively), which could realize NIR-Ⅱ fluorescence imaging-guided photothermal therapy for HeLa xenograft tumor. Given these promising characteristics, Xan-OH/FBS is an efficient NIR-Ⅱ fluorescent imaging agent for acute liver injury and a potential photothermal therapeutic agent for tumor.
The fluorophores Xan-OH and Xan-OH/FBS, based on xanthene structure, possess an effective near-infrared absorption, near-infrared Ⅱ (NIR-Ⅱ) fluorescent imaging ability, and excellent photothermal property. Xan-OH/FBS also has good viscosity-sensitivity, enabling the real-time in vivo visualization of acute liver injury induced by CCl4. Moreover, the photothermal conversion coefficient of Xan-OH and Xan-OH/FBS under 808 nm laser irradiation are significant (27.53% and 26.77%, respectively), which could realize NIR-Ⅱ fluorescence imaging-guided photothermal therapy for HeLa xenograft tumor. Given these promising characteristics, Xan-OH/FBS is an efficient NIR-Ⅱ fluorescent imaging agent for acute liver injury and a potential photothermal therapeutic agent for tumor.
2025, 36(10): 110773
doi: 10.1016/j.cclet.2024.110773
摘要:
Glycyrrhetinic acid (GA) sheds new light on liver-targeted therapy due to high-specific accumulation to GA receptors in liver, however, the limitation of commonly used macromolecular GA modification approaches as well as the application gap across various vector have constrained its use. In this study, we proposed a novel perspective to break out, disulfide bonds (SS) were employed as linkage to facilitate GA modification, which allowed further connections with various carriers, while provided additional glutathione (GSH)-responsive property. The superiority of GA-disulfide conjunction was validated using mesoporous silica nanoparticles (MSN) as model carriers, chemotherapeutic drug (doxorubicin) and photosensitizer (indocyanine green) were loaded into MSN-SS-GA to further achieve chemo-photothermal synergistic anti-tumor therapy. Based on results from multiple evaluations, the GA-disulfide drafted MSN (DI/MSN-SS-GA) demonstrated expected liver tumor targeting effect and exhibited GSH-stimuli release property to reduce preleakage. Taken together, this study presents an effective chemo-photothermal therapy for liver cancer (88.26%), offers a potential, robust and straightforward strategy on GA application for enhancing liver targeting therapy.
Glycyrrhetinic acid (GA) sheds new light on liver-targeted therapy due to high-specific accumulation to GA receptors in liver, however, the limitation of commonly used macromolecular GA modification approaches as well as the application gap across various vector have constrained its use. In this study, we proposed a novel perspective to break out, disulfide bonds (SS) were employed as linkage to facilitate GA modification, which allowed further connections with various carriers, while provided additional glutathione (GSH)-responsive property. The superiority of GA-disulfide conjunction was validated using mesoporous silica nanoparticles (MSN) as model carriers, chemotherapeutic drug (doxorubicin) and photosensitizer (indocyanine green) were loaded into MSN-SS-GA to further achieve chemo-photothermal synergistic anti-tumor therapy. Based on results from multiple evaluations, the GA-disulfide drafted MSN (DI/MSN-SS-GA) demonstrated expected liver tumor targeting effect and exhibited GSH-stimuli release property to reduce preleakage. Taken together, this study presents an effective chemo-photothermal therapy for liver cancer (88.26%), offers a potential, robust and straightforward strategy on GA application for enhancing liver targeting therapy.
2025, 36(10): 110774
doi: 10.1016/j.cclet.2024.110774
摘要:
MicroRNAs (miRNAs) are abundant in the brain and mounting evidence suggests their involvement in the critical processes such as neurodevelopment, synaptic plasticity, and the development of neurodegenerative diseases. Thus, miRNAs may be promising therapeutic drugs for the treatment of neurodegenerative disorders. However, naked miRNAs are not able to enter cells directly, especially brain cells. Therefore, suitable carriers for safe and efficient miRNA delivery to brain cells are of great importance. Chitosan nanoparticles, with the excellent properties such as good compatibility and brilliant degradability, may act as a promising carrier for miRNA drug delivery. In this study, chitosan nanoparticles were prepared and their properties such as particle size, zeta potential and encapsulation efficiency were optimized to encapsulate miRNAs. The delivery efficiency of miRNA-loaded nanoparticles was then evaluated in both neuronal and microglia cells. The results demonstrated chitosan nanoparticles encapsulated miRNAs efficiently and showed excellent sustained releasing in vitro. Moreover, chitosan nanoparticles delivered miRNA to both neurons and microglia with very low toxicity and high efficiency. In conclusion, chitosan nanoparticles are promising carriers for the delivery of miRNAs to brain cells, which may be used for the early intervention and treatment of neurodegenerative disorders.
MicroRNAs (miRNAs) are abundant in the brain and mounting evidence suggests their involvement in the critical processes such as neurodevelopment, synaptic plasticity, and the development of neurodegenerative diseases. Thus, miRNAs may be promising therapeutic drugs for the treatment of neurodegenerative disorders. However, naked miRNAs are not able to enter cells directly, especially brain cells. Therefore, suitable carriers for safe and efficient miRNA delivery to brain cells are of great importance. Chitosan nanoparticles, with the excellent properties such as good compatibility and brilliant degradability, may act as a promising carrier for miRNA drug delivery. In this study, chitosan nanoparticles were prepared and their properties such as particle size, zeta potential and encapsulation efficiency were optimized to encapsulate miRNAs. The delivery efficiency of miRNA-loaded nanoparticles was then evaluated in both neuronal and microglia cells. The results demonstrated chitosan nanoparticles encapsulated miRNAs efficiently and showed excellent sustained releasing in vitro. Moreover, chitosan nanoparticles delivered miRNA to both neurons and microglia with very low toxicity and high efficiency. In conclusion, chitosan nanoparticles are promising carriers for the delivery of miRNAs to brain cells, which may be used for the early intervention and treatment of neurodegenerative disorders.
2025, 36(10): 110775
doi: 10.1016/j.cclet.2024.110775
摘要:
Nanomedicine holds considerable promise for advancing cancer therapy, however, effective delivery of drugs to solid tumors remains a challenge due to rapid systemic clearance and inefficient cellular uptake. Herein, we have developed a novel charge-reversible nanogel to deliver paclitaxel (PTX) dimers (DPP) with enhanced stability and targeting precision. The nanogels exhibit a dynamic charge-reversal mechanism responsive to the acidic tumor microenvironment (TME), optimizing the cellular uptake of prodrugs. In the high glutathione (GSH) conditions within cancer cells, the disulfide bonds in the DPP are cleaved, resulting in the intracellular release of active PTX and reduced drug toxicity to normal cells. In vivo pharmacokinetic studies revealed an extended plasma elimination half-life for the charge-reversible nanocarriers, and antitumor efficacy studies demonstrated superior tumor suppression with minimal systemic toxicity. This research underscores the potential of integrating charge-reversal and responsive release mechanisms into one nanocarrier system, balancing the long circulation and high tumor cell internalization capacity of the nanocarrier, and providing a promising strategy for targeted delivery of nanomedicine.
Nanomedicine holds considerable promise for advancing cancer therapy, however, effective delivery of drugs to solid tumors remains a challenge due to rapid systemic clearance and inefficient cellular uptake. Herein, we have developed a novel charge-reversible nanogel to deliver paclitaxel (PTX) dimers (DPP) with enhanced stability and targeting precision. The nanogels exhibit a dynamic charge-reversal mechanism responsive to the acidic tumor microenvironment (TME), optimizing the cellular uptake of prodrugs. In the high glutathione (GSH) conditions within cancer cells, the disulfide bonds in the DPP are cleaved, resulting in the intracellular release of active PTX and reduced drug toxicity to normal cells. In vivo pharmacokinetic studies revealed an extended plasma elimination half-life for the charge-reversible nanocarriers, and antitumor efficacy studies demonstrated superior tumor suppression with minimal systemic toxicity. This research underscores the potential of integrating charge-reversal and responsive release mechanisms into one nanocarrier system, balancing the long circulation and high tumor cell internalization capacity of the nanocarrier, and providing a promising strategy for targeted delivery of nanomedicine.
2025, 36(10): 110776
doi: 10.1016/j.cclet.2024.110776
摘要:
Bisphenol A (BPA) has threatened ecological safety and human health due to its endocrine disrupting effect and widely diffused in the environment. Peroxymonosulfate (PMS) based on oxidation technology exhibits good potential for environmental remediation whereas the highly efficient activator needs to be developed. Herein, the BiOBr (BOB) was synthesized to efficiently activate PMS to remove 95.6% of BPA within 60 min. The observed rate constant of BPA removal in BOB/PMS system is 0.049 min-1, which is 60 and 148 times to that of the BOB and PMS processes separately and 129 times to the compared BiOCl (BOC)/PMS system, respectively. Comparison experiments and analytic methods demonstrate that BOB with a larger content of oxygen vacancies (Ov) can act as the bridge of electron transfer between Bi3+/Bi4+ with PMS to enhance the activation ability for PMS, resulting in the production of abundant reactive oxygen species (O2•− and 1O2). Additionally, the breakdown processes of BPA and the toxicity of its byproducts were uncovered, and the potential for actual water treatment was evaluated to confirm the detoxification, efficiency, stability and practical use of the BOB/PMS system for eliminating BPA. This study may widen the application of traditional semiconductors and develop the cost-effective PMS activation methods for environmental remediation.
Bisphenol A (BPA) has threatened ecological safety and human health due to its endocrine disrupting effect and widely diffused in the environment. Peroxymonosulfate (PMS) based on oxidation technology exhibits good potential for environmental remediation whereas the highly efficient activator needs to be developed. Herein, the BiOBr (BOB) was synthesized to efficiently activate PMS to remove 95.6% of BPA within 60 min. The observed rate constant of BPA removal in BOB/PMS system is 0.049 min-1, which is 60 and 148 times to that of the BOB and PMS processes separately and 129 times to the compared BiOCl (BOC)/PMS system, respectively. Comparison experiments and analytic methods demonstrate that BOB with a larger content of oxygen vacancies (Ov) can act as the bridge of electron transfer between Bi3+/Bi4+ with PMS to enhance the activation ability for PMS, resulting in the production of abundant reactive oxygen species (O2•− and 1O2). Additionally, the breakdown processes of BPA and the toxicity of its byproducts were uncovered, and the potential for actual water treatment was evaluated to confirm the detoxification, efficiency, stability and practical use of the BOB/PMS system for eliminating BPA. This study may widen the application of traditional semiconductors and develop the cost-effective PMS activation methods for environmental remediation.
2025, 36(10): 110778
doi: 10.1016/j.cclet.2024.110778
摘要:
The concurrence of primary sclerosing cholangitis (PSC) and inflammatory bowel disease (IBD) presents a therapeutic challenge, often necessitating liver transplantation in severe cases. Paeoniflorin (PAE), known for its immunomodulatory and anti-inflammatory properties but with very high-water solubility and low permeability, is formulated into a paeoniflorin/phospholipid complex microemulsion (PAE-ME) to enhance its delivery in this study. It demonstrated the PAE-ME's macrophage-regulating ability to repolarize the pro-inflammatory M1 subtype to the anti-inflammatory M2 type and reduce inflammatory cytokine release. In a PSC-IBD mouse model, PAE-ME alleviated the symptoms and regulated bile acid balance. Given the close connection and crosstalk between the liver and intestine, PAE-ME yielded a synergistic therapeutic effect on both the liver and intestinal lesions. These findings suggest a promising translational approach for complex comorbidities by acting on the liver-gut axis.
The concurrence of primary sclerosing cholangitis (PSC) and inflammatory bowel disease (IBD) presents a therapeutic challenge, often necessitating liver transplantation in severe cases. Paeoniflorin (PAE), known for its immunomodulatory and anti-inflammatory properties but with very high-water solubility and low permeability, is formulated into a paeoniflorin/phospholipid complex microemulsion (PAE-ME) to enhance its delivery in this study. It demonstrated the PAE-ME's macrophage-regulating ability to repolarize the pro-inflammatory M1 subtype to the anti-inflammatory M2 type and reduce inflammatory cytokine release. In a PSC-IBD mouse model, PAE-ME alleviated the symptoms and regulated bile acid balance. Given the close connection and crosstalk between the liver and intestine, PAE-ME yielded a synergistic therapeutic effect on both the liver and intestinal lesions. These findings suggest a promising translational approach for complex comorbidities by acting on the liver-gut axis.
2025, 36(10): 110779
doi: 10.1016/j.cclet.2024.110779
摘要:
Utilizing interfacial interaction between different components of a heterojunction to induce defect formation may be an interesting approach for improving the catalytic performance. Here, introducing 3 nm CdS clusters (S) on NH2−MIL-125(Ti) nanosheets (NMT-NS) to construct the heterojunction catalysts (Sx/NMT-NS) can induce the generation of abundant defects and Ti3+ sites due to the lattice distortion of NMT-NS and the transfer of interfacial charges. These defects and Ti3+ sites can chemisorb benzyl alcohol (BZO) molecules through a C-O⋯Ti coordination while capture and activate O2 molecules from air. Furthermore, Z-scheme heterojunction between CdS clusters and NMT-NS optimizes the transfer and separation of photogenerated electrons-holes, thus accelerating the production of ∙O2-. Therefore, S1.8/NMT-NS achieves a highly efficient conversion of benzylamine (BZA) (> 99%) and BZO to N-benzylidene benzylamine (N-BZA) in air atmosphere under visible light, with a selectivity of 99%. Finally, a photocatalytic mechanism involving the activation of reactants molecule and the transfer of photogenerated carriers is propounded at molecular level.
Utilizing interfacial interaction between different components of a heterojunction to induce defect formation may be an interesting approach for improving the catalytic performance. Here, introducing 3 nm CdS clusters (S) on NH2−MIL-125(Ti) nanosheets (NMT-NS) to construct the heterojunction catalysts (Sx/NMT-NS) can induce the generation of abundant defects and Ti3+ sites due to the lattice distortion of NMT-NS and the transfer of interfacial charges. These defects and Ti3+ sites can chemisorb benzyl alcohol (BZO) molecules through a C-O⋯Ti coordination while capture and activate O2 molecules from air. Furthermore, Z-scheme heterojunction between CdS clusters and NMT-NS optimizes the transfer and separation of photogenerated electrons-holes, thus accelerating the production of ∙O2-. Therefore, S1.8/NMT-NS achieves a highly efficient conversion of benzylamine (BZA) (> 99%) and BZO to N-benzylidene benzylamine (N-BZA) in air atmosphere under visible light, with a selectivity of 99%. Finally, a photocatalytic mechanism involving the activation of reactants molecule and the transfer of photogenerated carriers is propounded at molecular level.
2025, 36(10): 110780
doi: 10.1016/j.cclet.2024.110780
摘要:
The initial step in the resource utilization of Chinese medicine residues (CMRs) involves dehydration pretreatment, which results in high concentrations of organic wastewater and leads to environmental pollution. Meanwhile, to address the issue of anaerobic systems failing due to acidification under shock loading, a microaerobic expanded granular sludge bed (EGSB) and moving bed sequencing batch reactor (MBSBR) combined process was proposed in this study. Microaeration facilitated hydrolysis, improved the removal of nitrogen and phosphorus pollutants, maintained a low concentration of volatile fatty acids (VFAs), and enhanced system stability. In addition, microaeration promoted microbial richness and diversity, enriching three phyla: Bacteroidota, Synergistota and Firmicutes associated with hydrolytic acidification. Furthermore, aeration intensity in MBSBR was optimized. Elevated levels of dissolved oxygen (DO) impacted biofilm structure, suppressed denitrifying bacteria activity, led to nitrate accumulation, and hindered simultaneous nitrification and denitrification (SND). Maintaining a DO concentration of 2 mg/L enhanced the removal of nitrogen and phosphorus while conserving energy. The combined process achieved removal efficiencies of 98.25%, 90.49%, and 98.55% for chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP), respectively. Typical pollutants liquiritin (LQ) and glycyrrhizic acid (GA) were completely degraded. This study presents an innovative approach for the treatment of high-concentration organic wastewater and provides a reliable solution for the pollution control in utilization of CMRs resources.
The initial step in the resource utilization of Chinese medicine residues (CMRs) involves dehydration pretreatment, which results in high concentrations of organic wastewater and leads to environmental pollution. Meanwhile, to address the issue of anaerobic systems failing due to acidification under shock loading, a microaerobic expanded granular sludge bed (EGSB) and moving bed sequencing batch reactor (MBSBR) combined process was proposed in this study. Microaeration facilitated hydrolysis, improved the removal of nitrogen and phosphorus pollutants, maintained a low concentration of volatile fatty acids (VFAs), and enhanced system stability. In addition, microaeration promoted microbial richness and diversity, enriching three phyla: Bacteroidota, Synergistota and Firmicutes associated with hydrolytic acidification. Furthermore, aeration intensity in MBSBR was optimized. Elevated levels of dissolved oxygen (DO) impacted biofilm structure, suppressed denitrifying bacteria activity, led to nitrate accumulation, and hindered simultaneous nitrification and denitrification (SND). Maintaining a DO concentration of 2 mg/L enhanced the removal of nitrogen and phosphorus while conserving energy. The combined process achieved removal efficiencies of 98.25%, 90.49%, and 98.55% for chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP), respectively. Typical pollutants liquiritin (LQ) and glycyrrhizic acid (GA) were completely degraded. This study presents an innovative approach for the treatment of high-concentration organic wastewater and provides a reliable solution for the pollution control in utilization of CMRs resources.
2025, 36(10): 110781
doi: 10.1016/j.cclet.2024.110781
摘要:
Gravity-driven membrane filtration (GDM) has increasingly captured researchers' attention due to its low energy consumption and operation & maintenance. However, severe membrane fouling and permeate DOC increase restricted GDM's widespread application. This study combined granular active carbon (GAC) and magnetic particles to address this issue and results suggested that GDM3 achieved highly effective pollutant removals (85% CODMn, 95% UV254, and 65% DOC) and significant flux improvement (96%) than GDM itself. GAC pretreatment before the membrane mainly helped to reduce pollutant load and improve permeated quality while magnetic particles in situ on the membrane surface contributed to engineering more open and connected structures with less extracellular polymeric substance (EPS) and soluble microbial products (SMP) than other GDM groups due to their bioeffect. GDM3 was cost-effective and had the lowest total cost with a decrease of 7.5% and 5.7% to GDM1 and GDM2. The findings provided a deep insight into the combined GAC and magnetic particles in GDM performance improvement and played a fundamental role in developing sustainable and environmentally friendly GDM processes.
Gravity-driven membrane filtration (GDM) has increasingly captured researchers' attention due to its low energy consumption and operation & maintenance. However, severe membrane fouling and permeate DOC increase restricted GDM's widespread application. This study combined granular active carbon (GAC) and magnetic particles to address this issue and results suggested that GDM3 achieved highly effective pollutant removals (85% CODMn, 95% UV254, and 65% DOC) and significant flux improvement (96%) than GDM itself. GAC pretreatment before the membrane mainly helped to reduce pollutant load and improve permeated quality while magnetic particles in situ on the membrane surface contributed to engineering more open and connected structures with less extracellular polymeric substance (EPS) and soluble microbial products (SMP) than other GDM groups due to their bioeffect. GDM3 was cost-effective and had the lowest total cost with a decrease of 7.5% and 5.7% to GDM1 and GDM2. The findings provided a deep insight into the combined GAC and magnetic particles in GDM performance improvement and played a fundamental role in developing sustainable and environmentally friendly GDM processes.
2025, 36(10): 110782
doi: 10.1016/j.cclet.2024.110782
摘要:
Mercury ions (Hg2+) and bacteria are widely spread in water pollution and pose a great threat to human health and the environment. Herein, a multifunctional COF DmtaTph with significant Hg2+ adsorption capability and continuous sunlight-driven sterilization property is designed and synthesized by introducing thioether and photosensitive porphyrin in a single molecule. The obtained COF displays a high Hg2+ adsorption capacity of 657.9 mg/g at 298 K and a superior antibacterial effect toward Escherichia coli and Staphylococcus aureus under sunlight irradiation. Mechanistic studies reveal that the strong coordination between S species and Hg2+ is the main driving force for high Hg2+ adsorption capability. The sterilization mechanism clarifies that the inactivation of bacteria is caused by 1O2 produced from DmtaTph with the assistance of light irradiation. Noteworthy, when DmtaTph is applied in the treatment of wastewater, it displays high Hg2+ removal efficiency and remarkable antibacterial effect under complex conditions. This study has demonstrated a promising strategy for designing multifunctional COF-based materials, offering great potential in tackling the problem of heavy metal ions and bacteria pollution in water.
Mercury ions (Hg2+) and bacteria are widely spread in water pollution and pose a great threat to human health and the environment. Herein, a multifunctional COF DmtaTph with significant Hg2+ adsorption capability and continuous sunlight-driven sterilization property is designed and synthesized by introducing thioether and photosensitive porphyrin in a single molecule. The obtained COF displays a high Hg2+ adsorption capacity of 657.9 mg/g at 298 K and a superior antibacterial effect toward Escherichia coli and Staphylococcus aureus under sunlight irradiation. Mechanistic studies reveal that the strong coordination between S species and Hg2+ is the main driving force for high Hg2+ adsorption capability. The sterilization mechanism clarifies that the inactivation of bacteria is caused by 1O2 produced from DmtaTph with the assistance of light irradiation. Noteworthy, when DmtaTph is applied in the treatment of wastewater, it displays high Hg2+ removal efficiency and remarkable antibacterial effect under complex conditions. This study has demonstrated a promising strategy for designing multifunctional COF-based materials, offering great potential in tackling the problem of heavy metal ions and bacteria pollution in water.
2025, 36(10): 110788
doi: 10.1016/j.cclet.2024.110788
摘要:
Exploring efficient catalyst is critical for the application of persulfate-based advanced oxidation processes (AOPs) for environment remediation. Herein, perovskite CoTiO3 was demonstrated an efficient catalyst for peroxymonosulfate (PMS) activation, which shows superior performance compared with single metal oxide system and homogenous systems: It removes 98.2% of hydroxychloroquine (HCQ, drugs for effective treatment of COVID-19) within 20 min at low dose of PMS (0.5 mmol/L), showing high tolerance to the environmental pH range (3.5–10.6) and significant versatility for various refractory organics. Combined with the material characterization and DFT calculations, it is found Co–O–Ti bond in CoTiO3 serves as an electron mediator to facilitate the rapid redox cycles of Co2+/Co3+ during activation process, thus maintaining the high catalytic activity. Further mechanism exploration showed that fast regeneration of Co2+ ensures the production of high concentration of SO4•− and •OH, thus securing the rapid degradation of HCQ. Moreover, a designed CoTiO3-CNT-PVDF membrane reactor can effectively remove refractory pollutant via practically feasible filter-through mode, which delivers a highest removal efficiency and longest operation duration compared with previous developed membrane-based AOPs. The corresponding mechanism revealed in this work can serve as guidelines for the design of advanced heterogenous catalysts and membrane reactors for AOPs.
Exploring efficient catalyst is critical for the application of persulfate-based advanced oxidation processes (AOPs) for environment remediation. Herein, perovskite CoTiO3 was demonstrated an efficient catalyst for peroxymonosulfate (PMS) activation, which shows superior performance compared with single metal oxide system and homogenous systems: It removes 98.2% of hydroxychloroquine (HCQ, drugs for effective treatment of COVID-19) within 20 min at low dose of PMS (0.5 mmol/L), showing high tolerance to the environmental pH range (3.5–10.6) and significant versatility for various refractory organics. Combined with the material characterization and DFT calculations, it is found Co–O–Ti bond in CoTiO3 serves as an electron mediator to facilitate the rapid redox cycles of Co2+/Co3+ during activation process, thus maintaining the high catalytic activity. Further mechanism exploration showed that fast regeneration of Co2+ ensures the production of high concentration of SO4•− and •OH, thus securing the rapid degradation of HCQ. Moreover, a designed CoTiO3-CNT-PVDF membrane reactor can effectively remove refractory pollutant via practically feasible filter-through mode, which delivers a highest removal efficiency and longest operation duration compared with previous developed membrane-based AOPs. The corresponding mechanism revealed in this work can serve as guidelines for the design of advanced heterogenous catalysts and membrane reactors for AOPs.
2025, 36(10): 110793
doi: 10.1016/j.cclet.2024.110793
摘要:
Thin-film nanocomposite (TFN) membranes have garnered considerable attention for their potential to improve separation performance by incorporating nanomaterials. However, challenges such as these materials' uneven distribution and aggregation have hindered practical applications. While prior studies have largely concentrated on modifying nanosheets for compatibility with polymer matrices, the role of substrate pore size in influencing nanosheet distribution has been overlooked. In this work, MoS2 nanosheets were dispersed in an aqueous phase to fabricate TFN membranes, investigating the effect of substrate pore size relative to the nanosheets. By systematically varying the particle size of MoS2 and the pore size of the substrate, we reveal how these factors impact material distribution and structural uniformity within the membranes. Our findings reveal that larger substrate pores allow the MoS2-containing monomer solution to infiltrate more effectively, minimizing nanosheet aggregation. This enhances membrane performance by promoting better dispersion. Our results underscore the importance of considering the relative size of substrate pores and nanosheets in TFN membrane design, providing a pathway to improved material integration and higher membrane efficiency.
Thin-film nanocomposite (TFN) membranes have garnered considerable attention for their potential to improve separation performance by incorporating nanomaterials. However, challenges such as these materials' uneven distribution and aggregation have hindered practical applications. While prior studies have largely concentrated on modifying nanosheets for compatibility with polymer matrices, the role of substrate pore size in influencing nanosheet distribution has been overlooked. In this work, MoS2 nanosheets were dispersed in an aqueous phase to fabricate TFN membranes, investigating the effect of substrate pore size relative to the nanosheets. By systematically varying the particle size of MoS2 and the pore size of the substrate, we reveal how these factors impact material distribution and structural uniformity within the membranes. Our findings reveal that larger substrate pores allow the MoS2-containing monomer solution to infiltrate more effectively, minimizing nanosheet aggregation. This enhances membrane performance by promoting better dispersion. Our results underscore the importance of considering the relative size of substrate pores and nanosheets in TFN membrane design, providing a pathway to improved material integration and higher membrane efficiency.
2025, 36(10): 110794
doi: 10.1016/j.cclet.2024.110794
摘要:
Accurate classification of pulmonary nodules is critical for early diagnosis of lung cancer. However, non-invasive and accurate diagnosis of benign and malignant pulmonary nodules faces great challenges. In this study, we develop a nano zero-valent iron (nZVI)-assisted laser desorption/ionization mass spectrometry (LDI MS) platform, which enables ultra-high-throughput acquisition of abundant metabolic fingerprint information of serum in negative ion mode. We further recruit a large-scale multicenter prospective cohort and collect 1099 serum samples from participants with benign and malignant nodules. The accurate machine learning models are built and validated based on nZVI-assisted LDI MS metabolomics to achieve efficient classification of benign and malignant nodules. Using our established stacking ensemble learning model, the AUC of the ROC curve for benign and malignant lung nodule classification can be as high as 0.9, and the sensitivity can reach 85.5%, which is significantly better than existing clinical models. This work provides an integrated workflow from detection technology to diagnostic models for biomarker-based pulmonary nodule diagnosis, which would be widely used in rapid and large-scale screening of pulmonary nodules.
Accurate classification of pulmonary nodules is critical for early diagnosis of lung cancer. However, non-invasive and accurate diagnosis of benign and malignant pulmonary nodules faces great challenges. In this study, we develop a nano zero-valent iron (nZVI)-assisted laser desorption/ionization mass spectrometry (LDI MS) platform, which enables ultra-high-throughput acquisition of abundant metabolic fingerprint information of serum in negative ion mode. We further recruit a large-scale multicenter prospective cohort and collect 1099 serum samples from participants with benign and malignant nodules. The accurate machine learning models are built and validated based on nZVI-assisted LDI MS metabolomics to achieve efficient classification of benign and malignant nodules. Using our established stacking ensemble learning model, the AUC of the ROC curve for benign and malignant lung nodule classification can be as high as 0.9, and the sensitivity can reach 85.5%, which is significantly better than existing clinical models. This work provides an integrated workflow from detection technology to diagnostic models for biomarker-based pulmonary nodule diagnosis, which would be widely used in rapid and large-scale screening of pulmonary nodules.
2025, 36(10): 110795
doi: 10.1016/j.cclet.2024.110795
摘要:
Psoriasis is a common and chronic immune-mediated disorder that severely impacts the life quality of patients. Phosphodiesterase-4 (PDE4) inhibitors have attracted significant interests in the psoriasis treatment due to their ability to suppress the inflammatory cascades. In this study, extensive screening of an in-house library of 1200 Chinese medicinal plant extracts identified Platycladus orientalis (L.) Franco (P. orientalis) as a potent PDE4 inhibitor, exhibiting 42.7% inhibition at 0.2 µg/mL. Subsequent bioassay-guided isolation revealed flavonoids, particularly amentoflavone (AMF), as the principal component responsible for PDE4 inhibition. To enrich the effective ingredients, a purification protocol using microporous resin was developed, yielding a flavonoid-rich extract (FLDs) that efficiently increased AMF content from 6.2% to 72.3% and improved PDE4 inhibitory activity to 74.2% at 0.2 µg/mL. Notably, P. orientalis with favorable safety profiles demonstrated superior in vitro and in vivo anti-psoriasis effects to both AMF and the approved PDE4 inhibitor apremilast. These findings highlight the potential of P. orientalis as a novel therapeutic agent for psoriasis and provide valuable insights for its development in psoriasis treatment.
Psoriasis is a common and chronic immune-mediated disorder that severely impacts the life quality of patients. Phosphodiesterase-4 (PDE4) inhibitors have attracted significant interests in the psoriasis treatment due to their ability to suppress the inflammatory cascades. In this study, extensive screening of an in-house library of 1200 Chinese medicinal plant extracts identified Platycladus orientalis (L.) Franco (P. orientalis) as a potent PDE4 inhibitor, exhibiting 42.7% inhibition at 0.2 µg/mL. Subsequent bioassay-guided isolation revealed flavonoids, particularly amentoflavone (AMF), as the principal component responsible for PDE4 inhibition. To enrich the effective ingredients, a purification protocol using microporous resin was developed, yielding a flavonoid-rich extract (FLDs) that efficiently increased AMF content from 6.2% to 72.3% and improved PDE4 inhibitory activity to 74.2% at 0.2 µg/mL. Notably, P. orientalis with favorable safety profiles demonstrated superior in vitro and in vivo anti-psoriasis effects to both AMF and the approved PDE4 inhibitor apremilast. These findings highlight the potential of P. orientalis as a novel therapeutic agent for psoriasis and provide valuable insights for its development in psoriasis treatment.
2025, 36(10): 110796
doi: 10.1016/j.cclet.2024.110796
摘要:
The surface physiochemical features of nanomedicine are essential for controlling biointerfacial interactions in biological compartments and achieving the programmed delivery scenario to intracellular targets. This work presents a novel dynamic triple-transformable surface engineering strategy that can adapt to sequential variable biological microenvironments and intelligently managing the previously acknowledged biological obstacles. By employing click chemistry, the surface of a classical PEGylated pDNA delivery nanoparticles were tethered with a multiple of charge-reversible polymers to endow the dynamic biointerfacial surroundings. Crucially, the dynamic surroundings had negative charge under physiological circumstances (pH 7.4), which inhibited structural disintegration brought on by charged biological species and anionic nuclease degradation. In addition, by regulating the first pass effect, the nanoparticles demonstrated appreciable stealth function that led to persistent systemic retention and improved bioavailability and consistent internalization into the targeted cells. In subsequence to cell endocytosis, translocation from the digestive endolysosomes to the targeted cytosol was facilitated due to acidification (endosomal pH 5.5) of the dynamic surroundings into highly positive charge, consequently leading to explosive disruptive effects on the endolysosomal structures and retrieve the bio-vulnerable pDNA payloads. In conclusion, our proposed unique dynamic surface chemistry provides a viable delivery mechanism that successfully navigates a series of biological roadblocks and collaborates to effectively express the encapsulated pDNA at the targeted cells.
The surface physiochemical features of nanomedicine are essential for controlling biointerfacial interactions in biological compartments and achieving the programmed delivery scenario to intracellular targets. This work presents a novel dynamic triple-transformable surface engineering strategy that can adapt to sequential variable biological microenvironments and intelligently managing the previously acknowledged biological obstacles. By employing click chemistry, the surface of a classical PEGylated pDNA delivery nanoparticles were tethered with a multiple of charge-reversible polymers to endow the dynamic biointerfacial surroundings. Crucially, the dynamic surroundings had negative charge under physiological circumstances (pH 7.4), which inhibited structural disintegration brought on by charged biological species and anionic nuclease degradation. In addition, by regulating the first pass effect, the nanoparticles demonstrated appreciable stealth function that led to persistent systemic retention and improved bioavailability and consistent internalization into the targeted cells. In subsequence to cell endocytosis, translocation from the digestive endolysosomes to the targeted cytosol was facilitated due to acidification (endosomal pH 5.5) of the dynamic surroundings into highly positive charge, consequently leading to explosive disruptive effects on the endolysosomal structures and retrieve the bio-vulnerable pDNA payloads. In conclusion, our proposed unique dynamic surface chemistry provides a viable delivery mechanism that successfully navigates a series of biological roadblocks and collaborates to effectively express the encapsulated pDNA at the targeted cells.
2025, 36(10): 110800
doi: 10.1016/j.cclet.2024.110800
摘要:
Endometrial injury caused by intrauterine procedures can result in infertility and recurrent miscarriages, and the current clinical treatments are inadequate for effective endometrial repair. The implantation of anti-adhesion hydrogels combined with growth factors is a promising strategy to address endometrial injury. Insulin-like growth factor 1 is closely associated with endometrial growth and plays a crucial role in endometrial receptivity that is essential for fertility. However, its high cost, environmental sensitivity, and short biological half-life limit its practical applications. In this study, we developed a two-component peptide-based hydrogel consisting of a biotinylated peptide and an insulin-like growth factor 1 (IGF-1) mimetic peptide, both of which were designed with self-assembly capabilities. The resultant hydrogel exhibited significant mechanical properties and retained its native IGF-1 bioactivity. In vivo experiments demonstrated that the hydrogel significantly facilitated proliferation and vascular restoration. Additionally, it effectively reduced fibrosis by decreasing collagen accumulation, restoring the expression of progesterone receptors, and enhancing endometrial receptivity, which are crucial for embryo implantation. These findings highlight the potential of the two-component peptide-based hydrogel as an innovative therapeutic approach for treating endometrial injury.
Endometrial injury caused by intrauterine procedures can result in infertility and recurrent miscarriages, and the current clinical treatments are inadequate for effective endometrial repair. The implantation of anti-adhesion hydrogels combined with growth factors is a promising strategy to address endometrial injury. Insulin-like growth factor 1 is closely associated with endometrial growth and plays a crucial role in endometrial receptivity that is essential for fertility. However, its high cost, environmental sensitivity, and short biological half-life limit its practical applications. In this study, we developed a two-component peptide-based hydrogel consisting of a biotinylated peptide and an insulin-like growth factor 1 (IGF-1) mimetic peptide, both of which were designed with self-assembly capabilities. The resultant hydrogel exhibited significant mechanical properties and retained its native IGF-1 bioactivity. In vivo experiments demonstrated that the hydrogel significantly facilitated proliferation and vascular restoration. Additionally, it effectively reduced fibrosis by decreasing collagen accumulation, restoring the expression of progesterone receptors, and enhancing endometrial receptivity, which are crucial for embryo implantation. These findings highlight the potential of the two-component peptide-based hydrogel as an innovative therapeutic approach for treating endometrial injury.
2025, 36(10): 110801
doi: 10.1016/j.cclet.2024.110801
摘要:
The advancement of various types of fluorescent nanoparticles is crucial for enhancing the application of lateral flow immunoassays (LFIA) across multiple fields. Currently, the fluorescent nanoparticles utilized in LFIA predominantly consist of traditional dye-doped nanoparticles or aggregation-induced luminescence dye-doped nanoparticles. The reliance on specific types of nanoparticles limits the diversity of signal reporting groups available for LFIA. Herein, we developed a solid-state luminescent dye-doped nanoparticles (SLDNPs)-based LFIA system with exceptional stability for the detection of C-reactive protein (CRP) in serum. The synthesis of SLD520NPS was simplicity, efficient and eco-friendly, which was ideal for large-scale production of the LFIA test strip. And the SLD520NPS exhibits superior fluorescence quantum yield (49%), fully guarantees the performance of the LFIA test strip. The constructed SLD520NPs-mAb1-based LFIA demonstrated a satisfactory linear relationship with CRP concentrations ranging from 0.5 ng/mL to 100 ng/mL, with limits of detection (LOD) of 0.78 ng/mL and a visible LOD of 1 ng/mL using a handheld 405 nm lamp. Furthermore, the developed LFIA exhibited excellent recoveries in serum, ranging from 94.45% to 102.5%. Overall, the outstanding performance of the SLD520NPs-mAb1-based LFIA indicates that solid-state luminescent dyes have significant potential applications in the field of LFIA.
The advancement of various types of fluorescent nanoparticles is crucial for enhancing the application of lateral flow immunoassays (LFIA) across multiple fields. Currently, the fluorescent nanoparticles utilized in LFIA predominantly consist of traditional dye-doped nanoparticles or aggregation-induced luminescence dye-doped nanoparticles. The reliance on specific types of nanoparticles limits the diversity of signal reporting groups available for LFIA. Herein, we developed a solid-state luminescent dye-doped nanoparticles (SLDNPs)-based LFIA system with exceptional stability for the detection of C-reactive protein (CRP) in serum. The synthesis of SLD520NPS was simplicity, efficient and eco-friendly, which was ideal for large-scale production of the LFIA test strip. And the SLD520NPS exhibits superior fluorescence quantum yield (49%), fully guarantees the performance of the LFIA test strip. The constructed SLD520NPs-mAb1-based LFIA demonstrated a satisfactory linear relationship with CRP concentrations ranging from 0.5 ng/mL to 100 ng/mL, with limits of detection (LOD) of 0.78 ng/mL and a visible LOD of 1 ng/mL using a handheld 405 nm lamp. Furthermore, the developed LFIA exhibited excellent recoveries in serum, ranging from 94.45% to 102.5%. Overall, the outstanding performance of the SLD520NPs-mAb1-based LFIA indicates that solid-state luminescent dyes have significant potential applications in the field of LFIA.
2025, 36(10): 110803
doi: 10.1016/j.cclet.2024.110803
摘要:
Selenolate ligands are expected to endow fluorescent gold nanoclusters (AuNCs) with better stability and more bioactivity than thiolate ligands, making them promising in the biological field. However, there are few studies on the synthesis of water-soluble selenolate-protected AuNCs, and the impact of selenolate ligands on the optical properties of AuNCs is still unclear. In this study, we synthesized selenolate-costabilized water-soluble, near-infrared fluorescent AuNCs with four different amounts of benzeneselenol (PhSeH), and systematically investigated the role of PhSeH on their optical properties. It is discovered that an appropriate PhSeH content is favorable for the fluorescence enhancement of AuNCs due to the ligand to metal charge transfer effect. Moreover, AuNCs co-stabilized by selenolate ligands exhibit better photostability and long-term stability compared with AuNCs stabilized by thiolate ligands, owing to the introduction of Au-Se bond on their surfaces. Further cellular experiments revealed that selenolate ligands can also affect the cellular uptake efficiency of AuNCs and their imaging property. These results provide important knowledges for further development of new, robust selenolate-stabilized metal NCs for biological application.
Selenolate ligands are expected to endow fluorescent gold nanoclusters (AuNCs) with better stability and more bioactivity than thiolate ligands, making them promising in the biological field. However, there are few studies on the synthesis of water-soluble selenolate-protected AuNCs, and the impact of selenolate ligands on the optical properties of AuNCs is still unclear. In this study, we synthesized selenolate-costabilized water-soluble, near-infrared fluorescent AuNCs with four different amounts of benzeneselenol (PhSeH), and systematically investigated the role of PhSeH on their optical properties. It is discovered that an appropriate PhSeH content is favorable for the fluorescence enhancement of AuNCs due to the ligand to metal charge transfer effect. Moreover, AuNCs co-stabilized by selenolate ligands exhibit better photostability and long-term stability compared with AuNCs stabilized by thiolate ligands, owing to the introduction of Au-Se bond on their surfaces. Further cellular experiments revealed that selenolate ligands can also affect the cellular uptake efficiency of AuNCs and their imaging property. These results provide important knowledges for further development of new, robust selenolate-stabilized metal NCs for biological application.
2025, 36(10): 110804
doi: 10.1016/j.cclet.2024.110804
摘要:
Diabetes and insulinoma represent opposing alterations in pancreatic β-cell mass, with diabetes resulting from irreversible β-cells damage and insulinoma arising from abnormal proliferation. Early diagnosis of both conditions necessitates effective β-cell mass detection. Current detection methods are limited in diagnosing each condition individually or lacking timely and accurate detection. Diabetes is typically identified only after significant β-cell loss, while insulinoma can evade conventional imaging due to their small size. Positron emission tomography/computed tomography (PET/CT) imaging, combining anatomical and functional data, enhances diagnostic accuracy but faces challenges in specificity. This study employed two RNA aptamers (m12–3773 and 1–717) modified to enhance RNase resistance and conjugated with 68Ga to create 68Ga-NOTA-Ap. 68Ga-NOTA-Ap was administered to rats with pancreatic β-cell damage and mice with insulinoma to evaluate its ability to image islets, detect changes in pancreatic β-cell mass (BCM), and identify insulinoma. Modified with methoxy and fluoro, RNA aptamers exhibited enhanced stability and RNases resistance while retaining their dissociation constants (Kd). Furthermore, 68Ga-NOTA-Ap effectively detected changes of BCM in rats with pancreatic β-cell damage and imaged insulinoma in mice through recognition of abnormal β-cell proliferation by recognizing clusterin and transmembrane p24 trafficking protein 6 (TMED6) on pancreatic β-cell. The developed 68Ga-NOTA-Ap shows promise for early screening of diabetes and insulinoma due to its high sensitivity, specificity, and non-invasive nature. It has potential clinical applications for monitoring pancreatic β-cell function and diagnosing insulinoma.
Diabetes and insulinoma represent opposing alterations in pancreatic β-cell mass, with diabetes resulting from irreversible β-cells damage and insulinoma arising from abnormal proliferation. Early diagnosis of both conditions necessitates effective β-cell mass detection. Current detection methods are limited in diagnosing each condition individually or lacking timely and accurate detection. Diabetes is typically identified only after significant β-cell loss, while insulinoma can evade conventional imaging due to their small size. Positron emission tomography/computed tomography (PET/CT) imaging, combining anatomical and functional data, enhances diagnostic accuracy but faces challenges in specificity. This study employed two RNA aptamers (m12–3773 and 1–717) modified to enhance RNase resistance and conjugated with 68Ga to create 68Ga-NOTA-Ap. 68Ga-NOTA-Ap was administered to rats with pancreatic β-cell damage and mice with insulinoma to evaluate its ability to image islets, detect changes in pancreatic β-cell mass (BCM), and identify insulinoma. Modified with methoxy and fluoro, RNA aptamers exhibited enhanced stability and RNases resistance while retaining their dissociation constants (Kd). Furthermore, 68Ga-NOTA-Ap effectively detected changes of BCM in rats with pancreatic β-cell damage and imaged insulinoma in mice through recognition of abnormal β-cell proliferation by recognizing clusterin and transmembrane p24 trafficking protein 6 (TMED6) on pancreatic β-cell. The developed 68Ga-NOTA-Ap shows promise for early screening of diabetes and insulinoma due to its high sensitivity, specificity, and non-invasive nature. It has potential clinical applications for monitoring pancreatic β-cell function and diagnosing insulinoma.
2025, 36(10): 110811
doi: 10.1016/j.cclet.2024.110811
摘要:
Humic acid (HA) as a natural reducing ligand was employed to accelerate the Fenton and Fenton-like processes, however, the potential role of photosensitivity was overlooked. This research showed that HA exhibits more significant promotion for levofloxacin (LVF) degradation under light conditions compared to darkness. The study also proposed a mechanism involving complexation and photosensitization interactions. A strong inhibitor of ethylenediaminetetraacetic acid confirmed that the formation of organic-iron complexes was crucial. Firstly, it was proposed that complexed iron has a lower redox potential than free iron, which may be responsible for accelerating electron transfer from iron to peroxydisulfate (PDS). The density functional theory (DFT) calculations confirmed that complexed iron has a lower reaction energy barrier for PDS activation. Additionally, the excited state substances (*HA and *LVF) can transfer electrons to Fe(Ⅲ) and PDS, and the generation of HA/LVF-Fe(Ⅲ)-PDS can accelerate this process. These findings could offer fresh perspectives on the combined elimination of contaminants through natural organic compounds and light exposure.
Humic acid (HA) as a natural reducing ligand was employed to accelerate the Fenton and Fenton-like processes, however, the potential role of photosensitivity was overlooked. This research showed that HA exhibits more significant promotion for levofloxacin (LVF) degradation under light conditions compared to darkness. The study also proposed a mechanism involving complexation and photosensitization interactions. A strong inhibitor of ethylenediaminetetraacetic acid confirmed that the formation of organic-iron complexes was crucial. Firstly, it was proposed that complexed iron has a lower redox potential than free iron, which may be responsible for accelerating electron transfer from iron to peroxydisulfate (PDS). The density functional theory (DFT) calculations confirmed that complexed iron has a lower reaction energy barrier for PDS activation. Additionally, the excited state substances (*HA and *LVF) can transfer electrons to Fe(Ⅲ) and PDS, and the generation of HA/LVF-Fe(Ⅲ)-PDS can accelerate this process. These findings could offer fresh perspectives on the combined elimination of contaminants through natural organic compounds and light exposure.
2025, 36(10): 110890
doi: 10.1016/j.cclet.2025.110890
摘要:
The development of cost-effective and high-efficiency catalysts for sustainable hydrogen production through electrocatalytic hydrogen evolution reaction (HER) is crucial yet remains challenging. In this work, we synthesized two types of bimetallic PtNi nanoparticles embedded in N-doped porous carbons derived from Ni-ABDC (5-aminoisophthalate) using both in-situ and ex-situ Pt inclusion methods. The in-situ Pt doping notably disrupted the effective growth of Ni-ABDC nanostrips owing to strong interactions between Pt and ABDC, resulting in an amorphous nanostructure. The optimized PtinNi-NC exhibited remarkable HER performance with a low overpotential of 29 mV at 10 mA/cm2, a Tafel slope of 47.4 mV/dec, and a current retention of 91.2% after 200 h in 1.0 mol/L KOH solution, surpassing the performance of Ni-NC, PtexNi-NC, and Pt/C. This research demonstrates the rational design and preparation of transition metal-based coordination polymer-derived metal-carbon nanomaterials with low Pt loading, emphasizing their considerable potential in energy conversion and storage technologies.
The development of cost-effective and high-efficiency catalysts for sustainable hydrogen production through electrocatalytic hydrogen evolution reaction (HER) is crucial yet remains challenging. In this work, we synthesized two types of bimetallic PtNi nanoparticles embedded in N-doped porous carbons derived from Ni-ABDC (5-aminoisophthalate) using both in-situ and ex-situ Pt inclusion methods. The in-situ Pt doping notably disrupted the effective growth of Ni-ABDC nanostrips owing to strong interactions between Pt and ABDC, resulting in an amorphous nanostructure. The optimized PtinNi-NC exhibited remarkable HER performance with a low overpotential of 29 mV at 10 mA/cm2, a Tafel slope of 47.4 mV/dec, and a current retention of 91.2% after 200 h in 1.0 mol/L KOH solution, surpassing the performance of Ni-NC, PtexNi-NC, and Pt/C. This research demonstrates the rational design and preparation of transition metal-based coordination polymer-derived metal-carbon nanomaterials with low Pt loading, emphasizing their considerable potential in energy conversion and storage technologies.
2025, 36(10): 110894
doi: 10.1016/j.cclet.2025.110894
摘要:
Catalytic electron donor-acceptor (EDA) complex photochemistry has recently emerged as a popular and sustainable alternative to photoredox synthetic methods. Yet, the catalytic EDA strategy is still in its infancy for organic synthesis due to the challenges of designing novel catalytic paradigm and expanding the substrate and reaction scope. Here, we disclose a catalytic EDA/Cu cooperative strategy by employing NaI as a catalytic donor for copper-catalyzed radical asymmetric carbocyanation. A diverse range of synthetically useful chiral benzyl nitriles are produced with high enantioselectivities. This synergetic EDA/copper catalysis enables the decarboxylative cyanation without request of any photoredox catalysts, further expanding the synthetic potential of catalytic EDA chemistry in organic synthesis.
Catalytic electron donor-acceptor (EDA) complex photochemistry has recently emerged as a popular and sustainable alternative to photoredox synthetic methods. Yet, the catalytic EDA strategy is still in its infancy for organic synthesis due to the challenges of designing novel catalytic paradigm and expanding the substrate and reaction scope. Here, we disclose a catalytic EDA/Cu cooperative strategy by employing NaI as a catalytic donor for copper-catalyzed radical asymmetric carbocyanation. A diverse range of synthetically useful chiral benzyl nitriles are produced with high enantioselectivities. This synergetic EDA/copper catalysis enables the decarboxylative cyanation without request of any photoredox catalysts, further expanding the synthetic potential of catalytic EDA chemistry in organic synthesis.
2025, 36(10): 110897
doi: 10.1016/j.cclet.2025.110897
摘要:
This study investigates the intersystem crossing (ISC) mechanism in donor-acceptor (D-A) type distyryl-BODIPY photosensitizers, including previously reported M1 (benzene donor), M2, M3 (phenothiazine donors), and newly predicted M4 (triphenylamine donor), M5-M7 (nitrogen-containing aliphatic rings with thiophene donors). Using computational chemistry, we analyzed their geometric configurations, spectral properties, spin-orbit coupling, and electron-hole orbitals. We found that S2 is a charge transfer singlet state (1CT), T2 is a locally excited triplet state (3LE), and the S2 → T2 transition is the main ISC pathway in M2-M7, following the 1CT → 3LE mechanism. M5-M7 show near-vertical dihedral angles between donor and acceptor in the S2 state relative to M2-M4, facilitating charge transfer. The strain energies in the nitrogen-containing rings of M5-M7 affect oxidation potentials and ISC. M5, with the highest strain energy, shows the lowest oxidation potential, smaller ΔES2-T2, highest SOC, and fastest kisc, making it the most efficient predicted singlet oxygen producer. This research clarifies the structure-performance relationships of near-infrared D-A type distyryl-BODIPY photosensitizers and provides a theoretical foundation for developing heavy-atom-free photosensitizers with tuned fluorescence quantum yield and singlet oxygen quantum yield.
This study investigates the intersystem crossing (ISC) mechanism in donor-acceptor (D-A) type distyryl-BODIPY photosensitizers, including previously reported M1 (benzene donor), M2, M3 (phenothiazine donors), and newly predicted M4 (triphenylamine donor), M5-M7 (nitrogen-containing aliphatic rings with thiophene donors). Using computational chemistry, we analyzed their geometric configurations, spectral properties, spin-orbit coupling, and electron-hole orbitals. We found that S2 is a charge transfer singlet state (1CT), T2 is a locally excited triplet state (3LE), and the S2 → T2 transition is the main ISC pathway in M2-M7, following the 1CT → 3LE mechanism. M5-M7 show near-vertical dihedral angles between donor and acceptor in the S2 state relative to M2-M4, facilitating charge transfer. The strain energies in the nitrogen-containing rings of M5-M7 affect oxidation potentials and ISC. M5, with the highest strain energy, shows the lowest oxidation potential, smaller ΔES2-T2, highest SOC, and fastest kisc, making it the most efficient predicted singlet oxygen producer. This research clarifies the structure-performance relationships of near-infrared D-A type distyryl-BODIPY photosensitizers and provides a theoretical foundation for developing heavy-atom-free photosensitizers with tuned fluorescence quantum yield and singlet oxygen quantum yield.
2025, 36(10): 110899
doi: 10.1016/j.cclet.2025.110899
摘要:
Selective reduction of nitroarenes has long been a problem in organic synthesis, as a wide distribution of many different products could be generated from the multi-electron transfer processes. Development of a mild and preciously controllable strong reductive catalytic system is the key challenge to realize selective reduction of nitroarenes. In this work, the authors disclose a photocatalytic strategy with formate as the electron donor via generation of the highly reductive CO2 radical anion species. Various arylhydroxylamines or anilines could be synthesized selectively under visible-light irradiation by simply switching the photocatalysts. Moreover, in the presence of formaldehyde, the N-methyl anilines or imidazoline derivative could also be constructed in one-pot manner. Nitroalkanes were also amendable in this photocatalytic system to selectively yield oximes.
Selective reduction of nitroarenes has long been a problem in organic synthesis, as a wide distribution of many different products could be generated from the multi-electron transfer processes. Development of a mild and preciously controllable strong reductive catalytic system is the key challenge to realize selective reduction of nitroarenes. In this work, the authors disclose a photocatalytic strategy with formate as the electron donor via generation of the highly reductive CO2 radical anion species. Various arylhydroxylamines or anilines could be synthesized selectively under visible-light irradiation by simply switching the photocatalysts. Moreover, in the presence of formaldehyde, the N-methyl anilines or imidazoline derivative could also be constructed in one-pot manner. Nitroalkanes were also amendable in this photocatalytic system to selectively yield oximes.
2025, 36(10): 110900
doi: 10.1016/j.cclet.2025.110900
摘要:
Oxathiolene oxides are a significant class of bioactive compounds with promising implications in drug discovery, serving as bioisosteres/analogues of 2(5H)-furanones and 1, 3-propene sultones. However, existing methods are quite inadequate in their synthesis. Here, we introduced an innovative approach for the photoinduced, site-selective thiosulfinylation of alkynols, providing access to a diverse range of highly functionalized oxathiolene oxides through energy transfer followed by a radical chain process. This procedure efficiently maintains the catalytic cycle under mild and operationally simple conditions, offering excellent functional group tolerance and streamlining the synthesis of bioactive scaffolds and their derivatives that are often challenging with alternative approaches. Preliminary evaluation of live-cell cytotoxicity of oxathiolene oxides toward the 4T1 cancer cells was conducted, suggesting a potentially useable in chemical biology. The strategy presented in this study is not only mechanistically robust but also demonstrates broad versatility in late-stage functionalization, indicating its great potential application in organic synthesis and medicinal chemistry.
Oxathiolene oxides are a significant class of bioactive compounds with promising implications in drug discovery, serving as bioisosteres/analogues of 2(5H)-furanones and 1, 3-propene sultones. However, existing methods are quite inadequate in their synthesis. Here, we introduced an innovative approach for the photoinduced, site-selective thiosulfinylation of alkynols, providing access to a diverse range of highly functionalized oxathiolene oxides through energy transfer followed by a radical chain process. This procedure efficiently maintains the catalytic cycle under mild and operationally simple conditions, offering excellent functional group tolerance and streamlining the synthesis of bioactive scaffolds and their derivatives that are often challenging with alternative approaches. Preliminary evaluation of live-cell cytotoxicity of oxathiolene oxides toward the 4T1 cancer cells was conducted, suggesting a potentially useable in chemical biology. The strategy presented in this study is not only mechanistically robust but also demonstrates broad versatility in late-stage functionalization, indicating its great potential application in organic synthesis and medicinal chemistry.
2025, 36(10): 110901
doi: 10.1016/j.cclet.2025.110901
摘要:
A nickel-catalyzed C(sp2)–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the reaction step and atom economy. It has been investigated that the 2,4,6-trimethylpyridine ligand was critical to achieve the optimized reactivity. This protocol provides a straightforward route for synthesizing the alkynylated free benzylamines, featuring good substrate compatibility and monoselectivity.
A nickel-catalyzed C(sp2)–H alkynylation of unprotected α-substituted benzylamines is achieved by utilizing a transient directing group. The combination of a TDG with a nickel catalyst significantly improves the reaction step and atom economy. It has been investigated that the 2,4,6-trimethylpyridine ligand was critical to achieve the optimized reactivity. This protocol provides a straightforward route for synthesizing the alkynylated free benzylamines, featuring good substrate compatibility and monoselectivity.
2025, 36(10): 110913
doi: 10.1016/j.cclet.2025.110913
摘要:
A concise total synthesis of novel monoterpenoid indole alkaloid (-)-voacafricine A is described, which proceeded in 14 longest linear steps and 5.2% overall yield. Key transformations comprised of (a) an organocatalytically asymmetric Pictet-Spengler cyclization/lactamization cascade reaction generating the key tetracyclic lactam skeleton; (b) asymmetric α-alkylation of carbonyl group induced by Evans' chiral auxiliary with excellent diastereoselectivity; (c) a highly efficient one-pot desulfurization/hydrogenation/debenzylation transformation using Raney Ni under hydrogen atmosphere; as well as (d) an intramolecular Vorbürggen reaction constructing the quaternary ammonium motif and the final cagelike skeleton.
A concise total synthesis of novel monoterpenoid indole alkaloid (-)-voacafricine A is described, which proceeded in 14 longest linear steps and 5.2% overall yield. Key transformations comprised of (a) an organocatalytically asymmetric Pictet-Spengler cyclization/lactamization cascade reaction generating the key tetracyclic lactam skeleton; (b) asymmetric α-alkylation of carbonyl group induced by Evans' chiral auxiliary with excellent diastereoselectivity; (c) a highly efficient one-pot desulfurization/hydrogenation/debenzylation transformation using Raney Ni under hydrogen atmosphere; as well as (d) an intramolecular Vorbürggen reaction constructing the quaternary ammonium motif and the final cagelike skeleton.
2025, 36(10): 110914
doi: 10.1016/j.cclet.2025.110914
摘要:
Although the demand of 10B separation has arisen in the 1930s, 10B/11B are among the most difficult isotopes to separate due to the extremely similar relative atomic mass. Herein, we report an efficient separation of 10B isotopologue by engineering amino-galloyl synergistic materials via a selective adsorption and isotope exchange reaction, achieving a record-high single-stage separation factor of 1.048 with 10B abundance up to 21.42%. 11B MAS NMR results and DFT calculations reveal that the galloyl groups exhibit inherent high affinity for B(OH)4−, forming tetrahedral sp3 B-galloyl complexes. The relatively higher 10B–O bond energy of 10B-galloyl complexes facilitates the isotope exchange between 11B in B-galloyl complexes and 10B in B(OH)3. Flowthrough dynamic separation in fixed-bed demonstrates the feasibility and potential of large-scale deployment of this method in real-world, suggesting a promising avenue for the exploitation of more efficient enrichment of 10B for the sustainable nuclear energy and biomedical research.
Although the demand of 10B separation has arisen in the 1930s, 10B/11B are among the most difficult isotopes to separate due to the extremely similar relative atomic mass. Herein, we report an efficient separation of 10B isotopologue by engineering amino-galloyl synergistic materials via a selective adsorption and isotope exchange reaction, achieving a record-high single-stage separation factor of 1.048 with 10B abundance up to 21.42%. 11B MAS NMR results and DFT calculations reveal that the galloyl groups exhibit inherent high affinity for B(OH)4−, forming tetrahedral sp3 B-galloyl complexes. The relatively higher 10B–O bond energy of 10B-galloyl complexes facilitates the isotope exchange between 11B in B-galloyl complexes and 10B in B(OH)3. Flowthrough dynamic separation in fixed-bed demonstrates the feasibility and potential of large-scale deployment of this method in real-world, suggesting a promising avenue for the exploitation of more efficient enrichment of 10B for the sustainable nuclear energy and biomedical research.
2025, 36(10): 110915
doi: 10.1016/j.cclet.2025.110915
摘要:
The tricyclic pyrrolo[2,3-c]quinoline framework is the core structure of numerous natural products and bioactive molecules. Their syntheses usually rely on either forming middle pyridine ring by pyridannulation of 2-(1H-pyrrol-3-yl)anilines or building the pyrrole ring onto quinolines. We herein disclosed an unprecedented diheterocyclization-migration strategy for the de novo synthesis of 4-sulfonyl pyrrolo[2,3-c]quinolines from two distinct isocyanides. This methodology successively constructed the pyridine and pyrrole rings of this tricyclic scaffold in a single operation, along with remote migration of the sulfonyl group. Moreover, a collective total synthesis of alkaloids marinoquinoline A-C, H and K was accomplished by using the resulting 4-sulfonyl pyrrolo[2,3-c]quinoline as a common platform.
The tricyclic pyrrolo[2,3-c]quinoline framework is the core structure of numerous natural products and bioactive molecules. Their syntheses usually rely on either forming middle pyridine ring by pyridannulation of 2-(1H-pyrrol-3-yl)anilines or building the pyrrole ring onto quinolines. We herein disclosed an unprecedented diheterocyclization-migration strategy for the de novo synthesis of 4-sulfonyl pyrrolo[2,3-c]quinolines from two distinct isocyanides. This methodology successively constructed the pyridine and pyrrole rings of this tricyclic scaffold in a single operation, along with remote migration of the sulfonyl group. Moreover, a collective total synthesis of alkaloids marinoquinoline A-C, H and K was accomplished by using the resulting 4-sulfonyl pyrrolo[2,3-c]quinoline as a common platform.
2025, 36(10): 110923
doi: 10.1016/j.cclet.2025.110923
摘要:
Spiro-cyclopropyl oxindoles are widely found in natural products and medicinal molecules. Herein, we report a highly stereo- and enantio-selective procedure for accessing this class of compounds via tertiary amine mediated cyclopropanation of ammonium ylides with the in-situ Heck reaction-generated 3-alkenyl indolones as the Michael receptors. This reaction features mild conditions, excellent enantioselectivity (up to 98%) and diastereoselectivity (up to 99:1), high atom- and step-economy, broad substrate scopes, and good functional group tolerance. Additionally, this scalable synthetic process could offer a novel strategy for the efficient synthesis of enantiopure spirocyclopropyl oxindoles.
Spiro-cyclopropyl oxindoles are widely found in natural products and medicinal molecules. Herein, we report a highly stereo- and enantio-selective procedure for accessing this class of compounds via tertiary amine mediated cyclopropanation of ammonium ylides with the in-situ Heck reaction-generated 3-alkenyl indolones as the Michael receptors. This reaction features mild conditions, excellent enantioselectivity (up to 98%) and diastereoselectivity (up to 99:1), high atom- and step-economy, broad substrate scopes, and good functional group tolerance. Additionally, this scalable synthetic process could offer a novel strategy for the efficient synthesis of enantiopure spirocyclopropyl oxindoles.
2025, 36(10): 110938
doi: 10.1016/j.cclet.2025.110938
摘要:
The practical application of lithium-sulfur (Li-S) batteries is still impeded by the severe shuttle effect of lithium polysulfides (LiPSs) and sluggish reaction kinetics of active sulfur. Designing catalytic carriers with abundant active sites and strong chemisorption capability for LiPSs, is regarded as effective strategy to address these issues. Herein, Se-doping is introduced into the nitrogen-doped carbon coated CoP composite (Se-CoP@NC) to generate structural defects, which effectively enlarges the lattice spacing of CoP and reduces the conversion reaction energy barriers of LiPSs. Meanwhile, Se-doping sites bridges the interface of CoP and nitrogen-doped carbon, accelerating the charge transfer behavior and conversion reaction kinetics of LiPSs. Benefiting from the structural advantages, the assembled Li-S batteries with S/Se-CoP@NC as cathode exhibit high reversible capacity of 779.6 mAh/g at 0.5 C after 500 cycles, and high specific capacity of 805.9 mAh/g at 2 C. Even under extreme conditions (high sulfur-loading content of 6.9 mg/cm2; lean electrolyte dosage of 7 µL/mg), the corresponding Li-S batteries also keep high reversible areal capacity of 4.5 mAh/cm2 after 100 cycles at 0.1 C. This work will inspire the design of metal compounds-based catalysts from atomic level to facilitate the practicability of Li-S batteries.
The practical application of lithium-sulfur (Li-S) batteries is still impeded by the severe shuttle effect of lithium polysulfides (LiPSs) and sluggish reaction kinetics of active sulfur. Designing catalytic carriers with abundant active sites and strong chemisorption capability for LiPSs, is regarded as effective strategy to address these issues. Herein, Se-doping is introduced into the nitrogen-doped carbon coated CoP composite (Se-CoP@NC) to generate structural defects, which effectively enlarges the lattice spacing of CoP and reduces the conversion reaction energy barriers of LiPSs. Meanwhile, Se-doping sites bridges the interface of CoP and nitrogen-doped carbon, accelerating the charge transfer behavior and conversion reaction kinetics of LiPSs. Benefiting from the structural advantages, the assembled Li-S batteries with S/Se-CoP@NC as cathode exhibit high reversible capacity of 779.6 mAh/g at 0.5 C after 500 cycles, and high specific capacity of 805.9 mAh/g at 2 C. Even under extreme conditions (high sulfur-loading content of 6.9 mg/cm2; lean electrolyte dosage of 7 µL/mg), the corresponding Li-S batteries also keep high reversible areal capacity of 4.5 mAh/cm2 after 100 cycles at 0.1 C. This work will inspire the design of metal compounds-based catalysts from atomic level to facilitate the practicability of Li-S batteries.
2025, 36(10): 110984
doi: 10.1016/j.cclet.2025.110984
摘要:
Red fluorescent proteins with large Stokes shift (LSS-RFPs) are advantageous for multicolor imaging applications that allow simultaneous visualizations of multiple biological events. But it is difficult to develop LSS-RFPs by extending the emission wavelength of RFPs to far-red region. Here, we employed Förster resonance energy transfer (FRET) strategy to engineer the far-red fluorescent proteins with large Stokes shift. LSS-mApple and LSS-mCherry were constructed by fusing HaloTag to mApple and mCherry, allowing the fluorophore TMSiR to be connected to these RFPs. FRET between RFPs and TMSiR enabled them to apply the excitation of donor RFPs to emit far-red fluorescence of acceptor TMSiR. The Stokes shifts of LSS-mApple and LSS-mCherry were 97 nm and 75 nm, respectively. The high FRET efficiency of LSS-mCherry (EFRET = 83.7%) can greatly reduce the fluorescence from the donor channel, which did not affect co-imaging with mCherry. In addition, LSS-mCherry also showed excellent photostability (t1/2 = 449.3 s), enabling stable confocal fluorescence imaging for 15 min under continuous strong excitation. Furthermore, LSS-mCherry was applied for fluorescence labeling and imaging of the nucleus, mitochondria, lysosomes, and endoplasmic reticulum in living cells. Finally, we applied LSS-mCherry to perform multi-color bioimaging of 2–4 channels, and there was no obvious crosstalk between these channels.
Red fluorescent proteins with large Stokes shift (LSS-RFPs) are advantageous for multicolor imaging applications that allow simultaneous visualizations of multiple biological events. But it is difficult to develop LSS-RFPs by extending the emission wavelength of RFPs to far-red region. Here, we employed Förster resonance energy transfer (FRET) strategy to engineer the far-red fluorescent proteins with large Stokes shift. LSS-mApple and LSS-mCherry were constructed by fusing HaloTag to mApple and mCherry, allowing the fluorophore TMSiR to be connected to these RFPs. FRET between RFPs and TMSiR enabled them to apply the excitation of donor RFPs to emit far-red fluorescence of acceptor TMSiR. The Stokes shifts of LSS-mApple and LSS-mCherry were 97 nm and 75 nm, respectively. The high FRET efficiency of LSS-mCherry (EFRET = 83.7%) can greatly reduce the fluorescence from the donor channel, which did not affect co-imaging with mCherry. In addition, LSS-mCherry also showed excellent photostability (t1/2 = 449.3 s), enabling stable confocal fluorescence imaging for 15 min under continuous strong excitation. Furthermore, LSS-mCherry was applied for fluorescence labeling and imaging of the nucleus, mitochondria, lysosomes, and endoplasmic reticulum in living cells. Finally, we applied LSS-mCherry to perform multi-color bioimaging of 2–4 channels, and there was no obvious crosstalk between these channels.
2025, 36(10): 111005
doi: 10.1016/j.cclet.2025.111005
摘要:
The efficient separation of styrene (ST) and ethylbenzene (EB) remains a significant challenge in the petrochemical industry due to their similar physical properties and kinetic molecular sizes. In this study, we cleverly utilized the voids of a fluorescent flexible hydrogen-bonded organic framework (X-HOF-10) constructed from a pure organic phenothiazine derivative with three cyano groups (PTTCN) to selectively adsorb and separate ST and EB based on their slight size difference. Single crystal structure analysis and fluorescence spectra reveal that the adsorption process of ST involves a gate-opening mechanism accompanied by a fluorescent color switch behavior. Upon simple heating, ST can be released from the voids through a gate-closing process. Conversely, exposure to EB vapor does not promote X-HOF-10a to adsorb EB due to its slightly larger size in comparison with ST, facilitating a single crystal to single crystal transition, leading to the formation of a new non-porous crystal without EB. Under equimolar vapor condition, X-HOF-10a transforms into X-HOF-10 rather than X-HOF-11 owing to the superior stability of X-HOF-10 over X-HOF-11, accompanied by selective adsorption of ST. The purity of ST can reach 92% after release from the framework, which further increases to over 98% when exposed to the mixed vapor containing 90% ST. Additionally, this HOF material exhibits recyclability without any discernible loss in performance.
The efficient separation of styrene (ST) and ethylbenzene (EB) remains a significant challenge in the petrochemical industry due to their similar physical properties and kinetic molecular sizes. In this study, we cleverly utilized the voids of a fluorescent flexible hydrogen-bonded organic framework (X-HOF-10) constructed from a pure organic phenothiazine derivative with three cyano groups (PTTCN) to selectively adsorb and separate ST and EB based on their slight size difference. Single crystal structure analysis and fluorescence spectra reveal that the adsorption process of ST involves a gate-opening mechanism accompanied by a fluorescent color switch behavior. Upon simple heating, ST can be released from the voids through a gate-closing process. Conversely, exposure to EB vapor does not promote X-HOF-10a to adsorb EB due to its slightly larger size in comparison with ST, facilitating a single crystal to single crystal transition, leading to the formation of a new non-porous crystal without EB. Under equimolar vapor condition, X-HOF-10a transforms into X-HOF-10 rather than X-HOF-11 owing to the superior stability of X-HOF-10 over X-HOF-11, accompanied by selective adsorption of ST. The purity of ST can reach 92% after release from the framework, which further increases to over 98% when exposed to the mixed vapor containing 90% ST. Additionally, this HOF material exhibits recyclability without any discernible loss in performance.
Vanadium doping inhibit the Jahn−Teller effect of Mn3+ for high-performance aqueous zinc ion battery
2025, 36(10): 111009
doi: 10.1016/j.cclet.2025.111009
摘要:
The Jahn-Teller effect of Mn3+ brings drastic structural changes to MnO2-based materials and accelerates the destruction and deactivation of the internal structure of the materials, thus leading to severe capacity fading and phase change of MnO2-based materials in aqueous zinc ion batteries (AZIBs). Here, this study doped high valent vanadium ions into MnO2 (VMO-x) to inhibit manganese's Jahn−Teller effect. Through a series of characterizations, such as X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM), it was discovered that the introduction of vanadium ions effectively increased the interlayer spacing of MnO2, facilitating the transport of ions into the interlayer. Additionally, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) demonstrated vanadium doped could effectively adjust the electronic structure, decreasing the average oxidation state of manganese, thereby inhibiting the Jahn−Teller effect and significantly enhancing the stability of the VMO-x cathode. The theoretical calculation showed that introducing vanadium ions enhanced the interaction between the main material and Zn2+, optimized its electron transport capacity, and led to better electrical conductivity and reaction kinetics of the VMO-5. Benefiting from this, the VMO-5 cathode exhibited an outstanding capacity of 283 mAh/g and maintained a capacity retention rate of 79% after 2000 cycles, demonstrating excellent electrochemical performance. Furthermore, the mechanism of H+/Zn2+ co-intercalation/deintercalation was demonstrated through mechanism analysis. Finally, the test results of the pouch cell demonstrated the excellent flexibility and safety exhibited by the VMO-5 make it have great potential in flexible devices. This work presented a novel approach to doping high valence metal ions into manganese-based electrodes for AZIBs.
The Jahn-Teller effect of Mn3+ brings drastic structural changes to MnO2-based materials and accelerates the destruction and deactivation of the internal structure of the materials, thus leading to severe capacity fading and phase change of MnO2-based materials in aqueous zinc ion batteries (AZIBs). Here, this study doped high valent vanadium ions into MnO2 (VMO-x) to inhibit manganese's Jahn−Teller effect. Through a series of characterizations, such as X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM), it was discovered that the introduction of vanadium ions effectively increased the interlayer spacing of MnO2, facilitating the transport of ions into the interlayer. Additionally, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) demonstrated vanadium doped could effectively adjust the electronic structure, decreasing the average oxidation state of manganese, thereby inhibiting the Jahn−Teller effect and significantly enhancing the stability of the VMO-x cathode. The theoretical calculation showed that introducing vanadium ions enhanced the interaction between the main material and Zn2+, optimized its electron transport capacity, and led to better electrical conductivity and reaction kinetics of the VMO-5. Benefiting from this, the VMO-5 cathode exhibited an outstanding capacity of 283 mAh/g and maintained a capacity retention rate of 79% after 2000 cycles, demonstrating excellent electrochemical performance. Furthermore, the mechanism of H+/Zn2+ co-intercalation/deintercalation was demonstrated through mechanism analysis. Finally, the test results of the pouch cell demonstrated the excellent flexibility and safety exhibited by the VMO-5 make it have great potential in flexible devices. This work presented a novel approach to doping high valence metal ions into manganese-based electrodes for AZIBs.
2025, 36(10): 111021
doi: 10.1016/j.cclet.2025.111021
摘要:
π-Conjugated donor-acceptor-donor-acceptor-donor (D-A-D-A-D) type pyrenoviologens (PyV2+), with the 2,7 positions of pyrene serving as connection bridges, were synthesized through SN2 reactions. Specifically, pyrenoviologen 3c was modified with a methylnaphthalene group, while 3a and 3b were modified with methyl and benzyl groups, respectively, for comparison. These pyrenoviologens exhibit reversible redox properties and strong fluorescence emission. Electrochromic devices (ECDs) were prepared using pyrenoviologens as the active materials. Notably, naphthalene-containing pyrenoviologen 3c, with its D-A-D-A-D conjugated structure, possesses more stable free radicals, enabling it to maintain the radical color for a longer duration after power loss. A series of color-changing devices were successfully assembled. Due to the strong fluorescence of pyrenoviologens and the unique electron transfer effect between them and picric acid (PA), a sensor film with good selectivity and high sensitivity for PA in aqueous solution was prepared using pyrenoviologens as the fluorescent probe. Specifically, 3c exhibited the highest sensitivity to PA due to its lowest energy gap. The introduction of the D-A-D-A-D structure is a strategic approach to enhancing photoelectric performance and broadening the application of viologens.
π-Conjugated donor-acceptor-donor-acceptor-donor (D-A-D-A-D) type pyrenoviologens (PyV2+), with the 2,7 positions of pyrene serving as connection bridges, were synthesized through SN2 reactions. Specifically, pyrenoviologen 3c was modified with a methylnaphthalene group, while 3a and 3b were modified with methyl and benzyl groups, respectively, for comparison. These pyrenoviologens exhibit reversible redox properties and strong fluorescence emission. Electrochromic devices (ECDs) were prepared using pyrenoviologens as the active materials. Notably, naphthalene-containing pyrenoviologen 3c, with its D-A-D-A-D conjugated structure, possesses more stable free radicals, enabling it to maintain the radical color for a longer duration after power loss. A series of color-changing devices were successfully assembled. Due to the strong fluorescence of pyrenoviologens and the unique electron transfer effect between them and picric acid (PA), a sensor film with good selectivity and high sensitivity for PA in aqueous solution was prepared using pyrenoviologens as the fluorescent probe. Specifically, 3c exhibited the highest sensitivity to PA due to its lowest energy gap. The introduction of the D-A-D-A-D structure is a strategic approach to enhancing photoelectric performance and broadening the application of viologens.
2025, 36(10): 111022
doi: 10.1016/j.cclet.2025.111022
摘要:
Intracellular protein delivery is vital for the development of therapeutic proteins that act on intracellular targets. Although numerous carriers based on polymers and nanomaterials have been reported to facilitate cellular internalization of membrane impermeable proteins, it is still a great challenge to intracellularly deliver proteins with different sizes and isoelectric points through small molecule-based protein carrier. Herein, amidinium functionalized pillar[5]arene (AP5) was used as a small molecular carrier to facilitate intracellular delivery of proteins with different sizes and isoelectric points. The densely preorganized amidinium groups on pillar[5]arene skeleton could not only glue proteins together to form AP5@protein complex through multiple salt-bridges, but also promote cellular internalization AP5@protein complex. The bioactivities of the internalized proteins were well-maintained. This study provides a novel, versatile and macrocyclic-molecule based intracellular protein delivery carrier through the preorganization of amidiniums on pillar[5]arene.
Intracellular protein delivery is vital for the development of therapeutic proteins that act on intracellular targets. Although numerous carriers based on polymers and nanomaterials have been reported to facilitate cellular internalization of membrane impermeable proteins, it is still a great challenge to intracellularly deliver proteins with different sizes and isoelectric points through small molecule-based protein carrier. Herein, amidinium functionalized pillar[5]arene (AP5) was used as a small molecular carrier to facilitate intracellular delivery of proteins with different sizes and isoelectric points. The densely preorganized amidinium groups on pillar[5]arene skeleton could not only glue proteins together to form AP5@protein complex through multiple salt-bridges, but also promote cellular internalization AP5@protein complex. The bioactivities of the internalized proteins were well-maintained. This study provides a novel, versatile and macrocyclic-molecule based intracellular protein delivery carrier through the preorganization of amidiniums on pillar[5]arene.
2025, 36(10): 111089
doi: 10.1016/j.cclet.2025.111089
摘要:
There is growing evidence that lipid metabolism instability in depressive disorder may be a core early pathological event associated with numerous pathogenesis hypotheses. However, spatial distributions and quantitative changes of lipids in specific brain regions associated with depressive disorder are far from elucidated. In the present study, lipid profiling characteristics of whole brain sections are systematically determined by using matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI)-combined with histomorphological analysis in rats with depressive-like behavior induced by multiple early life stress (mELS) and unstressed control. Lipid dyshomeostasis and different degrees of metabolic disturbance occur in the eight paired representative brain sections from micro-region and molecular level. More specifically, 17 lipid molecules show the severe dyshomeostasis between inter-group (control and depressed rats) or intra-group (multiple emotion-regulation-related brain regions). Quite specially, phosphatidylcholine (PC) (39:6) expression in section 7 is significantly upregulated only in the amygdala of depressed rat relative to control rat, by contrast, up-regulated phosphatidylglycerol (PG) (34:2) in section 2 emerges in the medial prefrontal cortex, insular cortex, and nucleus accumbens simultaneously. Linking spatial distribution to quantitative variation of lipids from the whole brain sections contributes the uncovering of new insights in causal mechanism of lipid dyshomeostasis in depression investigation and related targeting interventions.
There is growing evidence that lipid metabolism instability in depressive disorder may be a core early pathological event associated with numerous pathogenesis hypotheses. However, spatial distributions and quantitative changes of lipids in specific brain regions associated with depressive disorder are far from elucidated. In the present study, lipid profiling characteristics of whole brain sections are systematically determined by using matrix-assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI)-combined with histomorphological analysis in rats with depressive-like behavior induced by multiple early life stress (mELS) and unstressed control. Lipid dyshomeostasis and different degrees of metabolic disturbance occur in the eight paired representative brain sections from micro-region and molecular level. More specifically, 17 lipid molecules show the severe dyshomeostasis between inter-group (control and depressed rats) or intra-group (multiple emotion-regulation-related brain regions). Quite specially, phosphatidylcholine (PC) (39:6) expression in section 7 is significantly upregulated only in the amygdala of depressed rat relative to control rat, by contrast, up-regulated phosphatidylglycerol (PG) (34:2) in section 2 emerges in the medial prefrontal cortex, insular cortex, and nucleus accumbens simultaneously. Linking spatial distribution to quantitative variation of lipids from the whole brain sections contributes the uncovering of new insights in causal mechanism of lipid dyshomeostasis in depression investigation and related targeting interventions.
2025, 36(10): 111256
doi: 10.1016/j.cclet.2025.111256
摘要:
Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features. Herein, we successfully synthesized an 11-core copper(Ⅰ)-alkynyl nanocluster (Cu11), which is stabilized by alkynyl ligands derived from a photosensitive rhodamine dye molecule. Notably, this Cu11 cluster exhibited excellent photocatalytic hydrogen evolution activity (8.13 mmol g−1h−1) even in the absence of a mediator and noble metal co-catalyst. Furthermore, when Cu11 clusters were loaded onto the surface of TiO2 nanosheets, the resultant Cu11@TiO2 nanocomposites exhibited a significant enhancement in hydrogen evolution efficiency, which is 60 times higher than that of pure TiO2 nanosheets. The incorporation of Cu11 clusters within the Cu11@TiO2 effectively inhibits the recombination of photogenerated electrons and holes, thereby accelerating the charge separation and migration in the composite material. This work introduces a novel perspective for designing highly active copper cluster-based photocatalysts.
Metal nanoclusters with well-defined atomic structures offer significant promise in the field of catalysis due to their sub-nanometer size and tunable organic-inorganic hybrid structural features. Herein, we successfully synthesized an 11-core copper(Ⅰ)-alkynyl nanocluster (Cu11), which is stabilized by alkynyl ligands derived from a photosensitive rhodamine dye molecule. Notably, this Cu11 cluster exhibited excellent photocatalytic hydrogen evolution activity (8.13 mmol g−1h−1) even in the absence of a mediator and noble metal co-catalyst. Furthermore, when Cu11 clusters were loaded onto the surface of TiO2 nanosheets, the resultant Cu11@TiO2 nanocomposites exhibited a significant enhancement in hydrogen evolution efficiency, which is 60 times higher than that of pure TiO2 nanosheets. The incorporation of Cu11 clusters within the Cu11@TiO2 effectively inhibits the recombination of photogenerated electrons and holes, thereby accelerating the charge separation and migration in the composite material. This work introduces a novel perspective for designing highly active copper cluster-based photocatalysts.
2025, 36(10): 111269
doi: 10.1016/j.cclet.2025.111269
摘要:
The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO2 conversion. This study demonstrates how controlled exposure of metal sites governs CO2 electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures. The Bi8-DMF cluster, constructed using tert-butylthiacalix[4 ]arene (TC4A) as the sole ligand, features two surface-exposed Bi active sites, while the dual-ligand Bi8-Fc (with TC4A/ferrocene carboxylate) forms a fully encapsulated structure. Electrocatalytic tests reveal Bi8-DMF achieves exceptional formate selectivity (> 90% Faradaic efficiency) across a broad potential window (-0.9 V to -1.6 V vs. RHE) with 20 h stability, outperforming Bi8-Fc (60% efficiency at -1.5 V). Theoretical calculations attribute Bi8-DMF's superiority to exposed Bi sites that stabilize the critical *OCHO intermediate via optimized orbital interactions. This work provides crucial guidance for polynuclear catalyst design: moderate exposure of metal active sites significantly enhances CO2 reduction performance.
The atomic-level exploration of structure-property correlations poses significant challenges in establishing precise design principles for electrocatalysts targeting efficient CO2 conversion. This study demonstrates how controlled exposure of metal sites governs CO2 electroreduction performance through two octanuclear bismuth-oxo clusters with distinct architectures. The Bi8-DMF cluster, constructed using tert-butylthiacalix[
2025, 36(10): 111293
doi: 10.1016/j.cclet.2025.111293
摘要:
The development of next-generation electromagnetic wave (EMW) absorbers requires a shift in interface design. By employing hierarchical work function programming, we propose an approach to tune interfacial polarization dynamics. This method utilizes multi-gradient work functions to guide carrier migration and polarization effectively, thereby enhancing energy dissipation under alternating electromagnetic fields. Here, we constructed a 1T/2H-MoS2/PPy/VS2 composite absorber with integrated gradient interfaces. The composite achieved a powerful absorption (RLmin) of -58.59 dB at 2.3 mm, and an effective absorption bandwidth (EAB) of 7.44 GHz at 2.5 mm, demonstrating improved broadband absorption. Radar cross-section (RCS) simulations show an EMW loss of -7.2 dB m2 at 0°, highlighting its potential for stealth and communication applications. This study introduces hierarchical work function programming as a promising strategy in EMW absorber design, contributing to advancements in material performance and functionality.
The development of next-generation electromagnetic wave (EMW) absorbers requires a shift in interface design. By employing hierarchical work function programming, we propose an approach to tune interfacial polarization dynamics. This method utilizes multi-gradient work functions to guide carrier migration and polarization effectively, thereby enhancing energy dissipation under alternating electromagnetic fields. Here, we constructed a 1T/2H-MoS2/PPy/VS2 composite absorber with integrated gradient interfaces. The composite achieved a powerful absorption (RLmin) of -58.59 dB at 2.3 mm, and an effective absorption bandwidth (EAB) of 7.44 GHz at 2.5 mm, demonstrating improved broadband absorption. Radar cross-section (RCS) simulations show an EMW loss of -7.2 dB m2 at 0°, highlighting its potential for stealth and communication applications. This study introduces hierarchical work function programming as a promising strategy in EMW absorber design, contributing to advancements in material performance and functionality.
2025, 36(10): 111294
doi: 10.1016/j.cclet.2025.111294
摘要:
Zinc-nitrate battery could produce electrical power, remove pollutant nitrate and obtain value-added ammonia, where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement of multi-electron transfer. Thus, highly efficient catalysts for nitrate reduction reaction (NO3RR) are greatly needed. In this work, we report a high entropy hydroxide (HE-OH) as an excellent NO3RR catalyst, which could achieve high NH3 Faradaic efficiencies (e.g., nearly 100% at −0.3 V versus reversible hydrogen electrode) and high yield rates (e.g., 30.4 mg h−1cm−2 at −0.4 V). Moreover, HE-OH could also deliver a current density of 10 mA/cm2 at an overpotential of 260 mV for oxygen evolution reaction. The assembled zinc-nitrate battery using HE-OH as the cathode demonstrates a high power density (e.g., 3.62 mW/cm2), rechargeability and stability.
Zinc-nitrate battery could produce electrical power, remove pollutant nitrate and obtain value-added ammonia, where the cathodic reaction of converting nitrate to ammonia is sluggish and complex due to the involvement of multi-electron transfer. Thus, highly efficient catalysts for nitrate reduction reaction (NO3RR) are greatly needed. In this work, we report a high entropy hydroxide (HE-OH) as an excellent NO3RR catalyst, which could achieve high NH3 Faradaic efficiencies (e.g., nearly 100% at −0.3 V versus reversible hydrogen electrode) and high yield rates (e.g., 30.4 mg h−1cm−2 at −0.4 V). Moreover, HE-OH could also deliver a current density of 10 mA/cm2 at an overpotential of 260 mV for oxygen evolution reaction. The assembled zinc-nitrate battery using HE-OH as the cathode demonstrates a high power density (e.g., 3.62 mW/cm2), rechargeability and stability.
2025, 36(10): 111296
doi: 10.1016/j.cclet.2025.111296
摘要:
Precise control of luminescence in carbon quantum dots (CQDs), from single-color to full-color emission, is crucial for advancing their applications in biomedical imaging and display technologies. While CQDs luminescence is primarily influenced by conjugated domains and surface states, the underlying interaction mechanisms remain poorly understood. This study explores a graded nitro-engineering approach to simultaneously regulate surface states and sp2 conjugated domains through nitro (-NO2) modulation, enabling comprehensive color tuning. Using o-phenylenediamine (o-PD) as the carbon source and adjusting nitric acid (HNO3) concentrations, we synthesized tricolor-emitting nitro-functionalized CQDs (NO2-CQDs). At lower -NO2 concentrations, luminescence is mainly influenced by surface states, where the electron-withdrawing effect of -NO2 enhances π-electron delocalization and stabilizes sp2 conjugation. With increasing -NO2 content, the lowest unoccupied molecular orbital (LUMO) energy level decreases (-2.12 eV to -3.39 eV), resulting in a red-shift in fluorescence. At higher -NO2 concentrations, luminescence is primarily affected by the sp2 conjugated domain, where steric hindrance reduces molecular planarity and conjugation, leading to a blue-shift in fluorescence as the sp2 domain size decreases (4.03 nm to 2.83 nm). Combining experimental results with density functional theory (DFT) calculations, we reveal the dual role of -NO2 in modulating CQDs luminescence, an approach rarely achieved through surface functionalization. This work presents a novel strategy for precise tuning of CQDs luminescence across the visible spectrum.
Precise control of luminescence in carbon quantum dots (CQDs), from single-color to full-color emission, is crucial for advancing their applications in biomedical imaging and display technologies. While CQDs luminescence is primarily influenced by conjugated domains and surface states, the underlying interaction mechanisms remain poorly understood. This study explores a graded nitro-engineering approach to simultaneously regulate surface states and sp2 conjugated domains through nitro (-NO2) modulation, enabling comprehensive color tuning. Using o-phenylenediamine (o-PD) as the carbon source and adjusting nitric acid (HNO3) concentrations, we synthesized tricolor-emitting nitro-functionalized CQDs (NO2-CQDs). At lower -NO2 concentrations, luminescence is mainly influenced by surface states, where the electron-withdrawing effect of -NO2 enhances π-electron delocalization and stabilizes sp2 conjugation. With increasing -NO2 content, the lowest unoccupied molecular orbital (LUMO) energy level decreases (-2.12 eV to -3.39 eV), resulting in a red-shift in fluorescence. At higher -NO2 concentrations, luminescence is primarily affected by the sp2 conjugated domain, where steric hindrance reduces molecular planarity and conjugation, leading to a blue-shift in fluorescence as the sp2 domain size decreases (4.03 nm to 2.83 nm). Combining experimental results with density functional theory (DFT) calculations, we reveal the dual role of -NO2 in modulating CQDs luminescence, an approach rarely achieved through surface functionalization. This work presents a novel strategy for precise tuning of CQDs luminescence across the visible spectrum.
2025, 36(10): 111302
doi: 10.1016/j.cclet.2025.111302
摘要:
The synergistic effects of piezoelectric catalysis and plasmonic photocatalysis hold significant promise for achieving high-efficiency solar energy conversion. Herein, SnFe2O4@ZnIn2S4 (SFO@ZIS) composites were prepared by a facile low-temperature water bath method, and an efficient and stable near-infrared (NIR) photothermal-assisted piezoelectric photocatalytic system was successfully constructed. The system achieved a synergistic effect of ultrasonic vibration and NIR illumination, driving a photocatalytic hydrogen (H2) production rate of 17.9 µmol g-1 h-1. Related photothermal test results demonstrate that the localized surface plasmon (LSPR) resonance effect of SFO not only significantly broadens the NIR light absorption of ZIS, but also improves the reaction temperature and reduces the activation energy of the reaction by efficiently converting the light energy into heat energy. In addition, photoelectrochemical analyses revealed that the SFO with excellent piezoelectric activity effectively facilitated carrier separation by transferring the energetic hot electrons generated by the LSPR effect to the conduction band of ZIS under external mechanical pressure. This study presents an effective design strategy and theoretical basis for constructing an efficient and robust NIR-driven photothermally assisted piezoelectric photo-catalytic system.
The synergistic effects of piezoelectric catalysis and plasmonic photocatalysis hold significant promise for achieving high-efficiency solar energy conversion. Herein, SnFe2O4@ZnIn2S4 (SFO@ZIS) composites were prepared by a facile low-temperature water bath method, and an efficient and stable near-infrared (NIR) photothermal-assisted piezoelectric photocatalytic system was successfully constructed. The system achieved a synergistic effect of ultrasonic vibration and NIR illumination, driving a photocatalytic hydrogen (H2) production rate of 17.9 µmol g-1 h-1. Related photothermal test results demonstrate that the localized surface plasmon (LSPR) resonance effect of SFO not only significantly broadens the NIR light absorption of ZIS, but also improves the reaction temperature and reduces the activation energy of the reaction by efficiently converting the light energy into heat energy. In addition, photoelectrochemical analyses revealed that the SFO with excellent piezoelectric activity effectively facilitated carrier separation by transferring the energetic hot electrons generated by the LSPR effect to the conduction band of ZIS under external mechanical pressure. This study presents an effective design strategy and theoretical basis for constructing an efficient and robust NIR-driven photothermally assisted piezoelectric photo-catalytic system.
2025, 36(10): 111303
doi: 10.1016/j.cclet.2025.111303
摘要:
A comprehensive understanding of the structure and dynamic evolution of catalytic active sites is vital for advancing the study of liquid-phase acetylene hydrochlorination. Here, we successfully developed a Ru-DIPEA/TMS catalyst optimised through systematic composition and condition tuning, demonstrating exceptional performance with 95.5% C2H2 conversion and sustaining over 91.1% activity along with nearly 100% selectivity for VCM during a continuous 900-h test. Using a combination of characterisation techniques, including UV–vis spectroscopy, FT-IR spectroscopy, X-ray photoelectron spectroscopy, single-crystal X-ray diffraction, and X-ray absorption spectroscopy, along with density functional theory (DFT) calculations, the structure and dynamic behaviour of the active sites were thoroughly investigated under the synergistic influence of ligands and HCl. The results revealed that HCl activation induces a significant structural transformation of the active sites, leading to the formation of a hexacoordinate complex, Ru(CO)2Cl2(C6H15N·HCl)2. DFT calculations further elucidated the mechanism underlying active site formation, revealing that an increased electron density around the Ru centre and corresponding changes in its coordination environment play critical roles in enhancing catalyst stability and activity. This study contributes to a deeper understanding of the structural basis of active site evolution during acetylene hydrochlorination, offering both practical insights into industrial applications and foundational knowledge for advancing liquid-phase catalysis.
A comprehensive understanding of the structure and dynamic evolution of catalytic active sites is vital for advancing the study of liquid-phase acetylene hydrochlorination. Here, we successfully developed a Ru-DIPEA/TMS catalyst optimised through systematic composition and condition tuning, demonstrating exceptional performance with 95.5% C2H2 conversion and sustaining over 91.1% activity along with nearly 100% selectivity for VCM during a continuous 900-h test. Using a combination of characterisation techniques, including UV–vis spectroscopy, FT-IR spectroscopy, X-ray photoelectron spectroscopy, single-crystal X-ray diffraction, and X-ray absorption spectroscopy, along with density functional theory (DFT) calculations, the structure and dynamic behaviour of the active sites were thoroughly investigated under the synergistic influence of ligands and HCl. The results revealed that HCl activation induces a significant structural transformation of the active sites, leading to the formation of a hexacoordinate complex, Ru(CO)2Cl2(C6H15N·HCl)2. DFT calculations further elucidated the mechanism underlying active site formation, revealing that an increased electron density around the Ru centre and corresponding changes in its coordination environment play critical roles in enhancing catalyst stability and activity. This study contributes to a deeper understanding of the structural basis of active site evolution during acetylene hydrochlorination, offering both practical insights into industrial applications and foundational knowledge for advancing liquid-phase catalysis.
2025, 36(10): 111313
doi: 10.1016/j.cclet.2025.111313
摘要:
Liposomal drugs have significantly improved cancer treatment in recent years. However, the clinical application of conventional liposomes is limited by factors such as the complexity of the preparation process and the multitude of auxiliary components. By replacing phospholipids and cholesterol with vitamin E succinate (VES), this study addresses these shortcomings by developing a novel modified nanoprodrug, and the new formulation is used to deliver cisplatin. Concurrently, liposomes encapsulating cisplatin were prepared by conventional formulations for comparative experiments. Moreover, VES can inhibit the expression of mitochondrial uncoupling protein 2 (UCP2), further enhancing mitochondrial damage in tumor cells within the tumor microenvironment (TME) and suppressing the tricarboxylic acid cycle, thereby reducing ATP production. Additionally, cisplatin damages DNA structure, affecting the binding of Nrf2 to the antioxidant response element (ARE), thereby inhibiting the signaling expression of heme oxygenase 1 (HO-1). The combined action of cisplatin and VES disrupts the redox balanceleading to a significant accumulation of reactive oxygen species (ROS). The nanoprodrug effectively alters the redox state of the TME and inhibits antioxidant defenses, thereby amplifying oxidative stress damage and enhancing the efficacy of cisplatin. Notably, compared to free cisplatin, the nanoprodrug demonstrates greater efficacy in both cell line-derived xenograft (CDX) and patient-derived tumor xenograft (PDX) liver cancer models. Overall, this study successfully develops a novel mitochondrial-targeted nanoprodrug by modifying the conventional liposome formulation. This provides a new strategy for amplifying oxidative stress in order to disrupt redox balance, and enhance cisplatin efficacy.
Liposomal drugs have significantly improved cancer treatment in recent years. However, the clinical application of conventional liposomes is limited by factors such as the complexity of the preparation process and the multitude of auxiliary components. By replacing phospholipids and cholesterol with vitamin E succinate (VES), this study addresses these shortcomings by developing a novel modified nanoprodrug, and the new formulation is used to deliver cisplatin. Concurrently, liposomes encapsulating cisplatin were prepared by conventional formulations for comparative experiments. Moreover, VES can inhibit the expression of mitochondrial uncoupling protein 2 (UCP2), further enhancing mitochondrial damage in tumor cells within the tumor microenvironment (TME) and suppressing the tricarboxylic acid cycle, thereby reducing ATP production. Additionally, cisplatin damages DNA structure, affecting the binding of Nrf2 to the antioxidant response element (ARE), thereby inhibiting the signaling expression of heme oxygenase 1 (HO-1). The combined action of cisplatin and VES disrupts the redox balanceleading to a significant accumulation of reactive oxygen species (ROS). The nanoprodrug effectively alters the redox state of the TME and inhibits antioxidant defenses, thereby amplifying oxidative stress damage and enhancing the efficacy of cisplatin. Notably, compared to free cisplatin, the nanoprodrug demonstrates greater efficacy in both cell line-derived xenograft (CDX) and patient-derived tumor xenograft (PDX) liver cancer models. Overall, this study successfully develops a novel mitochondrial-targeted nanoprodrug by modifying the conventional liposome formulation. This provides a new strategy for amplifying oxidative stress in order to disrupt redox balance, and enhance cisplatin efficacy.
2025, 36(10): 111325
doi: 10.1016/j.cclet.2025.111325
摘要:
Liver cancer is the fourth cause of cancer-related deaths and the primary cause of death in patients with compensated cirrhosis. In recent years, the role of traditional Chinese medicine in the treatment of liver cancer has attracted more and more attention and recognition. Luteolin (LUT) and glycyrrhetinic (GA) are natural compounds extracted from Chinese herbal medicine. LUT exhibits various biological activity including anti-inflammatory, antibacterial, antiviral, anti-tumor, and neuroprotective effects. GA significantly inhibits the growth and metastasis of cancer cells. However, the low water solubility of both compounds hinders their clinical applications. In this study, rod-shaped nanoparticles (NPs) self-assembled from LUT and GA were designed to enhance drug solubility and tumor-targeting capability. We verified that the assembly mechanism of the NPs was π-π stacking. These NPs significantly inhibited the proliferation of liver cancer cells while had no significant effect on normal liver cells. In a mouse model of liver cancer, these NPs demonstrated superior tumor-targeting ability due to the enhanced permeability and retention effect, and the affinity of GA for liver cancer cells, resulting in better therapeutic efficacy with lower systemic toxicity. Results of network pharmacology analysis showed that LUT and GA respectively targeted estrogen receptor 1 (ESR1) protein and cyclin-dependent kinase 1 (CDK1) protein to corporately induce tumor cell cycle arrest, which induced the inhibition of tumor cell proliferation. In conclusion, this study provides a novel reference for the treatment of liver cancer.
Liver cancer is the fourth cause of cancer-related deaths and the primary cause of death in patients with compensated cirrhosis. In recent years, the role of traditional Chinese medicine in the treatment of liver cancer has attracted more and more attention and recognition. Luteolin (LUT) and glycyrrhetinic (GA) are natural compounds extracted from Chinese herbal medicine. LUT exhibits various biological activity including anti-inflammatory, antibacterial, antiviral, anti-tumor, and neuroprotective effects. GA significantly inhibits the growth and metastasis of cancer cells. However, the low water solubility of both compounds hinders their clinical applications. In this study, rod-shaped nanoparticles (NPs) self-assembled from LUT and GA were designed to enhance drug solubility and tumor-targeting capability. We verified that the assembly mechanism of the NPs was π-π stacking. These NPs significantly inhibited the proliferation of liver cancer cells while had no significant effect on normal liver cells. In a mouse model of liver cancer, these NPs demonstrated superior tumor-targeting ability due to the enhanced permeability and retention effect, and the affinity of GA for liver cancer cells, resulting in better therapeutic efficacy with lower systemic toxicity. Results of network pharmacology analysis showed that LUT and GA respectively targeted estrogen receptor 1 (ESR1) protein and cyclin-dependent kinase 1 (CDK1) protein to corporately induce tumor cell cycle arrest, which induced the inhibition of tumor cell proliferation. In conclusion, this study provides a novel reference for the treatment of liver cancer.
2025, 36(10): 111332
doi: 10.1016/j.cclet.2025.111332
摘要:
Advanced oxidation processes are promising for degradation of the highly chemical stability and refractory methylisothiazolinone (MIT) bactericides in relevant industrial wastewater. In order to assemble a low cost and high performance electrochemical oxidation system for wastewater treatment, granular active carbon (GAC) was decorated by doping Ce, Sn, Sb to synthesize Sn-Sb-Ce/GAC using sol-gel method as particle electrode filled into a three-dimensional (3D) electrochemical reactor. Scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD) experiments revealed that the Sn-Sb-Ce/GAC particle electrode crystal particles were compact and uniform, and the surface structure was improved. The ten cyclic experiments indicated that the Sn-Sb-Ce/GAC particle electrode had high stability and low dissolution of the loaded active substance. The degradation mechanism of MIT was studied under the optimal working conditions of 3D electrode system with GAC of 5 g/L, current density of 20 mA/cm2, initial pH 5, electrolyte concentration of Na2SO4 0.02 mol/L and reaction time of 120 min. The indirect electrochemical degradation of MIT was dominated by active substance pathway that active chlorine rather than free radicals (•OH) played the main role. Comparing with conventional two-dimensional (2D) electrode system, the 3D electrochemical system has larger active electrode area, higher treatment efficiency and lower energy consumption than the former. The 3D electrochemical system could remove 96.5% of MIT from the actual high-salt reverse osmosis concentrate wastewater in 30 min. It has a certain removal effect on UV254 in wastewater, but has a better removal effect on fluorescent substances. This study proposed a new strategy to develop transition metal and rare earth metal particle electrodes using carbon-based materials for high efficient electrocatalytic oxidation in the electrochemical treatment system.
Advanced oxidation processes are promising for degradation of the highly chemical stability and refractory methylisothiazolinone (MIT) bactericides in relevant industrial wastewater. In order to assemble a low cost and high performance electrochemical oxidation system for wastewater treatment, granular active carbon (GAC) was decorated by doping Ce, Sn, Sb to synthesize Sn-Sb-Ce/GAC using sol-gel method as particle electrode filled into a three-dimensional (3D) electrochemical reactor. Scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS) and X-ray diffraction (XRD) experiments revealed that the Sn-Sb-Ce/GAC particle electrode crystal particles were compact and uniform, and the surface structure was improved. The ten cyclic experiments indicated that the Sn-Sb-Ce/GAC particle electrode had high stability and low dissolution of the loaded active substance. The degradation mechanism of MIT was studied under the optimal working conditions of 3D electrode system with GAC of 5 g/L, current density of 20 mA/cm2, initial pH 5, electrolyte concentration of Na2SO4 0.02 mol/L and reaction time of 120 min. The indirect electrochemical degradation of MIT was dominated by active substance pathway that active chlorine rather than free radicals (•OH) played the main role. Comparing with conventional two-dimensional (2D) electrode system, the 3D electrochemical system has larger active electrode area, higher treatment efficiency and lower energy consumption than the former. The 3D electrochemical system could remove 96.5% of MIT from the actual high-salt reverse osmosis concentrate wastewater in 30 min. It has a certain removal effect on UV254 in wastewater, but has a better removal effect on fluorescent substances. This study proposed a new strategy to develop transition metal and rare earth metal particle electrodes using carbon-based materials for high efficient electrocatalytic oxidation in the electrochemical treatment system.
2025, 36(10): 111395
doi: 10.1016/j.cclet.2025.111395
摘要:
To accomplish on-site separation, preconcentration and cold storage of highly volatile organic compounds (VOCs) from water samples as well as their rapid transportation to laboratory, a high-throughput miniaturized purge-and-trap (µP&T) device integrating semiconductor refrigeration storage was developed in this work. Water samples were poured into the purge vessels and purged with purified air generated by an air pump. The VOCs in water samples were then separated and preconcentrated with sorbent tubes. After their complete separation and preconcentration, the tubes were subsequently preserved in the semiconductor refrigeration unit of the µP&T device. Notably, the high integration, small size, light weight, and low power consumption of the device makes it easy to be hand-carried to the field and transport by drone from remote locations, significantly enhancing the flexibility of field sampling. The performances of the device were evaluated by comparing analytical figures of merit for the detection of four cyclic volatile methylsiloxanes (cVMSs) in water. Compared to conventional collection and preservation methods, our proposed device preserved the VOCs more consistently in the sorbent tubes, with less than 5% loss of all analytes, and maintained stability for at least 20 days at 4 °C. As a proof-of-concept, 10 municipal wastewater samples were pretreated using this device with recoveries ranging from 82.5% to 99.9% for the target VOCs.
To accomplish on-site separation, preconcentration and cold storage of highly volatile organic compounds (VOCs) from water samples as well as their rapid transportation to laboratory, a high-throughput miniaturized purge-and-trap (µP&T) device integrating semiconductor refrigeration storage was developed in this work. Water samples were poured into the purge vessels and purged with purified air generated by an air pump. The VOCs in water samples were then separated and preconcentrated with sorbent tubes. After their complete separation and preconcentration, the tubes were subsequently preserved in the semiconductor refrigeration unit of the µP&T device. Notably, the high integration, small size, light weight, and low power consumption of the device makes it easy to be hand-carried to the field and transport by drone from remote locations, significantly enhancing the flexibility of field sampling. The performances of the device were evaluated by comparing analytical figures of merit for the detection of four cyclic volatile methylsiloxanes (cVMSs) in water. Compared to conventional collection and preservation methods, our proposed device preserved the VOCs more consistently in the sorbent tubes, with less than 5% loss of all analytes, and maintained stability for at least 20 days at 4 °C. As a proof-of-concept, 10 municipal wastewater samples were pretreated using this device with recoveries ranging from 82.5% to 99.9% for the target VOCs.
2025, 36(10): 111444
doi: 10.1016/j.cclet.2025.111444
摘要:
We herein present an efficient denitrative iodination method of (hetero)nitroarenes mediated by commercially available and cost-effective hydroiodic acid (HI). During the reaction process, HI plays its dual roles as both the sustainable reductant of nitro group and iodine source in the iodination step, which successfully integrates three steps into a one-pot procedure and significantly simplifies the reaction system. This approach enables a smooth metal-free conversion of nitroarenes to corresponding aryl iodides via one-pot process, exhibits a broad substrate scope and good reaction efficiency, and was conveniently applied in the concise synthesis of pharmaceuticals.
We herein present an efficient denitrative iodination method of (hetero)nitroarenes mediated by commercially available and cost-effective hydroiodic acid (HI). During the reaction process, HI plays its dual roles as both the sustainable reductant of nitro group and iodine source in the iodination step, which successfully integrates three steps into a one-pot procedure and significantly simplifies the reaction system. This approach enables a smooth metal-free conversion of nitroarenes to corresponding aryl iodides via one-pot process, exhibits a broad substrate scope and good reaction efficiency, and was conveniently applied in the concise synthesis of pharmaceuticals.
2025, 36(10): 111521
doi: 10.1016/j.cclet.2025.111521
摘要:
Photothermal catalysis is a promising technology primarily utilized the solar energy to produce photogenerated e-/h+ pairs together with the production of heat energy. However, the inefficient separation of charge carriers and inadequate response to near-infrared (NIR) light usually leads to the unsatisfactory photocatalytic efficiency, hindering their application potentials. In this work, a significantly enhanced photothermal catalytic hydrogen evolution reaction over the lead-free perovskite Cs3Bi2Br9/FeS2 (CBB/FS) heterostructure is simultaneously verified, where the CBB/FS Z-scheme heterojunctions display the strong stability and superb photothermal catalytic activity. Under the simulated solar irradiation (AM 1.5G), the optimized CBB/FS-5 achieves a photocatalytic hydrogen evolution rate of 31.5 mmol g-1 h-1, which is 112.6 and 77.1 times higher than that of FS and CBB, respectively, together with an apparent quantum yield of 29.5% at 420 nm. This significantly improved photocatalytic H2 evolution can be mainly attributed to the Z-scheme charge transfer and photothermal-assisted synergistically enhanced photocatalytic H2 production, and the potential mechanism of the enhanced photocatalytic H2 evolution is also proposed by photoelectrochemical characterizations, in situ XPS, EPR spectra, and the DFT calculations. This work provides new insights to the design of high-efficient photothermal catalysts, leading to the sustainable and efficient solutions towards the energy and environmental challenges.
Photothermal catalysis is a promising technology primarily utilized the solar energy to produce photogenerated e-/h+ pairs together with the production of heat energy. However, the inefficient separation of charge carriers and inadequate response to near-infrared (NIR) light usually leads to the unsatisfactory photocatalytic efficiency, hindering their application potentials. In this work, a significantly enhanced photothermal catalytic hydrogen evolution reaction over the lead-free perovskite Cs3Bi2Br9/FeS2 (CBB/FS) heterostructure is simultaneously verified, where the CBB/FS Z-scheme heterojunctions display the strong stability and superb photothermal catalytic activity. Under the simulated solar irradiation (AM 1.5G), the optimized CBB/FS-5 achieves a photocatalytic hydrogen evolution rate of 31.5 mmol g-1 h-1, which is 112.6 and 77.1 times higher than that of FS and CBB, respectively, together with an apparent quantum yield of 29.5% at 420 nm. This significantly improved photocatalytic H2 evolution can be mainly attributed to the Z-scheme charge transfer and photothermal-assisted synergistically enhanced photocatalytic H2 production, and the potential mechanism of the enhanced photocatalytic H2 evolution is also proposed by photoelectrochemical characterizations, in situ XPS, EPR spectra, and the DFT calculations. This work provides new insights to the design of high-efficient photothermal catalysts, leading to the sustainable and efficient solutions towards the energy and environmental challenges.
2025, 36(10): 110386
doi: 10.1016/j.cclet.2024.110386
摘要:
For a long time, researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates (POMs). Modifying POMs with various types and properties of metals has broadened their applications in fields such as magnetism, luminescence, and catalysis. However, despite the discovery of numerous POM structures doped with transition metal ions, the development of aluminum (Al) as a ⅢA group metal in the POM field has been slow. Aluminum, the most abundant metal in nature, offers innate electron-deficient properties that, when combined with highly charged POMs, could introduce novel structures and excellent functionalities like proton conduction to this field. Therefore, this review will address the gap in summarizing Al-containing POMs by categorizing and summarizing the synthesis, structural characteristics, and properties of Al-containing POMs, aiming to provide a theoretical foundation for exploring POM structures doped with Al atoms. The review also analyzes and forecasts the prospects in this field.
For a long time, researchers have been fascinated by the structurally diverse and high-performance characteristics of polyoxometalates (POMs). Modifying POMs with various types and properties of metals has broadened their applications in fields such as magnetism, luminescence, and catalysis. However, despite the discovery of numerous POM structures doped with transition metal ions, the development of aluminum (Al) as a ⅢA group metal in the POM field has been slow. Aluminum, the most abundant metal in nature, offers innate electron-deficient properties that, when combined with highly charged POMs, could introduce novel structures and excellent functionalities like proton conduction to this field. Therefore, this review will address the gap in summarizing Al-containing POMs by categorizing and summarizing the synthesis, structural characteristics, and properties of Al-containing POMs, aiming to provide a theoretical foundation for exploring POM structures doped with Al atoms. The review also analyzes and forecasts the prospects in this field.
2025, 36(10): 110745
doi: 10.1016/j.cclet.2024.110745
摘要:
The harmful algal bloom primarily caused by Microcystis aeruginosa (M. aeruginosa) has become one of the serious biological pollution issues in actual water, which has received intense attention worldwide. Over the past years, increasing number of publications have reported that metal-organic frameworks (MOFs) based functional materials exhibited significant inhibition against M. aeruginosa via multiple mechanisms, but no review papers systematically presented progresses regarding MOFs-based materials for M. aeruginosa control up to now. With this review paper, we summarized the state-of-the-art studies of MOFs-based materials for M. aeruginosa removal, comparing and discussing the design strategies of MOFs-based materials and their antimicrobial mechanisms. Meanwhile, we discussed methods for evaluating the water purification performances of MOFs-based materials against M. aeruginosa. Finally, the perspectives for design of novel MOFs-based functional materials and application scenarios were proposed to provide an outlook on areas where greater efforts should be made in the future.
The harmful algal bloom primarily caused by Microcystis aeruginosa (M. aeruginosa) has become one of the serious biological pollution issues in actual water, which has received intense attention worldwide. Over the past years, increasing number of publications have reported that metal-organic frameworks (MOFs) based functional materials exhibited significant inhibition against M. aeruginosa via multiple mechanisms, but no review papers systematically presented progresses regarding MOFs-based materials for M. aeruginosa control up to now. With this review paper, we summarized the state-of-the-art studies of MOFs-based materials for M. aeruginosa removal, comparing and discussing the design strategies of MOFs-based materials and their antimicrobial mechanisms. Meanwhile, we discussed methods for evaluating the water purification performances of MOFs-based materials against M. aeruginosa. Finally, the perspectives for design of novel MOFs-based functional materials and application scenarios were proposed to provide an outlook on areas where greater efforts should be made in the future.
2025, 36(10): 110771
doi: 10.1016/j.cclet.2024.110771
摘要:
Cancer remains one of the major threats to public health. Traditional chemotherapy, radiotherapy, and other anti-tumor therapies have numerous limitations in clinical treatment. Notwithstanding the considerable advances made in recent years with regard to immunotherapy in both basic research and clinical practice, there remains scope for further improvement, particularly with respect to its efficacy against solid tumors. With advancements in nanotechnology, tumor nanovaccines hold immense potential for preventing tumor recurrence and treating metastatic tumors. Nevertheless, the considerable heterogeneity of tumor immunogenicity presents a number of significant challenges in the development of nanometre-scale vaccines targeting solid tumors. Recent findings indicate that immune checkpoint inhibitor (ICI) therapy can improve the immunosuppressive microenvironment within tumors, while nanovaccines can also augment tumor sensitivity toward ICIs. Consequently, combining tumor nanovaccine with ICI therapy holds promise for effectively eradicating tumors or controlling their recurrence and metastasis during cancer treatment. This review delves into the mechanism behind combining tumor nanovaccine with ICI while focusing on factors influencing this combined therapy approach. Moreover, it offers an overview of the current research status regarding the combination of tumor nanovaccines with chemotherapy, radiotherapy, photothermal therapy, and sonodynamic therapy, as well as prospects for future developments in this field.
Cancer remains one of the major threats to public health. Traditional chemotherapy, radiotherapy, and other anti-tumor therapies have numerous limitations in clinical treatment. Notwithstanding the considerable advances made in recent years with regard to immunotherapy in both basic research and clinical practice, there remains scope for further improvement, particularly with respect to its efficacy against solid tumors. With advancements in nanotechnology, tumor nanovaccines hold immense potential for preventing tumor recurrence and treating metastatic tumors. Nevertheless, the considerable heterogeneity of tumor immunogenicity presents a number of significant challenges in the development of nanometre-scale vaccines targeting solid tumors. Recent findings indicate that immune checkpoint inhibitor (ICI) therapy can improve the immunosuppressive microenvironment within tumors, while nanovaccines can also augment tumor sensitivity toward ICIs. Consequently, combining tumor nanovaccine with ICI therapy holds promise for effectively eradicating tumors or controlling their recurrence and metastasis during cancer treatment. This review delves into the mechanism behind combining tumor nanovaccine with ICI while focusing on factors influencing this combined therapy approach. Moreover, it offers an overview of the current research status regarding the combination of tumor nanovaccines with chemotherapy, radiotherapy, photothermal therapy, and sonodynamic therapy, as well as prospects for future developments in this field.
2025, 36(10): 110799
doi: 10.1016/j.cclet.2024.110799
摘要:
The evolution of cancer therapies has highlighted the limitations of traditional chemotherapy, particularly its lack of specificity and off-target toxicities, driving the development of targeted treatments like small molecule-drug conjugates (SMDCs). SMDCs offer distinct advantages over antibody-drug conjugates (ADCs), including simpler synthesis, lower production costs, and improved solid tumor penetration due to their smaller size. However, challenges remain, such as a limited variety of targeting ligands and the complexity of optimizing selectivity and efficacy within the tumor microenvironment. This review focuses on key aspects such as mechanisms of action, biomarker selection, and the optimization of each component of SMDCs. It also covers SMDCs that have been approved or are currently under active clinical trials, while providing insights into future developments in this promising field of targeted cancer therapies.
The evolution of cancer therapies has highlighted the limitations of traditional chemotherapy, particularly its lack of specificity and off-target toxicities, driving the development of targeted treatments like small molecule-drug conjugates (SMDCs). SMDCs offer distinct advantages over antibody-drug conjugates (ADCs), including simpler synthesis, lower production costs, and improved solid tumor penetration due to their smaller size. However, challenges remain, such as a limited variety of targeting ligands and the complexity of optimizing selectivity and efficacy within the tumor microenvironment. This review focuses on key aspects such as mechanisms of action, biomarker selection, and the optimization of each component of SMDCs. It also covers SMDCs that have been approved or are currently under active clinical trials, while providing insights into future developments in this promising field of targeted cancer therapies.
2025, 36(10): 110802
doi: 10.1016/j.cclet.2024.110802
摘要:
Acute kidney injury (AKI) is a prevalent clinical syndrome characterized by a rapid loss of renal filtration function, with high incidence and mortality rates that are steadily rising. AKI not only affects the short-term prognosis of patients but also considerably raises the risk of progression to chronic kidney disease and end-stage renal disease, making it a significant threat to human health. Nanomedicine offers innovative therapeutic strategies for AKI and shows considerable potential in its treatment. This review comprehensively summarizes the application of nanomedicines in AKI therapy, with a particular focus on recent advances in the development of antioxidant, anti-inflammatory, and combined nanomedicine-based therapies targeting oxidative stress and inflammation, two primary pathological features of AKI. Additionally, this review also summarizes recent progress in AKI model construction to facilitate a better understanding and investigation of AKI. Overall, the review provides insights into innovative nanomedicine application in the effective treatment of AKI, hoping to provide new ideas for the clinical treatment of AKI.
Acute kidney injury (AKI) is a prevalent clinical syndrome characterized by a rapid loss of renal filtration function, with high incidence and mortality rates that are steadily rising. AKI not only affects the short-term prognosis of patients but also considerably raises the risk of progression to chronic kidney disease and end-stage renal disease, making it a significant threat to human health. Nanomedicine offers innovative therapeutic strategies for AKI and shows considerable potential in its treatment. This review comprehensively summarizes the application of nanomedicines in AKI therapy, with a particular focus on recent advances in the development of antioxidant, anti-inflammatory, and combined nanomedicine-based therapies targeting oxidative stress and inflammation, two primary pathological features of AKI. Additionally, this review also summarizes recent progress in AKI model construction to facilitate a better understanding and investigation of AKI. Overall, the review provides insights into innovative nanomedicine application in the effective treatment of AKI, hoping to provide new ideas for the clinical treatment of AKI.
2025, 36(10): 111025
doi: 10.1016/j.cclet.2025.111025
摘要:
In 2024, the U.S. Food and Drug Administration approved a total of 50 drug marketing applications, with small molecule drugs accounting for half of the medications. Upon surveying these endorsed pharmaceuticals, it becomes evident that certain structures exhibit familiarity, potentially resulting from structural modifications applied to previously approved drugs. Consequently, exploring the latest advancements in drug research not only aids comprehension of cutting-edge technologies used in drug development but also fosters invaluable experience and knowledge accumulation while nurturing innovative ideas for future drug discovery. This review comprehensively analyzes the research progress related to approved small molecule drugs, including aspects such as drug design, structural modification, activity enhancement, and druggability improvement. The aim is to provide valuable insights and assistance for researchers in pharmacology.
In 2024, the U.S. Food and Drug Administration approved a total of 50 drug marketing applications, with small molecule drugs accounting for half of the medications. Upon surveying these endorsed pharmaceuticals, it becomes evident that certain structures exhibit familiarity, potentially resulting from structural modifications applied to previously approved drugs. Consequently, exploring the latest advancements in drug research not only aids comprehension of cutting-edge technologies used in drug development but also fosters invaluable experience and knowledge accumulation while nurturing innovative ideas for future drug discovery. This review comprehensively analyzes the research progress related to approved small molecule drugs, including aspects such as drug design, structural modification, activity enhancement, and druggability improvement. The aim is to provide valuable insights and assistance for researchers in pharmacology.
2025, 36(10): 111137
doi: 10.1016/j.cclet.2025.111137
摘要:
A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms. Compared to traditional polycyclic diterpenoids, their biosynthetic pathways are quite unique and diverse. Chemists have pinpointed a range of this type of unusual diterpenoids: cycloamphilectanes and isocycloamphilectanes, kempenes and rippertanes, hydropyrene and hydropyrenol, along with recently disclosed cephalotanes. This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.
A category of highly fused diterpenoid natural products possessing a characteristic perhydropyrene-like or rearranged tetracyclic skeleton structure are distributed in different life forms. Compared to traditional polycyclic diterpenoids, their biosynthetic pathways are quite unique and diverse. Chemists have pinpointed a range of this type of unusual diterpenoids: cycloamphilectanes and isocycloamphilectanes, kempenes and rippertanes, hydropyrene and hydropyrenol, along with recently disclosed cephalotanes. This review describes developments in this field and discusses the challenges associated with synthesizing this class of highly complex compounds.
2025, 36(10): 111185
doi: 10.1016/j.cclet.2025.111185
摘要:
Energy storage plays a critical role in sustainable development, with secondary batteries serving as vital technologies for efficient energy conversion and utilization. This review provides a comprehensive summary of recent advancements across various battery systems, including lithium-ion, sodium-ion, potassium-ion, and multivalent metal-ion batteries such as magnesium, zinc, calcium, and aluminum. Emerging technologies, including dual-ion, redox flow, and anion batteries, are also discussed. Particular attention is given to alkali metal rechargeable systems, such as lithium-sulfur, lithium-air, sodium-sulfur, sodium-selenium, potassium-sulfur, potassium-selenium, potassium-air, and zinc-air batteries, which have shown significant promise for high-energy applications. The optimization of key components—cathodes, anodes, electrolytes, and interfaces—is extensively analyzed, supported by advanced characterization techniques like time-of-flight secondary ion mass spectrometry (TOF-SIMS), synchrotron radiation, nuclear magnetic resonance (NMR), and in-situ spectroscopy. Moreover, sustainable strategies for recycling spent batteries, including pyrometallurgy, hydrometallurgy, and direct recycling, are critically evaluated to mitigate environmental impacts and resource scarcity. This review not only highlights the latest technological breakthroughs but also identifies key challenges in reaction mechanisms, material design, system integration, and waste battery recycling, and presents a roadmap for advancing high-performance and sustainable battery technologies.
Energy storage plays a critical role in sustainable development, with secondary batteries serving as vital technologies for efficient energy conversion and utilization. This review provides a comprehensive summary of recent advancements across various battery systems, including lithium-ion, sodium-ion, potassium-ion, and multivalent metal-ion batteries such as magnesium, zinc, calcium, and aluminum. Emerging technologies, including dual-ion, redox flow, and anion batteries, are also discussed. Particular attention is given to alkali metal rechargeable systems, such as lithium-sulfur, lithium-air, sodium-sulfur, sodium-selenium, potassium-sulfur, potassium-selenium, potassium-air, and zinc-air batteries, which have shown significant promise for high-energy applications. The optimization of key components—cathodes, anodes, electrolytes, and interfaces—is extensively analyzed, supported by advanced characterization techniques like time-of-flight secondary ion mass spectrometry (TOF-SIMS), synchrotron radiation, nuclear magnetic resonance (NMR), and in-situ spectroscopy. Moreover, sustainable strategies for recycling spent batteries, including pyrometallurgy, hydrometallurgy, and direct recycling, are critically evaluated to mitigate environmental impacts and resource scarcity. This review not only highlights the latest technological breakthroughs but also identifies key challenges in reaction mechanisms, material design, system integration, and waste battery recycling, and presents a roadmap for advancing high-performance and sustainable battery technologies.
2025, 36(10): 111418
doi: 10.1016/j.cclet.2025.111418
摘要:
Photocatalytic and photoelectrocatalytic H2O2 production has been identified as a significant pathway within environmental pollution control, green energy, medical treatment, sterilization and disinfection. However, conventional single-material photocatalysts struggle to fulfill the stringent criteria of high efficiency, stability, cost-effectiveness, and responsiveness to visible light. The elevated recombination rates of photogenerated charge carriers, coupled with the suboptimal utilization of visible light, have collectively constrained the photocatalytic and photoelectrocatalytic H2O2 production. Heterojunction catalysts for the production of H2O2 has become a focal point of research. This review commences by elucidating the fundaments underlying the photocatalytic and photoelectrocatalytic H2O2 production. Subsequently, it delineates the distinctive electron transfer mechanisms of Z-scheme and S-scheme heterojunctions, which exhibit enhanced efficiency in the photocatalytic and photoelectrocatalytic H2O2 production, along with a summary of strategies for the improvement of photocatalyst and photoelectrocatalyst performance. Furthermore, this review also outlines the latest fabrication strategies, state-of-the-art in-situ characterization techniques, machine learning and density functional theory (DFT) simulations for Z-scheme or S-scheme catalysts for the photocatalytic and photoelectrocatalytic H2O2 production, and briefly describes the multifunctional applications in H2O2 production. Ultimately, the review contemplates the prospective developmental trajectories and application potential of these heterojunction configurations for the photocatalytic and photoelectrocatalytic H2O2 production.
Photocatalytic and photoelectrocatalytic H2O2 production has been identified as a significant pathway within environmental pollution control, green energy, medical treatment, sterilization and disinfection. However, conventional single-material photocatalysts struggle to fulfill the stringent criteria of high efficiency, stability, cost-effectiveness, and responsiveness to visible light. The elevated recombination rates of photogenerated charge carriers, coupled with the suboptimal utilization of visible light, have collectively constrained the photocatalytic and photoelectrocatalytic H2O2 production. Heterojunction catalysts for the production of H2O2 has become a focal point of research. This review commences by elucidating the fundaments underlying the photocatalytic and photoelectrocatalytic H2O2 production. Subsequently, it delineates the distinctive electron transfer mechanisms of Z-scheme and S-scheme heterojunctions, which exhibit enhanced efficiency in the photocatalytic and photoelectrocatalytic H2O2 production, along with a summary of strategies for the improvement of photocatalyst and photoelectrocatalyst performance. Furthermore, this review also outlines the latest fabrication strategies, state-of-the-art in-situ characterization techniques, machine learning and density functional theory (DFT) simulations for Z-scheme or S-scheme catalysts for the photocatalytic and photoelectrocatalytic H2O2 production, and briefly describes the multifunctional applications in H2O2 production. Ultimately, the review contemplates the prospective developmental trajectories and application potential of these heterojunction configurations for the photocatalytic and photoelectrocatalytic H2O2 production.
2025, 36(10): 111451
doi: 10.1016/j.cclet.2025.111451
摘要:
Breast cancer is a severe problem for women worldwide. Among them, estrogen receptor (ER) positive breast cancer accounted for 70% of total breast cancer cases, which is the most common subtype. Currently, the main therapy that targeted ER positive breast cancer is endocrine therapy. Herein, we summarized the latest research advances in combination therapies for ER positive breast cancer, focusing on ER as the main therapeutic target. The therapeutic approaches, therapeutic mechanism and resistance will be reviewed and discussed. The combinatorial targets and synergistic effects such as cell cycle-dependent kinase 4/6, phosphatidylinositol-3 kinase, histone deacetylase, bromodomain and extraterminal domain were summarized. In addition, the chemical structures of the inhibitors were also illustrated, along with a brief structure-activity relationship study. Finally, perspective and future directions on breast cancer were proposed and discussed.
Breast cancer is a severe problem for women worldwide. Among them, estrogen receptor (ER) positive breast cancer accounted for 70% of total breast cancer cases, which is the most common subtype. Currently, the main therapy that targeted ER positive breast cancer is endocrine therapy. Herein, we summarized the latest research advances in combination therapies for ER positive breast cancer, focusing on ER as the main therapeutic target. The therapeutic approaches, therapeutic mechanism and resistance will be reviewed and discussed. The combinatorial targets and synergistic effects such as cell cycle-dependent kinase 4/6, phosphatidylinositol-3 kinase, histone deacetylase, bromodomain and extraterminal domain were summarized. In addition, the chemical structures of the inhibitors were also illustrated, along with a brief structure-activity relationship study. Finally, perspective and future directions on breast cancer were proposed and discussed.
2025, 36(10): 111550
doi: 10.1016/j.cclet.2025.111550
摘要:
Most carbon-based catalysts utilized in Fenton-like systems face challenges such as structural instability, susceptibility to deactivation, and a tendency to disperse during operation. Wood-derived catalysts have garnered considerable attention due to their well-defined structures, extensive pipeline networks, superior mechanical strength, and adaptability for device customization. However, there remains a paucity of research that systematically summarizes Fenton-like systems based on wood-derived catalysts. In this review, we first summarize the structural designs of wood-derived catalysts based on nano-metal sites and single-atom sites, while also outlining their advantages and limitations applied in Fenton-like systems. Furthermore, we evaluate catalytic modules of wood-derived catalysts for scale-up and continuous Fenton-like systems. Additionally, wood-inspired catalytic materials utilizing commercial textures and their applications in Fenton-like processes are also discussed. This paper aims to comprehensively explore the fundamental mechanisms (e.g., characteristics of catalytic sites, catalytic performance, and mechanisms) of wood-based catalysts in Fenton-like chemistry, as well as their equipment designs and application scenarios, as well as providing the insights into future developments.
Most carbon-based catalysts utilized in Fenton-like systems face challenges such as structural instability, susceptibility to deactivation, and a tendency to disperse during operation. Wood-derived catalysts have garnered considerable attention due to their well-defined structures, extensive pipeline networks, superior mechanical strength, and adaptability for device customization. However, there remains a paucity of research that systematically summarizes Fenton-like systems based on wood-derived catalysts. In this review, we first summarize the structural designs of wood-derived catalysts based on nano-metal sites and single-atom sites, while also outlining their advantages and limitations applied in Fenton-like systems. Furthermore, we evaluate catalytic modules of wood-derived catalysts for scale-up and continuous Fenton-like systems. Additionally, wood-inspired catalytic materials utilizing commercial textures and their applications in Fenton-like processes are also discussed. This paper aims to comprehensively explore the fundamental mechanisms (e.g., characteristics of catalytic sites, catalytic performance, and mechanisms) of wood-based catalysts in Fenton-like chemistry, as well as their equipment designs and application scenarios, as well as providing the insights into future developments.
2025, 36(10): 111287
doi: 10.1016/j.cclet.2025.111287
摘要:
2025, 36(10): 111408
doi: 10.1016/j.cclet.2025.111408
摘要:
2025, 36(10): 111504
doi: 10.1016/j.cclet.2025.111504
摘要:
2025, 36(5): 109726
doi: 10.1016/j.cclet.2024.109726
摘要:
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
Conventional hydrometallurgy recycling process for treating wasted lithium-ion batteries (LIBs) typically results in the consumption of large amounts of corrosive leachates. Recent research on reusable leachate is expected to significantly improve the economic and environmental benefits, but is usually limited to specific and unique chemical reactions which could only apply to one type of metal elements. Herein, we report the co-extraction of multiple metal elements can be extracted without adding precipitates by mixed crystal co-precipitation, which enables the reusability of the leachate. We show that an oxalic acid (OA): choline chloride (ChCl): ethylene glycol (EG) type DES leachate system can leach transition metals from wasted LiNixCoyMn1-x-yO2 (NCM) cathode materials with satisfactory efficiency (The time required for complete leaching at 120 ℃ is 1.5 h). The transition metals were then efficiently extracted (with a recovery efficiency of over 96% for all elements) by directly adding water without precipitants. Noteworthy, the leachate can be efficiently recovered by directly evaporating the added water. The successful realization of reusability of leachate for the synergistic extraction of multiple elements relies on the regulation of the mixed crystal co-precipitation coefficient, which is realized by rationally design the reaction condition (composition of leachate, temperature and time) and induces the extraction of originally soluble manganese element. Our strategy is expected to be generally applicable and highly competent for industrial applications.
2025, 36(5): 109853
doi: 10.1016/j.cclet.2024.109853
摘要:
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
Even the sulfur cathode in lithium-sulfur (Li-S) battery has the advantages of high theoretical energy density, wide source of raw materials, no pollution to the environment, and so on. It still suffers the sore points of easy electrode collapse due to large volume expansion during charge and discharge and low active materials utilization caused by the severe shuttle effect of lithium polysulfides (LiPSs). Therefore, in this work, ramie gum (RG) was extracted from ramie fiber degumming liquid and used as the functional binder to address the above problems and improve the Li-S battery's performance for the first time. Surprisingly, the sulfur cathode using RG binder illustrates a high initial capacity of 1152.2 mAh/g, and a reversible capacity of 644.6 mAh/g after 500 cycles at 0.5 C, far better than the sulfur cathode using polyvinylidene fluoride (PVDF) and sodium carboxymethyl cellulose (CMC) binder. More importantly, even if the active materials loading increased to as high as 4.30 mg/cm2, the area capacity is still around 3.1 mAh/cm2 after 200 cycles. Such excellent performances could be attributed to the abundant oxygen- and nitrogen-containing functional groups of RG that can effectively inhibit the shuttle effect of LiPSs, as well as the excellent viscosity and mechanical properties that can maintain electrode integrity during long-term charging/discharging. This work verifies the feasibility of RG as an eco-friendly and high-performance Li-S battery binder and provides a new idea for the utilization of agricultural biomass resources.
2025, 36(5): 109870
doi: 10.1016/j.cclet.2024.109870
摘要:
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
Although lithium-ion batteries (LIBs) currently dominate a wide spectrum of energy storage applications, they face challenges such as fast cycle life decay and poor stability that hinder their further application. To address these limitations, element doping has emerged as a prevalent strategy to enhance the discharge capacity and extend the durability of Li-Ni-Co-Mn (LNCM) ternary compounds. This study utilized a machine learning-driven feature screening method to effectively pinpoint four key features crucially impacting the initial discharge capacity (IC) of Li-Ni-Co-Mn (LNCM) ternary cathode materials. These features were also proved highly predictive for the 50th cycle discharge capacity (EC). Additionally, the application of SHAP value analysis yielded an in-depth understanding of the interplay between these features and discharge performance. This insight offers valuable direction for future advancements in the development of LNCM cathode materials, effectively promoting this field toward greater efficiency and sustainability.
2025, 36(5): 109873
doi: 10.1016/j.cclet.2024.109873
摘要:
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
In this work, the synthesis of uniform zeolitic imidazolate framework-coated Mo-glycerate spheres and their subsequent conversion into hierarchical architecture containing bimetallic selenides heterostructures and nitrogen-doped carbon shell are reported. Selenization temperature plays a significant role in determining the phases, morphology, and lithium-ion storage performance of the composite. Notably, the optimal electrode demonstrates an ultrahigh reversible capacity of 1298.2 mAh/g after 100 cycles at 0.2 A/g and an outstanding rate capability with the capacity still maintained 505.7 mAh/g after 300 cycles at 1.0 A/g, surpassing the calculated theoretical capacity according to individual component and most of the reported MoSe@C- or ZnSe@C-based anodes. Furthermore, ex-situ X-ray diffraction patterns reveal the combined conversion and alloying reaction mechanisms of the composite.
2025, 36(5): 109919
doi: 10.1016/j.cclet.2024.109919
摘要:
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
Industrial high-current-density oxygen evolution catalyst is the key to accelerating the practical application of hydrogen energy. Herein, Co9S8/CoS heterojunctions were rationally encapsulated in S, N-codoped carbon ((Co9S8/CoS)@SNC) microleaf arrays, which are rooted on S-doped carbonized wood fibers (SCWF). Benefiting from the synergistic electronic interactions on heterointerfaces and the accelerated mass transfer by array structure, the obtained self-supporting (Co9S8/CoS)@SNC/SCWF electrode exhibits superior performance toward alkaline oxygen evolution reaction (OER) with an ultra-low overpotential of 274 mV at 1000 mA/cm2, a small Tafel slope of 48.84 mV/dec, and ultralong stability up to 100 h. Theoretical calculations show that interfacing Co9S8 with CoS can upshift the d-band center of the Co atoms and strengthen the interactions with oxygen intermediates, thereby favoring OER performance. Furthermore, the (Co9S8/CoS)@SNC/SCWF electrode shows outstanding rechargeability and stable cycle life in aqueous Zn-air batteries with a peak power density of 201.3 mW/cm2, exceeding the commercial RuO2 and Pt/C hybrid catalysts. This work presents a promising strategy for the design of high-current-density OER electrocatalysts from sustainable wood fiber resources, thus promoting their practical applications in the field of electrochemical energy storage and conversion.
2025, 36(5): 109920
doi: 10.1016/j.cclet.2024.109920
摘要:
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
Aqueous proton batteries (APBs) embody a compelling alternative in the realm of economical and reliable energy technologies by virtue of their distinctive "Grotthuss mechanism". Sustainable production and adjustable molecular structure make organic polymers a promising choice for APB electrodes. However, inadequate proton-storage redox capability currently hinders their practical implementation. To address this issue, we introduce a pioneering phenazine-conjugated polymer (PPZ), synthesized through a straightforward polymerization process, marking its debut in APB applications. The inclusion of N-heteroaromatic fused-ring in the extended π-conjugated framework not only prevents the dissolution of redox-active units but also refines the energy bandgap and electronic properties, endowing the PPZ polymer with both structural integrity and enhanced redox activity. Consequently, the PPZ polymer as an electrode material achieves a remarkable proton-storage capacity of 211.5 mAh/g, maintaining a notable capacity of 158.3 mAh/g even under a high rate of 8 A/g with a minimal capacity fade of merely 0.00226% per cycle. The rapid, stable and impressive redox behavior is further elucidated through in-situ techniques and theoretical calculations. Ultimately, we fabricate an APB device featuring satisfactory electrochemical attributes with an extraordinary longevity over 10,000 cycles, thereby affirming its auspicious potential for eminent applications.
2025, 36(5): 109935
doi: 10.1016/j.cclet.2024.109935
摘要:
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
Developing effective strategy for constructing the electrocatalysts enable tri-functional electrocatalytic activity of hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is the premise to achieve both the zinc-air battery (ZAB) and overall water splitting. Herein, we utilize density functional theory to calculate the cobalt nitride (CoxN, x = 1, 2, 4, 5.47) system, revealing that the Co5.47N maybe exhibits a tri-functional activity due to the diverse valence states and high-density d-electron state of Co site. Furthermore, the electron of Co site is further delocalized by the electronic compensation effect of vanadium nitride (VN), thus improving the intermediates absorption and electrocatalytic activity. Accordingly, the Co5.47N/VN heterojunction is designed and synthesized via an electrospinning and a subsequent pyrolysis route. As expected, it displays excellent HER, OER, and ORR activity in alkaline electrolyte, which can be applied to assemble ZAB with a high power density of 207 mW/cm2 and overall water splitting system only requires a lower voltage of 1.53 V to achieve 10 mA/cm2. The electron regulation effect of VN makes the Co valence state decrease in the reduction reaction whereas increase in the oxidization reaction as evidenced by quasi-operando XPS analyses. Importantly, two ZABs connected in series could drive overall water splitting, indicating the potential application in renewable energy technologies.
2025, 36(5): 109936
doi: 10.1016/j.cclet.2024.109936
摘要:
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
Metal-organic frameworks (MOFs) provide great prospective in the photodegradation of pollutants. Nevertheless, the poor separation and recovery hamper their pilot- or industrial-scare applications because of their microcrystalline features. Herein, this challenge can be tackled by integrating Cu-MOFs into an alginate substrate to offer environmentally friendly, sustainable, facile separation, and high-performance MOF-based hydrogel photocatalysis platforms. The CuII-MOF 1 and CuI-MOF 2 were initially synthesized through a direct diffusion and single-crystal to single-crystal (SCSC) transformation method, respectively, and after the immobilization into alginate, more effective pollutant decontamination was achieved via the synergistic effect of the adsorption feature of hydrogel and in situ photodegradation of Cu-MOFs. Specifically, Cu-MOF-alginate composites present an improved and nearly completed Cr(VI) elimination at a short time of 15–25 min. Additionally, the congo red (CR) decolorization can be effectively enhanced in the presence of Cr(VI), and 1-alginate showed superior simultaneous decontamination efficiency of CR and Cr(VI) with 99% and 78%, respectively. Furthermore, Cu-MOF-alginate composites can maintain a high pollutant removal after over 10 continuous cycles (95% for Cr(VI) after 14 runs, and 90% for CR after 10 runs). Moreover, the Cr(VI)/CR degradation mechanism for Cu-MOF-alginate composite was investigated.
2025, 36(5): 109937
doi: 10.1016/j.cclet.2024.109937
摘要:
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
Cu-based metal-organic frameworks (MOFs) are widely employed in CO2 reduction reactions (CO2RR). Mostly, the in-situ reconstructed derivatives such as Cu or Cu oxides during CO2RR are regarded as the catalytic active center for the formation of catalytic products. However, in many cases, the pristine MOFs still exist during the catalytic process, the key role of these pristine MOFs is often ignored in revealing the catalytic mechanism. Here, we designed two Cu(imidazole) with different coordination environments, namely CuN2 and Cu2N4 for CO2RR. The structures of the two MOFs were still remained after the catalytic reaction. We discovered that the pristine MOFs served as activation catalysts for converting CO2 into CO. Sequentially, the Cu-based derivatives, in the two cases, Cu(111) converted the CO into C2+ products. The CuN2 with more exposed Cu-N centers showed a higher FECO and a higher final FEC2+ than Cu2N4. This auto-tandem catalytic mechanism was supported by electrocatalytic performance, TPD-CO, HRTEM, SAED, XPS, in-situ XANES and XES and DFT computation. The auto-tandem catalytic mechanism provides a new route to design Cu-based MOF electrocatalysts for high product selectivity in CO2RR.
2025, 36(5): 109939
doi: 10.1016/j.cclet.2024.109939
摘要:
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
Listeria monocytogenes (LM) is a dangerous foodborne pathogen for humans. One emerging and validated method of indirectly assessing LM in food is detecting 3-hydroxy-2-butanone (3H2B) gas. In this study, the synthesis of 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTMS) functionalized hierarchical hollow TiO2 nanospheres was achieved via precise controlling of solvothermal reaction temperature and post-grafting route. The sensors based on as-prepared materials exhibited excellent sensitivity (480 Hz@50 ppm), low detection limit (100 ppb), and outstanding selectivity. Moreover, the evaluation of LM with high sensitivity and specificity was achieved using the sensors. Such stable three-dimensional spheres, whose distinctive hierarchical and hollow nanostructure simultaneously improved both sensitivity and response/recovery speed dramatically, were spontaneously assembled by nanosheets. Meanwhile, the moderate loadings of AAPTMS significantly improved the selectivity of sensors. Then, the gas-sensing mechanism was explored by utilizing thermodynamic investigation, Gaussian 16 software, and in situ diffuse reflectance infrared transform spectroscopy, illustrating the weak chemisorption between the -NH- group and 3H2B molecules. These portable sensors are promising for real-time assessment of LM at room temperature, which will make a magnificent contribution to food safety.
2025, 36(5): 109940
doi: 10.1016/j.cclet.2024.109940
摘要:
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
Shape control of nickel sulfide (NiS2) catalysts is beneficial for boosting their catalytic performances, which is vital to their practical application as a class of advanced non-noble electro-catalysts. However, precisely controlling the formation kinetics and fabricate ultrathin NiS2 nanostructures still remains challenge. Herein, we provide an injection rate-mediated method to fabricate ultrathin NiS2 nanocages (HNCs) with hierarchical walls, high-density lattice defects and abundant grain boundaries (GBs). Through mechanism analysis, we find the injection rate determines the concentration of S2− in the steady state and thus control the growth pattern, leading to the formation of NiS2 HNCs at slow etching kinetics and NiCo PBA@NiS2 frames at fast etching kinetics, respectively. Benefiting from the ultrathin and hierarchical walls that minimize the mass transport restrictions, the high-density lattice defects and GBs that offer abundant unsaturated reaction sites, the NiS2 HNCs exhibit obviously enhanced electrocatalytic activity and stability toward OER, with overpotential of 255 mV to reach 10 mA/cm2 and a Tafel slope of 27.44 mV/dec, surpassing the performances of NiCo PBA@NiS2 frames and commercial RuO2.
2025, 36(5): 110015
doi: 10.1016/j.cclet.2024.110015
摘要:
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
Mn-based P2-type oxides are considered as promising cathodes for Na-ion batteries; however, they face significant challenges, including structural degradation when charged at high cutoff voltages and structural changes upon storing in a humid atmosphere. In response to these issues, we have designed an oxide with co-doping of Cu and Al which can balance both cost and structural stability. The redox reaction of Cu2+/3+ can provide certain charge compensation, and the introduction of Al can further suppress the Jahn-Teller effect of Mn, thereby achieving superior long-term cycling performance. The ex-situ XRD testing indicates that Cu/Al co-doping can effectively suppress the phase transition of P2-O2 at high voltage, thereby explaining the improvement in electrochemical performance. DFT calculations reveal a high chemical tolerance to moisture, with lower adsorption energy for H2O compared to pure Na0.67Cu0.25Mn0.75O2. A representative Na0.67Cu0.20Al0.05Mn0.75O2 cathode demonstrates impressive reversible capacities of 148.7 mAh/g at 0.2 C, along with a remarkable capacity retention of 79.1% (2 C, 500 cycles).
2025, 36(5): 110034
doi: 10.1016/j.cclet.2024.110034
摘要:
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
Environmentally friendly slow-release fertilizers are highly desired in sustainable agriculture. Encapsulating fertilizers can routinely achieve controlled releasing performances but suffers from short-term effectiveness or environmental unfriendliness. In this work, a bio-derived shellac incorporated with poly-dodecyl trimethoxysilane (SL-PDTMS) capsule was developed for long-term controlled releasing urea. Due to enhanced hydrophobicity and thus water resistance, the SL-PDTMS encapsulated urea fertilizer (SPEU) demonstrated a long-term effectiveness of 60 d, compared with SL encapsulated urea fertilizer (SEU, 30 d) and pure urea fertilizer (U, 5 min). In addition, SPEU showed a broad pH tolerance from 5.0 to 9.0, covering most various soil pH conditions. In the pot experiments, promoted growth of maize seedlings was observed after applying SPEU, rendering it promising as a high-performance controlled-released fertilizer.
2025, 36(5): 110043
doi: 10.1016/j.cclet.2024.110043
摘要:
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
Carbon monoxide (CO) is a crucial gaseous signaling molecule that regulates various physiological and pathological processes, and may exert an anti-inflammatory and protective role in drug-induced liver injury (DILI). Despite this, understanding the exact relationship between CO and the occurrence and development of DILI remains challenging. Hence, there is an urgent need to develop a reliable and robust tool for the rapid visual detection and assessment of CO in this context. Herein, we presented a novel near-infrared (NIR) fluorescent nanoprobe with aggregation-induced emission (AIE) properties and excited-state intramolecular proton transfer (ESIPT) characteristics for the detection and imaging of CO both in vitro and in vivo. Simultaneously, the nanoprobe enables self-assembly form nanoaggregates in aqueous media with high biocompatible, which can sense CO in situ through the conversion of yellow-to-red fluorescence facilitated aggregation-induced dual-color fluorescence. What is more, this nanoprobe shows ratiometric respond to CO, which demonstrates excellent stability, high sensitivity (with a detection limit of 12.5 nmol/L), and superior selectivity. Crucially, this nanoprobe enables the visual detection of exogenous and endogenous CO in living cells and tissues affected by DILI, offering a user-friendly tool for real-time visualization of CO in living system. Hence, it holds great promise in advancing our understanding of CO's role.
2025, 36(5): 110045
doi: 10.1016/j.cclet.2024.110045
摘要:
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
This study presents an approach to enhanced cancer immunotherapy through the in situ synthesis of potassium permanganate (KMnO4) derived manganese dioxide (MnO2) micro/nano-adjuvants. Addressing the limitations of traditional immunotherapy due to patient variability and the complexity of the tumor microenvironment, our research establishes KMnO4 as a potent immunomodulator that enhances the efficacy of anti-programmed death-ligand 1 (αPD-L1) antibodies. The in situ synthesized MnO2 adjuvants in the tumor exhibit direct interactions with biological systems, leading to the reduction of MnO2 to Mn2+ within the tumor, and thereby improving the microenvironment for immune cell activity. Our in vitro and in vivo models demonstrate KMnO4’s capability to induce concentration-dependent cytotoxicity in tumor cells, triggering DNA damage and apoptosis. It also potentiates immunogenic cell death by upregulating calreticulin and high mobility group box 1 (HMGB1) on the cell surface. The combination of KMnO4 with αPD-L1 antibodies substantially inhibits tumor growth, promotes dendritic cell maturation, and enhances CD8+ T cell infiltration, resulting in a significant phenotypic shift in tumor-associated macrophages towards a pro-inflammatory M1 profile. Our findings advocate for further research into the long-term efficacy of KMnO4 and its application in diverse tumor models, emphasizing its potential to redefine immune checkpoint blockade therapy and offering a new vista in the fight against cancer.
2025, 36(5): 110053
doi: 10.1016/j.cclet.2024.110053
摘要:
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
Crucial for mediating inflammation and the perception of pain, the ion channel known as transient receptor potential ankyrin 1 (TRPA1) holds significant importance. It contributes to the increased production of cytokines in the inflammatory cells of cartilage affected by osteoarthritis and represents a promising target for the treatment of this condition. By leveraging the unique advantages of liposomes, a composite microsphere drug delivery system with stable structural properties and high adaptability can be developed, providing a new strategy for osteoarthritis (OA) drug therapy. The liposomes as drug reservoirs for TRPA1 inhibitors were loaded into hyaluronic acid methacrylate (HAMA) hydrogels to make hydrogel microspheres via microfluidic technology. An in vitro inflammatory chondrocyte model was established with interleukin-1β (IL-1β) to demonstrate HAMA@Lipo@HC's capabilities. A destabilization of the medial meniscus (DMM) mouse model was also created to evaluate the efficacy of intra-articular injections for treating OA. HAMA@Lipo@HC has a uniform particle-size distribution and is injectable. The drug encapsulation rate was 64.29% ± 2.58%, with a sustained release period of 28 days. Inhibition of TRPA1 via HC-030031 effectively alleviated IL-1β-induced chondrocyte inflammation and matrix degradation. In DMM model OA mice, microspheres showed good long-term sustained drug release properties, improved joint inflammation microenvironment, reduced articular cartilage damage and decreased mechanical nociceptive threshold. This research pioneers the creation of a drug delivery system tailored for delivery into the joint cavity, focusing on TRPA1 as a therapeutic target for osteoarthritis. Additionally, it offers a cutting-edge drug delivery platform aimed at addressing diseases linked to inflammation.
2025, 36(5): 110067
doi: 10.1016/j.cclet.2024.110067
摘要:
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
Postoperative recurrence and metastasis are still the main challenges of cancer therapy. Tumor vaccines that induce potent and long-lasting immune activation have great potential for postoperative cancer therapy. However, the clinical effects of therapeutic tumor vaccines are unsatisfactory due to immune escape caused by the lack of immunogenicity after surgery and the local fibrosis barrier of the tumor which limits effector T cell infiltration. To overcome these challenges, we developed an injectable hydrogel-based tumor vaccine, RATG, which contains whole tumor cell lysates (TCL), Toll-like receptor (TLR) 7/8 agonist imiquimod (R837) and an antifibrotic drug ARV-825. TCL and R837 were loaded onto the hydrogel to achieve a powerful reservoir of antigens and adjuvants that induced potent and lasting immune activation. More importantly, ARV-825 could be slowly and sustainably released in the tumor resection cavity to downregulate α-smooth muscle actin (α-SMA) and collagen levels, disintegrate fibrosis barriers and promote T cell infiltration after immune activation to reduce immune escape. In addition, ARV-825 also directly acted on the remaining tumor cells to degrade bromodomain-containing protein 4 (BRD4) which is a critical epigenetic reader overexpressed in tumor cells, inhibiting tumor cell migration and invasion. Therefore, our injectable hydrogel created a powerful immune niche in postoperative tumor resection cavity, significantly enhancing the efficacy of tumor vaccines. Our strategy potently activates the immune system and disintegrates the fibrotic barrier of residual tumors with immune microenvironment remodeling in situ, showing anti-recurrence and anti-metastatic effects, and provides a new paradigm for postoperative treatment of tumors.
2025, 36(5): 110069
doi: 10.1016/j.cclet.2024.110069
摘要:
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
Efficient electrocatalysts for oxygen reduction reaction (ORR) show significant importance for advancing the performance and affordability of proton exchange membrane fuel cells and other energy conversion devices. Herein, PtCo3 nanoalloys dispersed on a carbon black support, were prepared using ultrafast Joule heating method. By tuning the heating modes, such as high-temperature shock and heating for 2 s, two kinds of PtCo3 nanoalloys with varying crystallinities were obtained, referred to as PtCo3HTS (average size of 5.4 nm) and PtCo3HT-2 s (average size of 6.4 nm), respectively. Impressively, PtCo3HTS exhibited superior electrocatalytic ORR activity and stability (E1/2 = 0.897 V vs. RHE and 36 mV negative shift after 50, 000 cycles), outperforming PtCo3HT-2 s (E1/2 = 0.872 V and 16.2 mV negative shift), as well as the commercial Pt/C (20 wt%) catalyst (E1/2 = 0.847 V and 21.0 mV negative shift). The enhanced ORR performance of PtCo3HTS may be attributed to its low crystallinity, which results in an active local electronic structure and chemical state, as confirmed by X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) analyses. The ultrafast Joule heating method showed great potential for crystallinity engineering, offering a promising pathway to revolutionize the manufacturing of cost-effective and environmentally friendly catalysts for clean energy applications.
2025, 36(5): 110073
doi: 10.1016/j.cclet.2024.110073
摘要:
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
Diseases associated with bacterial infection, especially those caused by gram-negative bacteria, have been posing a serious threat to human health. Photodynamic therapy based on aggregation-induced emission (AIE) photosensitizer have recently emerged and provided a promising approach for bacterial discrimination and efficient photodynamic antimicrobial applications. However, they often suffer from the shorter excitation wavelength and lower molar extinction coefficients in the visible region, severely limiting their further applications. Herein, three novel BF2-curcuminoid-based AIE photosensitizers, TBBC, TBC and TBBC-C8, have been rationally designed and successfully developed, in which OCH3- and OC8H17-substituted tetraphenylethene (TPE) groups serve as both electron donor (D) and AIE active moieties, BF2bdk group functions as electron acceptor (A), and styrene (or ethylene) group as π-bridge in this D-π-A-π-D system, respectively. As expected, these resulting BF2-curcuminoids presented solvent-dependent photophysical properties with large molar extinction coefficients in solutions and excellent AIE properties. Notably, TBBC showed an effective singlet oxygen generation efficiency thanks to the smaller singlet-triplet energy gap (ΔEST), and remarkable photostability under green light exposure at 530 nm (8.9 mW/cm2). More importantly, TBBC was demonstrated effectiveness in selective staining and photodynamic killing of Escherichia coli (E. coli) in vitro probably due to its optimal molecular size compared with TBC and TBBC-C8. Therefore, TBBC will have great potential as a novel AIE photosensitizer to apply in the discrimination and selective sterilization between Gram-positive and Gram-negative bacteria.
2025, 36(5): 110082
doi: 10.1016/j.cclet.2024.110082
摘要:
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
Acute lung injury (ALI) is a serious clinical condition with a high mortality rate. Oxidative stress and inflammatory responses play pivotal roles in the pathogenesis of ALI. ONOO− is a key mediator that exacerbates oxidative damage and microvascular permeability in ALI. Accurate detection of ONOO− would facilitate early diagnosis and intervention in ALI. Near-infrared fluorescence (NIRF) probes offer new solutions due to their sensitivity, depth of tissue penetration, and imaging capabilities. However, the developed ONOO− fluorescent probes face problems such as interference from other reactive oxygen species and easy intracellular diffusion. To address these issues, we introduced an innovative self-immobilizing NIRF probe, DCI2F-OTf, which was capable of monitoring ONOO− in vitro and in vivo. Importantly, leveraging the high reactivity of the methylene quinone (QM) intermediate, DCI2F-OTf was able to covalently label proteins in the presence of ONOO−, enabling in situ imaging. In mice models of ALI, DCI2F-OTf enabled real-time imaging of ONOO− levels and found that ONOO− was tightly correlated with the progression of ALI. Our findings demonstrated that DCI2F-OTf was a promising chemical tool for the detection of ONOO−, which could help to gain insight into the pathogenesis of ALI and monitor treatment efficacy.
2025, 36(5): 110084
doi: 10.1016/j.cclet.2024.110084
摘要:
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
Glioma is a severe malignant brain tumor marked by an exceedingly dire prognosis and elevated incidence of recurrence. The resilience of such tumors to chemotherapeutic agents, coupled with the formidable obstacle the blood-brain barrier (BBB) presents to most pharmacological interventions are major challenges in anti-glioma therapy. In an endeavor to surmount these impediments, we have synergized pH-sensitive nanoparticles carrying doxorubicin and apatinib to amplify the anti-neoplastic efficacy with cyclic arginine–glycine–aspartate acid (cRGD) modification. In this study, we found that the combination of doxorubicin (DOX) and apatinib (AP) showed a significant synergistic effect, achieved through cytotoxicity and induction of apoptosis, which might be due to the increased intracellular uptake of DOX following AP treatment. Besides, polycaprolactone-polyethylene glycol-cRGD (PCL-PEG-cRGD) drug carrier could cross the BBB by its targeting ability, and then deliver the drug to the glioma site via pH-responsive release, increasing the concentration of the drugs in the tumor. Meanwhile, DOX/AP-loaded PCL-PEG-cRGD nanoparticles effectively inhibited cell proliferation, enhanced glioma cell apoptosis, and retarded tumor growth in vivo. These results collectively identified DOX/AP-loaded PCL-PEG-cRGD nanoparticles as a promising therapeutic candidate for the treatment of glioma.
2025, 36(5): 110097
doi: 10.1016/j.cclet.2024.110097
摘要:
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
Insufficient endogenous H2O2 for generation of hydroxyl radicals (•OH) has strikingly compromised anti-tumor benefits of ferroptosis. Herein, we develop a H2O2 self-supplying nanoparticle based on a pH-responsive lipopeptide C18-pHis10. Inspired by the coordinate pattern of hemoglobin binding heme, Fe2+ and tetrakis(4-carboxyphenyl)porphyrin (TCPP) were delicately encapsulated by formation of coordination compounds with His. Ascorbgyl palmitate (AscP) was also incorporated into the nanoparticles for generation of H2O2 by reduction 1O2 produced from TCPP, meanwhile prevented Fe2+ from being oxidized. The protonation of pHis in acidic endo-lysosome induced the breakage of Fe2+/His/TCPP coordinate interactions, leading to accelerated release of payloads and the following escape to cytoplasm. Upon laser irradiation, TCPP produces excessive 1O2 followed by conversion to H2O2 in the presence of AscP, which is further catalyzed to lethal •OH by Fe2+ via Fenton reaction. The self-supplying H2O2 was found to result significantly higher accumulation of lipid peroxides and more effective tumor inhibition. Overall, this work sheds new a light on H2O2 self-supplying strategy to enhance ferroptosis by taking advantage of 1O2 generated by photodynamic therapy (PDT).
2025, 36(5): 110098
doi: 10.1016/j.cclet.2024.110098
摘要:
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
D-D'-A type aza-borondipyrromethenes (aza-BODIPYs) were prepared by Suzuki cross-coupling reaction. Photothermal conversion efficiency of self-assemble aza-BODIPY-based nanoparticles (DA-azaBDP-NPs) with NIR-II emission (λem = 1065 nm) was 37.2% under near infrared (NIR) irradiation, and the outstanding cytotoxicity was triggered by coexistence of DA-azaBDP-NPs and the NIR irradiation, with the decrease of glioblastoma migration and the inhibition of glioblastoma proliferation. DA-azaBDP-NPs could promote glioblastoma autophagy and accelerate the process of cell death. The photothermal therapy (PTT) of DA-azaBDP-NPs can effectively induce glioblastoma death by apoptosis under the NIR irradiation, which is highly promising to be applied in vivo experiments of brain.
2025, 36(5): 110105
doi: 10.1016/j.cclet.2024.110105
摘要:
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
Singlet oxygen (1O2), as the primary reactive oxygen species in photodynamic therapy, can effectively induce excessive oxidative stress to ablate tumors and kill germs in clinical treatment. However, monitoring endogenous 1O2 is greatly challenging due to its extremely short lifetime and high reactivity in biological condition. Herein, we report an ultra-high signal-to-ratio near-infrared chemiluminescent probe (DCM-Cy) for the precise detection of endogenous 1O2 during photodynamic therapy (PDT). The methoxy moiety was removed from enolether unit in DCM-Cy to suppress the potential self-photooxidation reaction, thus greatly eliminating the photoinduced background signals during PDT. Additionally, the compact cyclobutane modification of DCM-Cy resulted in a significant 6-fold increase in cell permeability compared to conventional adamantane-dioxane probes. Therefore, our "step-by-step" strategy for DCM-Cy addressed the limitations of traditional chemiluminescent (CL) probes for 1O2, enabling effectively tracking of endogenous 1O2 level changes in living cells, pathogenic bacteria and mice in PDT.
2025, 36(5): 110106
doi: 10.1016/j.cclet.2024.110106
摘要:
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
Interstitial hypertension and extracellular matrix (ECM) barriers imposed by cancer-associated fibroblasts (CAFs) at the tumor site significantly impede the retention of intratumorally administered oncolytic viruses (OVs) as well as their efficacy in infecting and eradicating tumor cells. Herein, a stable, controllable, and easily prepared hydrogel was developed for employing a differential release strategy to deliver OVs. The oncolytic herpes simplex virus-2 (oH2) particles were loaded within sodium alginate (ALG), together with the small molecule drug PT-100 targeting CAFs. The rapid release of PT-100 functions as an anti-CAFs agent, reducing ECM, and alleviating interstitial pressure at the tumor site. Consequently, the delayed release of oH2 could more effectively invade and eradicate tumor cells while also facilitating enhanced infiltration of immune cells into the tumor microenvironment, thereby establishing an immunologically favorable milieu against tumors. This approach holds significant potential for achieving highly efficient oncolytic virus therapy with minimal toxicity, particularly in tumors rich in stromal components.
2025, 36(5): 110116
doi: 10.1016/j.cclet.2024.110116
摘要:
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
Constructing multi-dimensional hydrogen bond (H-bond) regulated single-molecule systems with multi-emission remains a challenge. Herein, we report the design of a new excited-state intramolecular proton transfer (ESIPT) featured chromophore (HBT-DPI) that shows flexible emission tunability via the multi-dimensional regulation of intra- and intermolecular H-bonds. The feature of switchable intramolecular H-bonds is induced via incorporating several hydrogen bond acceptors and donors into one single HBT-DPI molecule, allowing the "turn on/off" of ESIPT process by forming isomers with distinct intramolecular H-bonds configurations. In response to different external H-bonding environments, the obtained four types of crystal/cocrystals vary in the contents of isomers and the molecular packing modes, which are mainly guided by the intermolecular H-bonds, exhibiting non-emissive features or emissions ranging from green to orange. Utilizing the feature of intermolecular H-bond guided molecular packing, we demonstrate the utility of this fluorescent material for visualizing hydrophobic/hydrophilic areas on large-scale heterogeneous surfaces of modified poly(1,1-difluoroethylene) (PVDF) membranes and quantitatively estimating the surface hydrophobicity, providing a new approach for hydrophobicity/hydrophilicity monitoring and measurement. Overall, this study represents a new design strategy for constructing multi-dimensional hydrogen bond regulated ESIPT-based fluorescent materials that enable multiple emissions and unique applications.
2025, 36(5): 110119
doi: 10.1016/j.cclet.2024.110119
摘要:
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
Photodynamic therapy (PDT) has emerged as a promising approach for tumor treatment due to its non-invasiveness and high selectivity. However, the off-target activation of phototoxicity and the limited availability of tumor-specific biomarkers pose challenges for effective PDT. Here, we present the development of a novel ratiometric near-infrared-Ⅱ (NIR-Ⅱ) fluorescent organic nanoprobe, BTz-IC@IR1061, which responds specifically to hypochlorite (HClO) within tumors. This nanoprobe allows ratiometric fluorescence imaging to monitor and guide activated tumor PDT. BTz-IC@IR1061 nanoparticles were synthesized by codoping the small molecule dye BTz-IC, which generates reactive oxygen species (ROS), with the commercial dye IR1061. The presence of HClO selectively activates the fluorescence and photodynamic properties of BTz-IC while destroying IR1061, enabling controlled release of ROS for tumor therapy. We demonstrated the high selectivity of the nanoprobe for HClO, as well as its excellent photostability, photoacoustic imaging capability, and photothermal effects. Furthermore, in vivo studies revealed effective tumor targeting and remarkable tumor growth inhibition through tumor-activated PDT. Our findings highlight the potential of BTz-IC@IR1061 as a promising tool for tumor-specific PDT, providing new opportunities for precise and controlled cancer therapy.
2025, 36(5): 110128
doi: 10.1016/j.cclet.2024.110128
摘要:
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
The bioactive constituents found in natural products (NPs) are crucial in protein-ligand interactions and drug discovery. However, it is difficult to identify ligand molecules from complex NPs that specifically bind to target protein, which often requires time-consuming and labor-intensive processes such as isolation and enrichment. To address this issue, in this study we developed a method that combines ultra-high performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) with molecular dynamics (MD) simulation to identify and observe, rapidly and efficiently, the bioactive components in NPs that bind to specific protein target. In this method, a specific protein target was introduced online using a three-way valve to form a protein-ligand complex. The complex was then detected in real time using high-resolution MS to identify potential ligands. Based on our method, only 10 molecules from green tea (a representative natural product), including the commonly reported epigallocatechin gallate (EGCG) and epicatechin gallate (ECG), as well as the previously unreported eepicatechin (4β→8)-epigallocatechin 3-O-gallate (EC-EGCG) and eepiafzelechin 3-O-gallate-(4β→8)-epigallocatechin 3-O-gallate (EFG-EGCG), were screened out, which could form complexes with Aβ1–42 (a representative protein target), and could be potential ligands of Aβ1–42. Among of them, EC-EGCG demonstrated the highest binding free energy with Aβ1–42 (−68.54 ± 3.82 kcal/mol). On the other side, even though the caffeine had the highest signal among green tea extracts, it was not observed to form a complex with Aβ1–42. Compared to other methods such as affinity selection mass spectrometry (ASMS) and native MS, our method is easy to operate and interpret the data. Undoubtedly, it provides a new methodology for potential drug discovery in NPs, and will accelerate the research on screening ligands for specific proteins from complex NPs.
2025, 36(5): 110130
doi: 10.1016/j.cclet.2024.110130
摘要:
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
The overuse of surfactants has made them well-known environmental pollutants. So far, it is still a challenge to simultaneously distinguish cationic, anionic, zwitterionic, nonionic surfactants and surfactants with similar structures based on traditional analytical techniques. We developed a high-throughput method for distinguishing various surfactants based on the adaptive emission profile as fingerprints (AEPF). The fluorescence response of the sensor was based on the interaction between surfactants and 1,3-diacetylpyrene (o-DAP) probe. The interaction affected the reversible conversion of free molecules and two aggregates in the solution, thereby changing the relative abundance and the fluorescence intensity ratio of two aggregates emitting different fluorescence. The o-DAP sensor can distinguish four types of surfactants (16 surfactants), especially surfactants of the same type with similar structures. The o-DAP sensor sensitively determined the critical micelle concentration (CMC) of 16 surfactants based on the interaction between o-DAP and surfactants. Additionally, the o-DAP sensor can detect and distinguish artificial vesicles made from different surfactants.
2025, 36(5): 110133
doi: 10.1016/j.cclet.2024.110133
摘要:
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
Severe traumatic bone healing relies on the involvement of growth factors. However, excessive supplementation of growth factors can lead to ectopic ossification and inflammation. In this study, utilizing the neural regulatory mechanism of bone regeneration, we have developed a multifunctional three dimensions (3D) printed scaffold containing both vasoactive intestinal peptide (VIP) and nerve growth factor (NGF) as an effective new method for achieving bone defect regeneration. The scaffold is provided by a controlled biodegradable and biomechanically matched poly(lactide-ethylene glycol-trimethylene carbonate) (PLTG), providing long-term support for the bone healing cycle. Factor loading is provided by peptide fiber-reinforced biomimetic antimicrobial extracellular matrix (ECM) (B-ECM) hydrogels with different release kinetics, the hydrogel guides rapid bone growth and resists bacterial infection at the early stage of healing. Physical and chemical characterization indicates that the scaffold has good structural stability and mechanical properties, providing an ideal 3D microenvironment for bone reconstruction. In the skull defect model, compared to releasing VIP or NGF alone, this drug delivery system can simulate a natural healing cascade of controllable release factors, significantly accelerating nerve/vascular bone regeneration. In conclusion, this study provides a promising strategy for implanting materials to repair bone defects by utilizing neuroregulatory mechanisms during bone regeneration.
2025, 36(5): 110135
doi: 10.1016/j.cclet.2024.110135
摘要:
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
Biomolecular condensates, also known as membraneless organelles, play a crucial role in cellular organization by concentrating or sequestering biomolecules. Despite their importance, synthetically mimicking these organelles using non-peptidic small organic molecules has posed a significant challenge. The present study reports the discovery of D008, a self-assembling small molecule that sequesters a unique subset of RNA-binding proteins. Analysis and screening of a comprehensive collection of approximately 1 million compounds in the Chinese National Compound Library (Shanghai) identified 44 self-assembling small molecules in aqueous solutions. Subsequent screening of the focused library, coupled with proteome analysis, led to the discovery of D008 as a small organic molecule with the ability to condensate a specific subset of RNA-binding proteins. In vitro experiments demonstrated that the D008-induced sequestration of RNA-binding proteins impeded mRNA translation. D008 may offer a unique opportunity for studying the condensations of RNA-binding proteins and for developing an unprecedented class of small molecules that control gene expression.
2025, 36(5): 110140
doi: 10.1016/j.cclet.2024.110140
摘要:
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
Diabetic kidney disease (DKD) is recognized as a severe complication in the development of diabetes mellitus (DM), posing a significant burden for global health. Major characteristics of DKD kidneys include tubulointerstitial oxidative stress, inflammation, excessive extracellular matrix deposition, and progressing renal fibrosis. However, current treatment options are limited and cannot offer enough efficacy, thus urgently requiring novel therapeutic approaches. Tetrahedral framework nucleic acids (tFNAs) are a novel type of self-assembled DNA nanomaterial with excellent structural stability, biocompatibility, tailorable functionality, and regulatory effects on cellular behaviors. In this study, we established an in vitro high glucose (HG)-induced human renal tubular epithelial cells (HK-2 cells) pro-fibrogenic model and explored the antioxidative, anti-inflammatory, and antifibrotic capacity of tFNAs and the potential molecular mechanisms. tFNAs not only effectively alleviated oxidative stress through reactive oxygen species (ROS)-scavenging and activating the serine and threonine kinase (Akt)/nuclear factor erythroid 2-related factor 2 (Nrf2)/heme oxygenase-1 (HO-1) signaling pathway but also inhibited the production of pro-inflammatory factors such as tumor necrosis factor (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6) in diabetic HK-2 cells. Additionally, tFNAs significantly downregulated the expression of Collagen I and α-smooth muscle actin (α-SMA), two representative biomarkers of pro-fibrogenic myofibroblasts in the renal tubular epithelial-mesenchymal transition (EMT). Furthermore, we found that tFNAs exerted this function by inhibiting the Wnt/β-catenin signaling pathway, preventing the occurrence of EMT and fibrosis. The findings of this study demonstrated that tFNAs are naturally endowed with great potential to prevent fibrosis progress in DKD kidneys and can be further combined with emerging pharmacotherapies, providing a secure and efficient drug delivery strategy for future DKD therapy.
2025, 36(5): 110141
doi: 10.1016/j.cclet.2024.110141
摘要:
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
A computer-assisted chemical investigation of an intriguing photoreaction of norditerpenoids (3‒7) has been first reported, leading to not only their biomimetic conversion, but also the generation of several new products with uncommon 4,14-dioxabicyclo[10.2.1]pentadecane scaffold (8, 9, 12‒14). In bioassay, compounds 10 and 15 exhibited significant stimulation of GLP-1 secretion. This study has given an insight for the application of computational methods on the late-stage skeleton transformation of complex natural products towards new bioactive compounds.
2025, 36(5): 110146
doi: 10.1016/j.cclet.2024.110146
摘要:
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
Tumor blockade therapy inhibits tumor progression by cutting off essential supplies of nutrients, oxygen, and biomolecules from the surrounding microenvironments. Inspired by natural processes, tumor biomineralization has evolved due to its biocompatibility, self-reinforcing capability, and penetration-independent mechanism. However, the selective induction of tumor biomineralization using synthetic tools presents a significant challenge. Herein, a metabolic glycoengineering-assistant tumor biomineralization strategy was developed. Specifically, the azido group (N3) was introduced onto the cytomembrane by incubating tumor cells with glycose analog Ac4ManNAz. In addition, a bisphosphonate-containing polymer, dibenzocyclooctyne-poly(ethylene glycol)-alendronate (DBCO-PEG-ALN, DBPA) was synthesized, which attached to the tumor cell surface via "click chemistry" reaction between DBCO and N3. Subsequently, the bisphosphonate group on the cell surface chelated with positively charged ions in the microenvironments, triggering a consecutive process of biomineralization. This physical barrier significantly reduced tumor cell viability and mobility in a calcium ion concentration-dependent manner, suggesting its potential as an effective anti-tumor strategy for in vivo applications.
2025, 36(5): 110147
doi: 10.1016/j.cclet.2024.110147
摘要:
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
The aggressive nature and high mortality rate of lung cancer underscore the imperative need for early diagnosis of the disease. Thus, aminopeptidase N (APN), a potential biomarker for lung cancer, should be thoroughly investigated in this context. This report describes the development of HA-apn, a novel near-infrared fluorescent probe, specifically engineered for the sensitive detection of endogenous APN. Characterized by its high selectivity, straightforward molecular architecture, and suitable optical properties, including a long-wavelength emission at 835 nm and a large Stokes shift of 285 nm, HA-apn had high efficacy in identifying overexpressed APN in tumor cells, which shows its potential in pinpointing malignancies. To further validate its applicability and effectiveness in facilitating the direct and enhanced visualization of pulmonary alterations, an in situ lung cancer mouse model was employed. Notably, HA-apn was applied for in vivo imaging of APN activity in the lung cancer mouse model receiving the probe through aerosol inhalation, and rapid and precise diagnostic results were achieved within 30 min post-administration. Overall, HA-apn can be applied as an effective, non-intrusive tool for the rapid and accurate detection of pulmonary conditions.
2025, 36(5): 110149
doi: 10.1016/j.cclet.2024.110149
摘要:
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
[2+2]-Type cyclobutane derivatives comprise a large family of natural products with diverse molecular architectures. However, the structure elucidation of the cyclobutane ring, including its connection mode and stereochemistry, presents a significant challenge. Plumerubradins A–C (1–3), three novel iridoid glycoside [2+2] dimers featuring a highly functionalized cyclobutane core and multiple stereogenic centers, were isolated from the flowers of Plumeria rubra. Through biomimetic semisynthesis and chemical degradation of compounds 1–3, synthesis of phenylpropanoid-derived [2+2] dimers 7–10, combined with extensive spectroscopic analysis, single-crystal X-ray crystallography, and microcrystal electron diffraction experiments, the structures with absolute configurations of 1–3 were unequivocally elucidated. Furthermore, quantum mechanics-based 1H NMR iterative full spin analysis successfully established the correlations between the signal patterns of cyclobutane protons and the structural information of the cyclobutane ring in phenylpropanoid-derived [2+2] dimers, providing a diagnostic tool for the rapid structural elucidation of [2+2]-type cyclobutane derivatives.
2025, 36(5): 110166
doi: 10.1016/j.cclet.2024.110166
摘要:
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
Early recognition is key to improving the prognosis of ischemic stroke (IS), while available imaging methods tend to target events that have already undergone ischemia. A new method to detect early IS is urgently needed, as well as further study of its mechanisms. Viscosity and cysteine (Cys) levels of mitochondria have been associated with ferroptosis and IS. It is possible to identify IS and ferroptosis accurately and early by monitoring changes in mitochondrial Cys and viscosity simultaneously. In this work, a viscosity/Cys dual-responsive mitochondrial-targeted near-infrared (NIR) fluorescent probe (NVCP) was constructed for the precise tracking of IS using a two-dimensional design strategy. NVCP consists of a chromophore dyad containing diethylaminostyrene quinolinium rotor and chloro-sulfonylbenzoxadiazole (SBD-Cl) derivative with two easily distinguished emission bands (λem = 592 and 670 nm). NVCP performs the way of killing two birds with one stone, that is, the probe exhibits excellent selectivity and sensitivity for detecting viscosity and Cys in living cells with excellent biocompatibility and accurate mitochondrial targeting capability by dual channel imaging mode. In addition, NVCP recognized that the viscosity increases and Cys level decreases in cells when undergoing ferroptosis and oxygen-glucose deprivation (OGD) stress by confocal imaging, flow cytometry, and Western blot experiments. Treatment of ferroptosis inhibitors (ferrostatin-1 (Fer-1) and deferoxamine (DFO)) could reverse the variation tendency of viscosity and Cys. This is the first time that the relationship between ferroptosis and IS was identified through an analysis of Cys and viscosity. More importantly, the ischemic area was also instantly distinguished from normal tissues through fluorescence imaging of NVCP in vivo. The developed NIR dual-responsive probe NVCP toward viscosity and Cys could serve as a sensitive and reliable tool for tracking ferroptosis-related pathological processes during IS.
2025, 36(5): 110168
doi: 10.1016/j.cclet.2024.110168
摘要:
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
Photodynamic therapy (PDT) has received much attention in recent years. However, traditional photosensitizers (PSs) applied in PDT usually suffer from aggregation-caused quenching (ACQ) effect in H2O, single and inefficient photochemical mechanism of action (MoA), poor cancer targeting ability, etc. In this work, two novel Ru(Ⅱ)-based aggregation-induced emission (AIE) agents (Ru1 and Ru2) were developed. Both complexes exhibited long triplet excited lifetimes and nearly 100% singlet oxygen quantum yields in H2O. In addition, Ru1 and Ru2 displayed potent photo-catalytic reduced nicotinamide adenine dinucleotide (NADH) oxidation activity with turnover frequency (TOF) values of about 1779 and 2000 h−1, respectively. Therefore, both Ru1 and Ru2 showed efficient PDT activity towards a series of cancer cells. Moreover, Ru2 was further loaded in bovine serum albumin (BSA) to enhance the tumor targeting ability in vivo, and the obtained Ru2@BSA could selectively accumulate in tumor tissues and effectively inhibit tumor growth on a 4T1 tumor-bearing mouse model. So far as we know, this work represents the first report about Ru(Ⅱ) AIE agents that possess high singlet oxygen quantum yields and also potent photo-catalytic NADH oxidation activity, and may provide new ideas for rational design of novel PSs with efficient PDT activity.
2025, 36(5): 110178
doi: 10.1016/j.cclet.2024.110178
摘要:
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
Chemodynamic therapy (CDT), using Fenton agents to generate highly cytotoxic •OH from H2O2 has been demonstrated as a powerful anticancer method. However, the insufficient endogenous H2O2 in tumor cells greatly limited its therapeutic effect. Herein, we prepared a pH-responsive β-lapachone-loaded iron-polyphenol nanocomplex (LIPN) through a one-pot method. β-Lapachone in LIPN selectively enhanced H2O2 concentration in tumor cells, and ferrous ions cascadely generated abundant cytotoxic •OH. Therefore, LIPN with cascade amplification of reactive oxygen species (ROS) showed high chemodynamic cytotoxicity in tumor cells, efficiently improving the expression of damage-associated molecular patterns (DAMPs), and exerting strong immunogenic cell death (ICD). As a result, LIPN exhibited efficient tumor inhibition ability in 4T1 subcutaneous tumor model in vivo with great biocompatibility. Additionally, the infiltration of cytotoxic CD8+ T lymphocytes and inhibition of regulatory CD4+ FoxP3+ T lymphocytes in tumors demonstrated the activation of immunosuppressive tumor microenvironment by LIPN-induced ICD. Therefore, this work provided a new approach to enhance ICD of chemodynamic therapy through selective cascade amplification of ROS in cancer cells.
2025, 36(5): 110179
doi: 10.1016/j.cclet.2024.110179
摘要:
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants, with little attention to the involved selectivity which may correlate with toxicant residues. Herein, an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy (Co-OV) on the Co/BiOCl-OV photocatalyst was developed for photocatalytic degradation of glyphosate (GLP) wastewater of high performance/selectivity. Under full-spectrum-light irradiation, a high GLP degradation rate of 99.8% with over 90% C‒P bond-breaking selectivity was achieved within 2 h, while effectively circumventing toxicant residues such as aminomethylphosphonic acid (AMPA). X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-OV carrier and photothermal/pyroelectric effect. The oriented formation of more •O2− on Co/BiOCl-OV could be achieved with the Co-OV coupled center that had excellent O2 adsorption/activation capacity, as demonstrated by quantum calculations. The formed unique Co-OV active sites could largely decrease the C‒P bond-breaking energy barrier, thus greatly improving the selectivity toward the initial C‒P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP. The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C‒X bonds.
2025, 36(5): 110183
doi: 10.1016/j.cclet.2024.110183
摘要:
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
Lipids serve as fundamental constituents of cell membranes and organelles. Recent studies have highlighted the significance of lipids as biomarkers in the diagnosis of breast cancer. Although liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is widely employed for lipid analysis in complex samples, it suffers from limitations such as complexity and time-consuming procedures. In this study, we have developed dopamine-modified TiO2 nanoparticles (TiO2-DA) and applied the materials to assist the analysis of lipids by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The TiO2-DA can provide large specific surface area and acidic environment, well suited for lipid analysis. The method was initially validated using standard lipid molecules. Good sensitivity, reproducibility and quantification performance was observed. Then, the method was applied to the analysis of 90 serum samples from 30 patients with breast cancer, 30 patients with benign breast disease and 30 healthy controls. Five lipid molecules were identified as potential biomarkers for breast cancer. We constructed a classification model based on the MALDI-TOF MS signal of the 5 lipid molecules, and achieved high sensitivity, specificity and accuracy for the differentiation of breast cancer from benign breast disease and healthy control. We further collected another 60 serum samples from 20 healthy controls, 20 patients with benign breast disease and 20 patients with breast cancer for MALDI-TOF MS analysis to verify the accuracy of the classification model. This advancement holds great promise for the development of diagnostic models for other lipid metabolism-related diseases.
2025, 36(5): 110190
doi: 10.1016/j.cclet.2024.110190
摘要:
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
Boron neutron capture therapy (BNCT) has emerged as a promising treatment for cancers, offering a unique approach to selectively target tumor cells while sparing healthy tissues. Despite its clinical utility, the widespread use of fructose-BPA (F-BPA) has been hampered by its limited ability to penetrate the blood-brain barrier (BBB) and potential risks for patients with certain complications such as diabetes, hyperuricemia, and gout, particularly with substantial dosages. Herein, a series of novel BPA derivatives were synthesized. After the primary screening, geniposide-BPA (G-BPA) and salidroside-BPA (S-BPA) exhibited high water solubility, low cytotoxicity and safe profiles for intravenous injection. Furthermore, both G-BPA and S-BPA had demonstrated superior efficacy in vitro against the 4T1 cell line compared with F-BPA. Notably, S-BPA displayed optimal BBB penetration capability, as evidenced by in vitro BBB models and glioblastoma models in vivo, surpassing all other BPA derivative candidates. Meanwhile, G-BPA also exhibited enhanced performance relative to the clinical drug F-BPA. In brief, G-BPA and S-BPA, as novel BPA derivatives, demonstrated notable safety profiles and remarkable boron delivery capabilities, thereby offering promising therapeutic options for BNCT in the clinic.
2025, 36(5): 110191
doi: 10.1016/j.cclet.2024.110191
摘要:
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
Gallstones are a common disease worldwide, often leading to obstruction and inflammatory complications, which seriously affect the quality of life of patients. Research has shown that gallstone disease is associated with ferroptosis, lipid droplets (LDs), and abnormal levels of nitric oxide (NO). Fluorescent probes provide a sensitive and convenient method for detecting important substances in life systems and diseases. However, so far, no fluorescent probes for NO and LDs in gallstone disease have been reported. In this work, an effective ratiometric fluorescent probe LR-NH was designed for the detection of NO in LDs. With an anthracimide fluorophore and a secondary amine as a response site for NO, LR-NH exhibits high selectivity, sensitivity, and attractive ratiometric capability in detecting NO. Importantly, it can target LDs and shows excellent imaging ability for NO in cells and ferroptosis. Moreover, LR-NH can target the gallbladder and image NO in gallstone disease models, providing a unique and unprecedented tool for studying NO in LDs and gallbladder.
2025, 36(5): 110192
doi: 10.1016/j.cclet.2024.110192
摘要:
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
Photocatalytic overall water splitting is a promising method for producing clean hydrogen energy, but faces challenges such as low light utilization efficiency and high charge carrier recombination rates. This study demonstrates that dielectric Mie resonance in TiO2 hollow nanoshells can enhance electric field intensity and increase light absorption through resonant energy transfer, compared to crushed TiO2 nanoparticles. The Mie resonance effect was confirmed through fluorescence spectra, photo-response current measurements, photocatalytic water splitting experiments, and Mie calculation. The incident electric-field amplitude was doubled in hollow nanoshells, allowing for increased light trapping. Additionally, the spatially separated Pt and RuO2 cocatalysts on the inner and outer surfaces facilitated the separation of photoinduced electrons and holes. Pt@TiO2@RuO2 hollow nanoshells exhibited superior photocatalytic water splitting performance, with a stable H2 generation rate of 50.1 µmol g−1 h−1 and O2 evolution rate of 25.1 µmol g−1 h−1, outperforming other nanostructures such as TiO2, Pt@TiO2, and TiO2@RuO2 hollow nanoshells. This study suggests that dielectric Mie resonance and spatially-separated cocatalysts offer a new approach to simultaneously enhance light absorption and charge carrier transfer in photocatalysis.
2025, 36(5): 110195
doi: 10.1016/j.cclet.2024.110195
摘要:
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
Traditional Pt/C electrode materials are prone to corrosion and detachment during H2S detection, leading to a decrease in fuel cell-type sensor performance. Here, a high-performance H2S sensor based on Pt loaded Ti3C2 electrode material with -O/-OH terminal groups was designed and prepared. Experimental tests showed that the Pt/Ti3C2 sensor has good sensitivity (0.162 µA/ppm) and a very low detection limit to H2S (10 ppb). After 90 days of stability testing, the response of the Pt/Ti3C2 sensor shows a smaller decrease of 2% compared to that of the Pt/C sensor (22.9%). Meanwhile, the sensor also has high selectivity and repeatability. The density functional theory (DFT) calculation combined with the experiment results revealed that the improved H2S sensing mechanism is attributed to the fact that the strong interaction between Pt and Ti3C2 via the Pt-O-Ti bonding can reduce the formation energy of Pt and Ti3C2, ultimately prolonging the sensor’s service life. Furthermore, the catalytic property of Pt can decrease the adsorption energy and dissociation barrier of H2S on Pt/Ti3C2 surface, greatly enhance the ability to generate protons and effectively transfer charges, realizing good sensitivity and high selectivity of the sensor. The sensor works at room temperature, making it very promising in the field of H2S detection in future.
2025, 36(5): 110196
doi: 10.1016/j.cclet.2024.110196
摘要:
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
The addition of cold flow improvers (CFIs) is considered as the optimum strategy to improve the cold flow properties (CFPs) of diesel fuels, but this strategy is always limited by the required large dosage. To obtain low-dosage and high-efficiency CFIs for diesel, 1,2,3,6-tetrahydrophthalic anhydride (THPA) was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylate-trans anethole copolymers (C14MC-TA). The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride (C14MC-TA-THPA) were synthesized and compared with the binary copolymers of C14MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride (C14MC-THPA). Results showed that C14MC -THPA achieved the best depressive effects on the cold filter plugging point (CFPP) and solid point (SP) by 11 ℃ and 16 ℃ at a dosage of 1250 mg/L and monomer ratio of 6:1, while 1500 mg/L C14MC-TA (1:1) reached the optimal depressive effects on the CFPP and SP by 12 ℃ and 18 ℃. THPA introduction significantly improved the depressive effects of C14MC-TA. Lower dosages of C14MC-TA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C14MC-TA and C14MC-THPA. When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L, the improvement effect of C14MC-TA-THPA on diesel reached the optimum level, and the CFPP and SP were reduced by 13 ℃ and 19 ℃, respectively. A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios, dosages, and depressive effects of CFIs in diesel. Surface analysis results showed that C14MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L, and the CFPP and SP decreased by 14 ℃ and 19 ℃, respectively. The predicted results were consistent with the actual ones. Additionally, the improvement mechanism of these copolymers in diesel was also explored.
2025, 36(5): 110200
doi: 10.1016/j.cclet.2024.110200
摘要:
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3N4) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2Nb2O6·H2O via thermal dehydration at the interface of g-C3N4. The optimized NbNC/g-C3N4–1 was a type-Ⅰ heterojunction, which showed a high conduction band (CB) level of −1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, •O2−. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e– transferred from NaNbO3 to g-C3N4 in NbNC/g-C3N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3N4–1 had 3.3- and 2.3-fold of CIP degradation rate constants (k1 = 0.173 min−1) compared with those of pristine g-C3N4 and NaNbO3, respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by •O2−, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
2025, 36(5): 110201
doi: 10.1016/j.cclet.2024.110201
摘要:
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks, but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system. MIL-68(In) was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity. However, its catalytic activity was constrained by severe carrier recombination and a lack of active sites. Herein, increased (001) facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In) through a one-pot solvothermal strategy. Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In) and other MIL-68(In/Co). The reaction kinetic constant and degradation efficiency of MIL-68(In/Co) were approximately twice and 17% higher than the pristine MIL-68(In) in 36 min reaction, respectively. Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In) facets, facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate (PMS). This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system, it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
2025, 36(5): 110202
doi: 10.1016/j.cclet.2024.110202
摘要:
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
As antibiotic pollutants cannot be incompletely removed by conventional wastewater treatment plants, ultraviolet (UV) based advanced oxidation processes (AOPs) such as UV/persulfate (UV/PS) and UV/chlorine are increasingly concerned for the effective removal of antibiotics from wastewaters. However, the specific mechanisms involving degradation kinetics and transformation mechanisms are not well elucidated. Here we report a detailed examination of SO4•−/Cl•-mediated degradation kinetics, products, and toxicities of sulfathiazole (ST), sarafloxacin (SAR), and lomefloxacin (LOM) in the two processes. Both SO4•−/Cl•-mediated transformation kinetics were found to be dependent on pH (P < 0.05), which was attributed to the disparate reactivities of their individual dissociated forms. Based on competition kinetic experiments and matrix calculations, the cationic forms (H2ST+, H2SAR+, and H2LOM+) were more highly reactive towards SO4•− in most cases, while the neutral forms (e.g., HSAR0 and HLOM0) reacted the fastest with Cl• for the most of the antibiotics tested. Based on the identification of 31 key intermediates using tandem mass spectrometry, these reactions generated different products, of which the majority still retained the core chemical structure of the parent compounds. The corresponding diverse transformation pathways were proposed, involving S−N breaking, hydroxylation, defluorination, and chlorination reactions. Furthermore, the toxicity changes of their reaction solutions as well as the toxicity of each intermediate were evaluated by the vibrio fischeri and ECOSAR model, respectively. Many primary by-products were proven to be more toxic than the parent chemicals, raising the wider issue of extended potency for these compounds with regards to their ecotoxicity. These results have implications for assessing the degradative fate and risk of these chemicals during the AOPs.
2025, 36(5): 110203
doi: 10.1016/j.cclet.2024.110203
摘要:
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress. Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues. The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity. For covalent inhibitors, the pull down-based methods including activity-based protein profiling (ABPP) are commonly used to profile their target proteins. For covalent reversible inhibitors, it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner. Here, we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules. This pair of isotopic probes consists of a lysine-reactive warhead, a desthiobiotin moiety and isotopicable linker. This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process. To demonstrate the feasibility of our newly-developed probes for the protein target identification, we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner. Finally, we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol. Interestingly, pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins. Together, our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
2025, 36(5): 110206
doi: 10.1016/j.cclet.2024.110206
摘要:
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
The selective conversion of CO2 and NH3 into valuable nitriles presents significant potential for CO2 utilization. In this study, we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups, utilizing CO2 and NH3 as the CN source. Our methodology exhibited exceptional compatibility with diverse functional groups, such as alcohols, ketones, ethers, esters, nitriles, olefins, pyridines, and quinolines, among others, as demonstrated by the successful synthesis of 58 different nitriles. Notably, we achieved high yields in the preparation of bifunctionalized molecules, including intermediates for perampanel, derived from o-silylaryl triflates, which are well-known as aryne precursors. Remarkably, no degradation of substrates or formation of aryne intermediates were observed. Mechanistic studies imply that the formation of penta-coordinated silyl isocyanate intermediates is crucial for the key C–C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
2025, 36(5): 110207
doi: 10.1016/j.cclet.2024.110207
摘要:
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
The development of general and practical strategies toward the construction of medium-sized rings is still challenging in organic synthesis, especially for the multiple stereocenters control of substituted groups on the ring owing to the long distance between groups. Thus, stereoselective synthesis of multi-substituted ten-membered rings is attractive. Herein, a rapid assembly of various highly substituted ten-membered nitrogen heterocycles between two 1,3-dipoles through a tandem [3 + 3] cycloaddition/aza-Claisen rearrangement of N-vinyl-α,β-unsaturated nitrones and aza-oxyallyl or oxyallyl cations are disclosed. Products containing two or multiple stereocenters could be obtained in up to 96% yield with high regioselectivity and diastereoselectivity. Selective N-O bond cleavages of ten-membered nitrogen heterocycles lead to various novel 5,6,6-perifused benzofurans, bicyclo[4.4.0] or bicyclo[5.3.0] skeletons containing three or multiple continuous stereocenters in good yields and high diastereoselectivity. Biological tests show that the obtained ten-membered N-heterocycles and bicyclo[4.4.0] skeletons inhibited nitric oxide generation in LPS-stimulated RAW264.7 cells and might serve as good anti-inflammatory agents.
2025, 36(5): 110209
doi: 10.1016/j.cclet.2024.110209
摘要:
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
Algal copper uptake (i.e., Cu bioavailability) in the euphotic zone plays a vital role in algal photosynthesis and respiration, affecting the primary productivity and the source and sink of atmospheric carbon. Algal Cu uptake is controlled by natural dissolved organic Cu (DOCu) speciation (i.e., complexed with the dissolved organic matter) that conventionally could be tested by model prediction or molecular-level characterizations in the lab, while DOCu uptake are hardly directly assessed. Thus, the new chemistry-biology insight into the mechanisms of the Cu uptake process in algae is urgent. The DOCu speciation transformation (organic DOCu to free Cu(Ⅱ) ions), enzymatic reduction-induced valence change (reduction of free Cu(Ⅱ) to Cu(Ⅰ) ions), and algal Cu uptake at the algae-water interface are imitated. Herein, an intelligent system with DOCu colorimetric sensor is developed for real-time monitoring of newly generated Cu(Ⅰ) ions. Deep learning with whole sample image-based characterization and powerful feature extraction capabilities facilitates colorimetric measurement. In this context, the Cu bioavailability with 7 kinds of organic ligands (e.g., amino acids, organic acids, carbohydrates) can be predicted by the mimetic intelligent biosensor within 15.0 min, i.e., the DOCu uptake and speciation is successfully predicted and streamlined by the biomimetic approach.
2025, 36(5): 110213
doi: 10.1016/j.cclet.2024.110213
摘要:
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
Bridged bicyclic cores have been recognized as valuable bioisosteres of benzene ring, which are of great value in medicinal chemistry. However, the development of fluorinated bicyclic skeletons, which encompass two privileged elements widely acknowledged for fine tuning the working effect of target molecules, are far less common. Herein, we present a general and practical synthesis of gem–difluorobicyclo[2.1.1]hexanes (diF-BCHs) from readily available difluorinated hexa-1,5-dienes through energy transfer photocatalysis. By taking advantage of an efficient Cope rearrangement, the preparation of both constitutional isomers of diF-BCHs is readily achieved under identical conditions. The operational simplicity, mild conditions and wide scope further highlight the potential application of this protocol. Moreover, computational studies indicated a positive effect of fluorine atoms in lowering either the triplet or FMO energies of the hexa-1,5-diene substrates, thus promoting the present photoinduced [2 + 2] cycloaddition.
2025, 36(5): 110227
doi: 10.1016/j.cclet.2024.110227
摘要:
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
Combining cytotoxic drugs with tumor microenvironment (TME) modulator agents is an effective strategy to enhance anti-tumor effects. In this study, two natural anti-tumor active ingredients celastrol (CEL) and glycyrrhetinic acid (GA) were combined for tumor treatment. In order to ensure the precise co-delivery and controllable synchronous release of combined drugs to tumors, it is necessary to construct a suitable nano-drug delivery platform. Based on this, we coupled hyaluronic acid (HA) with CEL by amide reaction to obtain an amphiphilic polymer prodrug HA-SS-CEL, and GA was spontaneously loaded into polymer micelles by self-assembly to obtain G/HSSC-M. G/HSSC-M has ideal size distribution, redox-responsive synchronous drug release, enhanced tumor cell internalization and in vivo tumor targeting. Compared with free drugs, the construction of multifunctional polymer micelles makes G/HSSC-M show better anticancer effect at the same concentration, and can significantly inhibit the proliferation and migration of HepG2 and 4T1 cells. In the in vivo experiments, G/HSSC-M achieved a tumor inhibition rate as high as 75.12% in H22 tumor-bearing mice. The mechanism included regulation of M1/M2 macrophage polarization, inhibition of Janus kinase 1/signal transducer and activator of transcription 3 (JAK1/STAT3) signaling pathway, and remodeling of tumor blood vessels. Therefore, the development of prodrug micelles co-loaded with CEL and GA provides a promising drug co-delivery strategy for combined cancer therapy.
2025, 36(5): 110230
doi: 10.1016/j.cclet.2024.110230
摘要:
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
Self-assembled prodrug nanomedicine has emerged as an advanced platform for antitumor therapy, mainly comprise drug modules, response modules and modification modules. However, existing studies usually compare the differences between single types of modification modules, neglecting the impact of steric-hindrance effect caused by chemical structure. Herein, single-tailed modification module with low-steric-hindrance effect and two-tailed modification module with high-steric-hindrance effect were selected to construct paclitaxel prodrugs (P-LAC18 and P-BAC18), and the in-depth insights of the steric-hindrance effect on prodrug nanoassemblies were explored. Notably, the size stability of the two-tailed prodrugs was enhanced due to improved intermolecular interactions and steric hindrance. Single-tailed prodrug nanoassemblies were more susceptible to attack by redox agents, showing faster drug release and stronger antitumor efficacy, but with poorer safety. In contrast, two-tailed prodrug nanoassemblies exhibited significant advantages in terms of pharmacokinetics, tumor accumulation and safety due to the good size stability, thus ensuring equivalent antitumor efficacy at tolerance dose. These findings highlighted the critical role of steric-hindrance effect of the modification module in regulating the structure-activity relationship of prodrug nanoassemblies and proposed new perspectives into the precise design of self-assembled prodrugs for high-performance cancer therapeutics.
2025, 36(5): 110231
doi: 10.1016/j.cclet.2024.110231
摘要:
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
The chemo-, regio-, and enantio-controlled synthesis of P-chiral phosphines in a general and efficient manner remains a significant synthetic challenge. In this study, a Pd-catalyzed hydrofunctionalization is developed for the highly selective synthesis of P-stereogenic alkenylphosphinates and alkenylphosphine oxides via conjugate addition of enynes. Notably, this methodology is suitable for both phosphine oxide and phosphinate nucleophiles, providing a versatile approach for the construction of diverse P-chiral organophosphosphorus compound.
2025, 36(5): 110237
doi: 10.1016/j.cclet.2024.110237
摘要:
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
Traditional electrospray ionization tandem mass spectrometry (ESI-MSn) has been a powerful tool in diverse research areas, however, it faces great limitations in the study of protein-small molecule interactions. In this article, the state-of-the-art temperature-controlled electrospray ionization tandem mass spectrometry (TC-ESI-MSn) is applied to investigate interactions between ubiquitin and two flavonol molecules, respectively. The combination of collision-induced dissociation (CID) and MS solution-melting experiments facilitates the understanding of flavonol-protein interactions in a new dimension across varying temperature ranges. While structural changes of proteins disturbed by small molecules are unseen in ESI-MSn, TC-ESI-MSn allows a simultaneous assessment of the stability of the complex in both gas and liquid phases under various temperature conditions, meanwhile investigating the impact on the protein’s structure and tracking changes in thermodynamic data, and the characteristics of structural intermediates.
2025, 36(5): 110238
doi: 10.1016/j.cclet.2024.110238
摘要:
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
Neutrophil extracellular traps (NETs) formation (NETosis), is a crucial immune system mechanism mediated by neutrophils, measuring the capacity to induce NETosis is proposed as a clinical biomarker indicating the severity of COVID-19 and long COVID. Azvudine (FNC), has shown efficacy in treating SARS-CoV-2 infection and potential for alleviating inflammation. However, the molecular mechanism underlying its anti-inflammatory effects has not been extensively investigated. Therefore, a series of experiments were conducted on SARS-CoV-2 infected rhesus macaques (RMs) to investigate the anti-inflammatory effects of FNC. The experiments involved HE staining, mass spectrometry-based proteomics, validation experiments conducted in vivo using RMs tissues and in vitro differentiation of HL-60 cells. Additionally, interaction investigations were carried out utilizing LiP-MS, CETSA, Co-IP along with molecular docking. The results demonstrated that FNC treatment effectively alleviated neutrophil infiltration and attenuated inflammatory injury following infection. In addition to exhibiting antiviral effects, FNC treatment exhibited a reduction in inflammation-associated proteins and pathways such as myeloperoxidase (MPO) and the formation of NETs, respectively. Validation experiments confirmed the impact of FNC on regulating NETs formation, interaction experiments suggested that MPO may serves as a therapeutic target. The multifaceted properties of FNC, including its antiviral and anti-inflammatory characteristics, highlight the therapeutic potential in diseases associated with NETosis, particularly those involving concurrent SARS-CoV-2 infection, providing insights for drug development targeting MPO and NETosis-associated diseases.
2025, 36(5): 110239
doi: 10.1016/j.cclet.2024.110239
摘要:
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
Here we present a highly efficient protocol utilizing nickel-hydride hydrogen atom transfer catalysis for the regio- and enantioselective hydrofluorination of internal alkenes. This method efficiently assembles a wide array of enantioenriched β-fluoro amides with excellent regio- and enantioselectivity from internal unactivated alkenes. Mechanistic investigations suggest that this transformation proceeds via a NiH-hydrogen atom transfer to alkene, followed by a stereoselective fluorine atom transfer process. The weak coordination effect of the tethered amide group is identified as a crucial factor governing the observed regio- and enantioselectivity.
2025, 36(5): 110240
doi: 10.1016/j.cclet.2024.110240
摘要:
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
Nanoplastics exhibit greater environmental biotoxicity than microplastics and can be ingested by humans through major routes such as tap water, bottled water and other drinking water. Nanoplastics present a challenge for air flotation due to their minute particle size, negative surface potential, and similar density to water. This study employed dodecyltrimethylammonium chloride (DTAC) as a modifier to improve conventional air flotation, which significantly enhanced the removal of polystyrene nanoplastics (PSNPs). Conventional air flotation removed only 3.09% of PSNPs, while air flotation modified by dodecyltrimethylammonium chloride (DTAC-modified air flotation) increased the removal of PSNPs to 98.05%. The analysis of the DTAC-modified air flotation mechanism was conducted using a combination of instruments, including a zeta potential analyzer, contact angle meter, laser particle size meter, high definition camera, scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and Fourier transform infrared spectrometer (FTIR). The results indicated that the incorporation of DTAC reversed the electrostatic repulsion between bubbles and PSNPs to electrostatic attraction, significantly enhancing the hydrophobic force in the system. This, in turn, improved the collision adhesion effect between bubbles and PSNPs. The experimental results indicated that even when the flotation time was reduced to 7 min, the DTAC-modified air flotation still achieved a high removal rate of 96.26%. Furthermore, changes in aeration, pH, and ionic strength did not significantly affect the performance of the modified air flotation for the removal of PSNPs. The removal rate of PSNPs in all three water bodies exceeded 95%. The DTAC-modified air flotation has excellent resistance to interference from complex conditions and shows great potential for practical application.
2025, 36(5): 110241
doi: 10.1016/j.cclet.2024.110241
摘要:
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
Hyperglycemia resulting from diabetes mellitus (DM) exacerbates osteoporosis and fractures, damaging bone regeneration due to impaired healing capacity. Stem cell therapy offers the potential for bone repair, accelerating the healing of bone defects by introducing stem cells with osteogenic differentiation ability. Dental follicle stem cells (DFSCs) are a newly emerging type of dental stem cells that not only have the potential for multipotent differentiation but also hold easy accessibility and can stand long-term storage. However, DM-associated oxidative stress and inflammation elevate the risk of DFSCs dysfunction and apoptosis, diminishing stem cell therapy efficacy. Recent nanomaterial advances, particularly in DNA nanostructures like tetrahedral framework nucleic acids (tFNAs), have been promising candidates for modulating cellular behaviors. Accumulating experiments have shown that tFNAs' cell proliferation and migration-promoting ability and induce osteogenic differentiation of stem cells. Meanwhile, tFNAs can scavenge reactive oxygen species (ROS) and downregulate the secretion of inflammatory factors by inhibiting various inflammation-related signaling pathways. Here, we applied tFNAs to modify DFSCs and observed enhanced osteogenic differentiation alongside ROS scavenging and anti-inflammatory effects mediated by suppressing the ROS/mitogen-activated protein kinases (MAPKs)/nuclear factor kappa-B (NF-κB) signaling pathway. This intervention reduced stem cell apoptosis, bolstering stem cell therapy efficacy in DM. Our study establishes a simple yet potent tFNAs-DFSCs system, offering potential as a bone repair agent for future DM treatment.
2025, 36(5): 110243
doi: 10.1016/j.cclet.2024.110243
摘要:
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
The asymmetric addition of aromatic organometallic compounds to the carbonyl group (C-3) of isatins, catalyzed by transition metals, has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles. Here, an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides (both aryl and heteroaryl). Utilizing chiral cobalt complexes as catalysts, and the presence of a diboron reagent B2nep2 as both a reducing agent and determinant in enantiocontrol, has resulted in the triumphantly achieved synthesis of enantioenriched products. Compared to reported strategies, this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups, such as halides and borate esters, while also eliminating the need for organometallic reagents as required in previous strategies. Through experimental investigations, the presence of aryl-cobalt species during the addition process was confirmed, rather than in-situ generation of an arylboron reagent. Furthermore, the successful attainment of the R absolute configuration through aryl addition was demonstrated.
2025, 36(5): 110244
doi: 10.1016/j.cclet.2024.110244
摘要:
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
Humic acid (HA), as a represent of natural organic matter widely existing in water body, dose harm to water quality and human health; however, it was commonly treated as an environmental background substance while not targeted contaminant in advanced oxidation processes (AOPs). Herein, we investigated the removal of HA in the alkali-activated biochar (KBC)/peroxymonosulfate (PMS) system. The modification of the original biochar (BC) resulted in an increased adsorption capacity and catalytic activity due to the introduction of more micropores, mesopores, and oxygen-containing functional groups, particularly carbonyl groups. Mechanistic insights indicated that HA is primarily chemically adsorbed on the KBC surface, while singlet oxygen (1O2) produced by the PMS decomposition served as the major reactive species for the degradation of HA. An underlying synergistic adsorption and oxidation mechanism involving a local high concentration reaction region around the KBC interface was then proposed. This work not only provides a cost-effective solution for the elimination of HA but also advances our understanding of the nonradical oxidation at the biochar interface.
2025, 36(5): 110249
doi: 10.1016/j.cclet.2024.110249
摘要:
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
Nanobelts are a rapidly developing family of macrocycles with appealing features. However, their host-guest chemistry is currently limited to the recognition of fullerenes via π–π interactions. Herein, we report two heteroatom-bridged [8]cyclophenoxathiin nanobelts ([8]CP-Me and [8]CP) encapsulate corannulene (Cora) to form bowl-in-bowl supramolecular structures stabilized mainly through CH–π interactions in solid-state. The convex surface of corannulene is oriented towards the cavity due to geometry complementarity. The complex Cora⊂[8]CP exhibits a unique 2:2 capsule-like structure in crystal packing, in which corannulene adopts a concave-to-concave assembling fashion. This work enriches the molecular recognition of nanobelts and demonstrates that CH–π interactions can act as the main driving force for nanobelts host-guest complexes.
2025, 36(5): 110253
doi: 10.1016/j.cclet.2024.110253
摘要:
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives. However, both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited. We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes, employing arylsulfonyl acetate as the bifunctional reagent. This approach involves a radical addition/Smiles rearrangement cascade process, offering a robust alternative for the synthesis of valuable γ,γ-diaryl and γ-aryl esters. A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions, facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity. Noteworthy features of this method include mild reaction conditions, organophotocatalysis, high atom- and step-economy, excellent functional group compatibility and great structural diversity.
2025, 36(5): 110258
doi: 10.1016/j.cclet.2024.110258
摘要:
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
The continuous mutation and rapid spread of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) have led to the ineffectiveness of many antiviral drugs targeting the original strain. To keep pace with the virus' evolutionary speed, there is a crucial need for the development of rapid, cost-effective, and efficient inhibitor screening methods. In this study, we created a novel approach based on fluorescence resonance energy transfer (FRET) technology for in vitro detection of inhibitors targeting the interaction between the SARS-CoV-2 spike protein RBD (s-RBD) and the virus receptor angiotensin-converting enzyme 2 (ACE2). Utilizing crystallographic insights into the s-RBD/ACE2 interaction, we modified ACE2 by fusing SNAP tag to its N-terminus (resulting in SA740) and Halo tag to s-RBD’s C-terminus (producing R525H and R541H), thereby ensuring the proximity (< 10 nm) of labeled FRET dyes. We found that relative to the R541H fusion protein, R525H exhibited higher FRET efficiency, which attributed to the shortened distance between FRET dyes due to the truncation of s-RBD. Utilizing the sensitive FRET effect between SA740 and R525H, we evaluated its efficacy in detecting inhibitors of SARS-CoV-2 entry in solution and live cells. Ultimately, this FRET-based detection method was demonstrated high sensitivity, rapidity, and simplicity in solution and held promise for high-throughput screening of SARS-CoV-2 inhibitors.
2025, 36(5): 110260
doi: 10.1016/j.cclet.2024.110260
摘要:
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
Perovskite oxides have been widely applied as an effective catalyst in heterogeneous catalysis. However, the rational design of active catalysts has been restricted by the lack of understanding of the electronic structure. The correlations between surface properties and bulk electronic structure have been ignored. Herein, a simple handler of LaFeO3 with diluted HNO3 was employed to tune the electronic structure and catalytic properties. Experimental analysis and theoretical calculations elucidate that acid etching could raise the Fe valence and enhance Fe–O covalency in the octahedral structure, thereby lessening charge transfer energy. Enhanced Fe–O covalency could lower oxygen vacancy formation energy and enhance oxygen mobility. In-situ DRIFTS results indicated the inherent adsorption capability of Toluene and CO molecules has been greatly improved owing to higher Fe–O covalency. As compared, the catalysts after acid etching exhibited higher catalytic activity, and the T90 had a great reduction of 45 and 58 ℃ for toluene and CO oxidation, respectively. A deeper understanding of electronic structure in perovskite oxides may inspire the design of high-performance catalysts.
2025, 36(5): 110282
doi: 10.1016/j.cclet.2024.110282
摘要:
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
As a renovator in the field of gene editing, CRISPR-Cas9 has demonstrated immense potential for advancing next-generation gene therapy owing to its simplicity and precision. However, this potential faces significant challenges primarily stemming from the difficulty in efficiently delivering large-sized genome editing system (including Cas9 protein and sgRNA) into targeted cells and spatiotemporally controlling their activity in vitro and in vivo. Therefore, the development of CRISPR/Cas9 nanovectors that integrate high loading capacity, efficient encapsulation and spatiotemporally-controlled release is highly desirable. Herein, we have engineered a near-infrared (NIR) light-activated upconversion-DNA nanocapsule for the remote control of CRISPR-Cas9 genome editing. The light-responsive upconversion-DNA nanocapsules consist of macroporous silica (mSiO2) coated upconversion nanoparticles (UCNPs) and photocleavable o-nitrobenzyl-phosphate-modified DNA shells. The UCNPs act as a "nanotransducers" to convert NIR light (980 nm) into local ultraviolet light, thereby facilitating the cleavage of photosensitive DNA nanocapsules and enabling on-demand release of CRISPR-Cas9 encapsuled in the macroporous silica. Furthermore, by formulating a sgRNA targeted to a tumor gene (polo-like kinase-1, PLK-1), the CRISPR-Cas9 loaded UCNP-DNA nanocapsules (crUCNP-DNA nanocapsules) have effectively suppressed the proliferation of tumor cells through NIR light-activated gene editing both in vitro and in vivo. Overall, this UCNP-DNA nanocapsule holds tremendous potential for CRISPR-Cas9 delivery and remote-controlled gene editing in deep tissues, as well as the treatment of diverse diseases.
2025, 36(5): 110291
doi: 10.1016/j.cclet.2024.110291
摘要:
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
Metal hydrides serve as crucial intermediates in many chemical processes, facilitating the utilization of hydrogen resources. Traditionally, three-centre metal hydrides have been viewed as less reactive due to their multi-stabilization effects. However, recent discoveries show the "three-centre four-electron" (3c-4e) bridging hydride bond exhibits significant activity in boryl transition metal systems. This research employs computational techniques to explore the factors that influence the formation of the 3c-4e bridging hydride, focusing on boryl 3d non-noble transition metals ranging from chromium (Cr) to nickel (Ni). By analyzing bond distances and bond orders, the study sheds light on the electronic and structural characteristics of the B-H-M bridging hydride. It reveals a clear link between the metal centre's redox properties and the emergence of bridging hydrides. Specifically, metal centres like Cr and Co, which have lower oxidation states and electronegativity, are more inclined to form active 3c-4e bridging hydrides. These insights, derived from computational analyses, offer valuable guidelines for the development of active 3c-4e bridging metal hydrides, thereby contributing to the advancement of new hydrogen transformation catalysts.
2025, 36(5): 110293
doi: 10.1016/j.cclet.2024.110293
摘要:
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
Singlet oxygen (1O2), as an electrophilic oxidant, is essential for the selective water decontamination of pollutants from water. Herein, we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles (CoFeCNT) to selectively facilitate the electrochemical activation of O2 to 1O2. Benefiting from the prominently featured bimetal active sites of CoFeCNT, nearly complete production of 1O2 is achieved by the electrocatalytic activation of O2. Additionally, the proposed system exhibits a consistent pollutant removal efficiency > 90% in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance, highlighting the dependable stability of the system for practical applications. The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor. This work provides a molecular level understanding of the oxygen reduction reaction, showing promising potential for the selective removal of emerging organic contaminants from water.
2025, 36(5): 110295
doi: 10.1016/j.cclet.2024.110295
摘要:
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
Developing a high-efficiency catalyst with both superior low-temperature activity and good N2 selectivity is still challenging for the NH3 selective catalytic reduction (SCR) of NOx from mobile sources. Herein, we demonstrate the improved low-temperature activity and N2 selectivity by regulating the redox and acidic properties of MnCe oxides supported on etched ZSM-5 supports. The etched ZSM-5 enables the highly dispersed state of MnCeOx species and strong interaction between Mn and Ce species, which promotes the reduction of CeO2, facilitates electron transfer from Mn to Ce, and generates more Mn4+ and Ce3+ species. The strong redox capacity contributes to forming the reactive nitrate species and -NH2 species from oxidative dehydrogenation of NH3. Moreover, the adsorbed NH3 and -NH2 species are the reactive intermediates that promote the formation of N2. This work demonstrates an effective strategy to enhance the low-temperature activity and N2 selectivity of SCR catalysts, contributing to the NOx control for the low-temperature exhaust gas during the cold-start of diesel vehicles.
2025, 36(5): 110306
doi: 10.1016/j.cclet.2024.110306
摘要:
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
The intrinsic clustering behavior and kinetically sluggish conversion process of lithium polysulfides seriously limit the electrochemical reversibility of sulfur redox reactions in lithium-sulfur (Li-S) batteries. Here, we introduce molybdenum pentachloride (MoCl5) into the electrolyte which could coordinate with lithium polysulfides and inhibit their intrinsic clustering behavior, subsequently serving as an improved mediator with the bi-functional catalytic effect for Li2S deposition and activation. Moreover, the coordination bonding and accelerated conversion reaction can also greatly suppress the dissolution and shuttling of polysulfides. Consequently, such polysulfide complexes enable the Li-S coin cell to exhibit good long-term cycling stability with a capacity decay of 0.078% per cycle after 400 cycles at 2 C, and excellent rate performance with a discharge capacity of 589 mAh/g at 4 C. An area capacity of 3.94 mAh/cm2 is also achieved with a high sulfur loading of 4.5 mg/cm2 at 0.2 C. Even at -20 ℃, the modified cell maintains standard discharge plateaus with low overpotential, delivering a high capacity of 741 mAh/g at 0.2 C after 80 cycles. The low-cost and convenient MoCl5 additive opens a new avenue for the effective regulation of polysulfides and significant enhancement in sulfur redox conversion.
2025, 36(5): 110310
doi: 10.1016/j.cclet.2024.110310
摘要:
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
An electronic circular dichroism (ECD)-based chiroptical sensing method has been developed for β- and γ-chiral primary amines via a C–H activation reaction. With the addition of Pd(OAc)2, the flexible remote chiral primary amine fragment in the bidentate ligand intermediate was fixed to form a cyclopalladium complex, producing an intense ECD response. The correlation between the sign of Cotton effects and the absolute configuration of substrates was proposed, together with theoretical verification using time-dependent density functional theory (TDDFT). Chiroptical sensing of an important drug raw material was performed to provide rapid and accurate information on the absolute optical purity. This work introduces an alternative perspective of C–H activation reaction as well as a feasible chiroptical sensing method of remote chiral amines.
2025, 36(5): 110311
doi: 10.1016/j.cclet.2024.110311
摘要:
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
Achieving artificial simulations of multi-step energy transfer processes and conversions in nature remains a challenge. In this study, we present a three-step sequential energy transfer process, which was constructed through host-guest interactions between a piperazine derivative (PPE-BPI) with aggregation-induced emission (AIE) and cucurbit[7]uril (CB[7]) in water to serve as ideal energy donors. To achieve multi-step sequential energy transfer, we employ three distinct fluorescent dyes Eosin B (EsB), Sulforhodamine 101 (SR101), and Cyanine 5 (Cy5) as energy acceptors. The PPE-PBI-2CB[7]+EsB+SR101+Cy5 system demonstrates a highly efficient three-step sequential energy transfer mechanism, starting with PPE-PBI-2CB[7] and transferring energy successively to EsB, SR101, and finally to Cy5, with remarkable energy transfer efficiencies. More interestingly, with the progressive transfer of energy in the multi-step energy transfer system, the generation efficiency of superoxide anion radical (O2•–) increased gradually, which can be used as photocatalysts for selectively photooxidation of N-phenyltetrahydroisoquinoline in an aqueous medium with a high yield of 86% after irradiation for 18 h. This study offers a valuable investigation into the simulation of multi-step energy transfer processes and transformations in the natural world, paving the way for further research in the field.
2025, 36(5): 110312
doi: 10.1016/j.cclet.2024.110312
摘要:
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
A sp2 carbon-conjugated covalent organic framework (BDATN) was modified through γ-ray radiation reduction and subsequent acidification with hydrochloric acid to yield a novel functional COF (named rBDATN-HCl) for Cr(VI) removal. The morphology and structure of rBDATN-HCl were analyzed and identified by SEM, FTIR, XRD and solid-state 13C NMR. It is found that the active functional groups, such as hydroxyl and amide, were introduced into BDATN after radiation reduction and acidification. The prepared rBDATN-HCl demonstrates a photocatalytic reduction removal rate of Cr(VI) above 99% after 60 min of illumination with a solid-liquid ratio of 0.5 mg/mL, showing outstanding performance, which is attributed to the increase of dispersibility and adsorption sites of rBDATN-HCl. In comparison to the cBDATN-HCl synthesized with chemical reduction, rBDATN-HCl exhibits a better photoreduction performance for Cr(VI), demonstrating the advantages of radiation preparation of rBDATN-HCl. It is expected that more functionalized sp2 carbon-conjugated COFs could be obtained by this radiation-induced reduction strategy.
2025, 36(5): 110334
doi: 10.1016/j.cclet.2024.110334
摘要:
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
An unprecedented 2,3-arylacylation reaction of allenes with aryl iodides and aldehydes was developed by resorting to Pd/NHC synergetic catalysis. It is the first time that allene was introduced into transition metal and NHC synergetic catalysis, which demonstrated a versatile three-component reaction pattern, thus enabling two C-C bonds forged regioselectively in the reaction. The important reaction intermediates were successfully captured and characterized by HRMS analysis, and the migrative insertion of allene to the Ph-Pd species was identified as the reaction rate-limiting step by kinetic experiments.
2025, 36(5): 110432
doi: 10.1016/j.cclet.2024.110432
摘要:
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
Chirality, ubiquitous in living matter, plays vital roles in a series of physiological processes. The clarification of the multiple functions of chirality in bioapplications may provide innovative methodologies for engineering anti-tumor agents. Nevertheless, the related research has been rarely explored. In this study, the chiral supramolecular l/d-cysteine (Cys)-Zn2+-indocyanine green (ICG) nanoparticles were constructed through the coordination interaction between l/d-Cys and Zn2+, followed by the encapsulation of ICG. Experimental findings revealed that the d-Cys-Zn2+-ICG exhibited 17.31 times higher binding affinity toward phospholipid-composed liposomes compared to l-Cys-Zn2+-ICG. Furthermore, driven by chirality-specific interaction, a 2.07 folds greater cellular internalization of d-Cys-Zn2+-ICG than l-Cys-Zn2+-ICG was demonstrated. Additionally, the triple-level chirality-dependent photothermal, photodynamic and Zn2+ releasing anti-tumor effects of l/d Cys-Zn2+-ICG in vitro were verified. As a result, the d-formed nanoparticles achieved 1.93 times higher anti-tumor efficiency than the l-formed ones. The triple-level chirality-mediated anti-tumor effect highlighted in this study underscores the enormous potential of chirality in biomedicine and holds substantial significance in improving cancer therapeutic efficacy.
2025, 36(5): 110437
doi: 10.1016/j.cclet.2024.110437
摘要:
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
Ferroptosis in combination with immune therapy emerges as a promising approach for cancer therapy. Herein, dual-responsive metal-polyphenol coordinated nanomedicines were developed for pH/glutathione (GSH)-responsive synergistic ferroptosis and immunotherapy. Our innovative strategy involves the development of a manganese-polyphenol coordinated nanostructure, leveraging the biocompatibility of bovine serum albumin (BSA) as a template to encapsulate the anticancer drug sorafenib. The tumor microenvironment (pH/GSH) prompts the disassembly of MnO2 and epigallocatechin gallate (EGCG), thereby releases the anticancer payload. Concurrently, MnO2 acts to deplete intracellular GSH, which in turn suppresses glutathione peroxidase activity, leading to an accumulation of lipid peroxides with cell ferroptosis. Additionally, the release of Mn2+ ions bolster the cyclic guanosine monophosphlic acid (GMP)-adenosine monophosphlic acid (AMP) synthase-stimulator of interferon gene (cGAS-STING) pathway, which, in conjunction with the immunogenic cell death (ICD) effect induced by tumor cell apoptosis, significantly promotes dendritic cell (DC) maturation and enhances the presentation of tumor antigens. This successively ignites a robust innate and adaptive immune response. Both in vitro and in vivo experiments have demonstrated that the concurrent administration of ferroptosis-inducing and immune-stimulating therapies can significantly inhibit tumor growth.
2025, 36(5): 110508
doi: 10.1016/j.cclet.2024.110508
摘要:
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
Candida albicans is one of the most common pathogens causing invasive fungal infections, with a mortality rate of up to 20%–50%. Amphotericin B (AmB), a biopharmaceutics classification system (BCS) IV drug, significantly inhibits Candida albicans. AmB is primarily administered via oral and intravenous infusion, but severe infusion adverse effects, nephrotoxicity, and potential hepatotoxicity limit its clinical application. Deep eutectic solvents (DESs), with excellent solubilization ability and skin permeability, are attractive for transdermal delivery. Herein, we used DESs to deliver AmB for antifungal therapy transdermally. We first prepared and characterized DESs with different stoichiometric ratios of choline (Ch) and geranate (Ge). DESs increased the solubility of AmB by a thousand-fold. In vitro and in vivo, skin permeation studies indicated that DES1:2 (Ch and Ge in 1:2 ratio) had the most outstanding penetration and delivered fluorescence dye to the dermis layer. Then, DES1:2-AmB was prepared and in vitro antifungal tests demonstrated that DES1:2-AmB had superior antifungal effects compared to AmB and DES1:2. Furthermore, DES1:2-AmB was skin-irritating and biocompatible. In conclusion, DES-AmB provides a new and effective therapeutic solution for fungal infections.
2025, 36(5): 110561
doi: 10.1016/j.cclet.2024.110561
摘要:
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
Nanochannel technology based on ionic current rectification has emerged as a powerful tool for the detection of biomolecules owing to unique advantages. Nevertheless, existing nanochannel sensors mainly focus on the detection of targets in solution or inside the cells, moreover, they only have a single function, greatly limiting their application. Herein, we fabricated SuperDNA self-assembled conical nanochannel, which was clamped in the middle of self-made device for two functions: Online detecting living cells released TNF-α and studying intercellular communication. Polyethylene terephthalate (PET) membrane incubated tumor associated macrophages and tumor cells was rolled up and inserted into the left and right chamber of the device, respectively. Through monitoring the ion current change in the nanochannel, tumor associated macrophages released TNF-α could be in situ and noninvasive detected with a detection limit of 0.23 pg/mL. Furthermore, the secreted TNF-α induced epithelial-mesenchymal transformation of tumor cells in the right chamber was also studied. The presented strategy displayed outstanding performance and multi-function, providing a promising platform for in situ non-destructive detection of cell secretions and related intercellular communication analysis.
2025, 36(5): 110629
doi: 10.1016/j.cclet.2024.110629
摘要:
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
Room-temperature phosphorescence (RTP) materials exhibiting long emission lifetimes have gained increasing attention owing to their potential applications in encryption, anti-counterfeiting, and sensing. However, most polymers exhibit a short RTP lifetime (<1 s) because of their unstable triplet excitons. Herein, a new strategy of polymer chain stabilized phosphorescence (PCSP), which yields a new kind of RTP polymers with an ultralong lifetime and a sensitive oxygen response, has been reported. The rigid polymer chains of poly(methyl mathacrylate) (PMMA) immobilize the emitter molecules through multiple interactions between them, giving rise to efficient RTP. Meanwhile, the loosely-packed amorphous polymer chains allow oxygen to diffuse inside, endowing the doped polymers with oxygen sensitivity. Flexible and transparent polymer films exhibited an impressive ultralong RTP lifetime of 2.57 s at room temperature in vacuum, which was among the best performance of PMMA. Intriguingly, their RTP was rapidly quenched in the presence of oxygen. Furthermore, RTP microparticles with a diameter of 1.63 µm were synthesized using in situ dispersion polymerization technique. Finally, oxygen sensors for quick, visual, and quantitative oxygen detection were developed based on the RTP microparticles through phosphorescence lifetime and image analysis. With distinctive advantages such as an ultralong lifetime, oxygen sensitivity, ease of fabrication, and cost-effectiveness, PCSP opens a new avenue to sensitive materials for oxygen detection.
2025, 36(5): 110663
doi: 10.1016/j.cclet.2024.110663
摘要:
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
Transition metal cobalt exhibits strong activation capabilities for alkanes, however, the instability of Co sites leads to sintering and coke deposition, resulting in rapid deactivation. Hierarchical zeolites, with their diverse pore structures and high surface areas, are used to effectively anchor metals and enhance coke tolerance. Herein, a post-treatment method using an alkaline solution was employed to synthesize meso-microporous zeolite supports, which were subsequently loaded with Co species for propane dehydrogenation catalyst. The results indicate that the application of NaOH, an inorganic base, produces supports with a larger mesopore volume and more abundant hydroxyl nests compared to TPAOH, an organic base. UV–vis, Raman, and XPS analyses reveal that Co in the 0.5Co/SN-1–0.05 catalyst is mainly in the form of tetrahedral Co2+, which effectively activates CH bonds. In contrast, the 0.5Co/S-1 catalyst contains mainly Co3O4 species. Co2+ supported on hierarchical zeolites shows better propane conversion (58.6%) and propylene selectivity (>96%) compared to pure silica zeolites. Coke characterization indicates that hierarchical zeolites accumulate more coke, but it is mostly in the form of easily removable disordered carbon. The mesopores in the microporous zeolite support help disperse the active Co metal and facilitate coke removal during dehydrogenation, effectively preventing deactivation from sintering and coke coverage.
2025, 36(5): 110672
doi: 10.1016/j.cclet.2024.110672
摘要:
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
On-demand droplet manipulation plays a critical role in microfluidics, bio/chemical detection and micro-reactions. Acoustic droplet manipulation has emerged as a promising technique due to its non-contact nature, biocompatibility and precision, circumventing the complexities associated with other methods requiring surface or droplet pretreatment. Despite their promise, existing methods for acoustic droplet manipulation often involve complex hardware setups and difficulty for controlling individual droplet amidst multiple ones. Here we fabricate simple yet effective acoustic tweezers for in-surface and out-of-surface droplet manipulation. It is found that droplets can be transported on the superhydrophobic surfaces when the acoustic radiation force surpasses the friction force. Using a two-axis acoustic tweezer, droplets can be maneuvered along arbitrarily programmed paths on the surfaces. By introducing multiple labyrinthine structures on the superhydrophobic surface, individual droplet manipulation is realized by constraining the unselected droplets in the labyrinthine structures. In addition, a three-axis acoustic tweezer is developed for manipulating droplets in three-dimensional space. Potential applications of the acoustic tweezers for micro-reaction, bio-assay and chemical analysis are also demonstrated.
2025, 36(5): 110699
doi: 10.1016/j.cclet.2024.110699
摘要:
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
Generally, gaining fundamental insights into chain processes during the combustion of flame-retardant polymers relies on the qualitative and quantitative characterization of key chain carriers. However, polymer combustion processes based on conventional solid-fuel combustion strategies, due to the high coupling of pyrolysis, combustion, soot formation and oxidation, exhibit relatively high complexity and poor flame stability, and lead to a huge obstacle to the use of optical diagnostics. Herein, a spatial-confinement combustion strategy, which can produce a special staged flame with multi-jets secondary wave, is devised to provide a highly decoupled combustion environment. Glowing soot particles are therefore decoupled from main chemiluminescence region and confined to the flame tip to provide a well-controlled, optical-thin test environment for combustion diagnostic. Based on this strategy, a multi-nozzle-separation (MNS) burner is designed and fabricated, and the combustion processes associated with four model compounds, PVC, PS, PP/TBBA blends and PP/RP blends are investigated by spontaneous spectral diagnosis, and the chemiluminescence fingerprint of key diatomic/triatomic intermediates (such as OH, CH, C2, ClO, Br2, and PHO) are clearly observed. This encouraging result means that the strategy of spatial-confinement combustion we proposed shows promising prospect in many subjects associated with combustion chain regulation, such as efficient design of flame retardants.
2025, 36(5): 110700
doi: 10.1016/j.cclet.2024.110700
摘要:
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
Heterocyclic compounds play an important role in organic hole transport materials (HTMs) for perovskite solar cells (PSCs). Herein, a series of linear D-π-D HTMs (OCBz, S-CBz, SO2-CBz) with different dibenzo-heterocycles core (dibenzofuran, dibenzothiophene, dibenzothiophene sulfone) were designed and synthesized, and their applications in PSCs were investigated. The intrinsic properties (CV, UV–vis, hole mobility and conductivity) were systematically investigated, demonstrating that all three materials are suitable HTMs for planar n-i-p type PSCs. Benefiting from the excellent hole mobility and conductivity, good film forming ability, and outstanding charge extraction and transport capability of S-CBz, FAPbI3-based PSCs using S-CBz as HTM achieved a PCE of 25.0%, which is superior to that of Spiro-OMeTAD-based PSCs fabricated under the same conditions (23.9%). Furthermore, due to the interaction between S and Pb2+, S-CBz-based PSC devices exhibited improved stability. This work demonstrates that dibenzothiophene-based architectures are promising candidates for high-performance HTMs in perovskite solar cell architectures.
2025, 36(5): 110719
doi: 10.1016/j.cclet.2024.110719
摘要:
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
Crystalized CeO2 structures were typically considered potential photocatalysts due to their great capacity to alter the active sites’ size and ability to absorb light. However, the controllable fabrication of well-defined hierarchical structures of CeO2 with high reactive facets is significant and challenging. Herein, a series of CeO2 supports including hierarchical flower-like (F-CeO2), ball-like (B-CeO2), cube-like (CCeO2), and rod-like CeO2(R-CeO2) supports were prepared by hydrothermal method (B-CeO2, R-CeO2 and CCeO2) or ice-bath method (F-CeO2) respectively. V atoms were selected as the active atoms and loaded on these supports. Their structure-activity relationship in photo-assisted thermal propane dehydrogenation (PTPDH) was investigated systematically. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption isotherms, and Fourier transform infrared spectrum. Results show that R-CeO2 support exhibits the biggest surface area thus achieving the best dispersion of VOx species. UV–vis spectrum and photoluminescence spectrum indicate that V/F-CeO2 has the best light adsorption property and V/R-CeO2 has the best carrier migration capacity. The activity tests demonstrate that the V/R-CeO2 has the largest net growth rate and the V/F-CeO2 has the biggest relative growth ratio. Furthermore, the non-thermal effect was confirmed by the kinetic method, which lowers the propane reaction orders, selectively promoting the first C–H bond activation. The light radiation TPSR experiment confirmed this point. DFT calculations show a good linear relationship between the energy barrier and the exchanged electron number. It inspires the design of high-reactive facets for boosting the intrinsic activity of the C–H bond in photo-assisted thermal chemical processes.
2025, 36(5): 110724
doi: 10.1016/j.cclet.2024.110724
摘要:
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
To get large dissymmetric factor (glum) of organic circularly polarized luminescence (CPL) materials is still a great challenge. Although helical chirality and planar chirality are usual efficient access to enhancement of CPL, they are not combined together to boost CPL. Here, a new tetraphenylethylene (TPE) tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized. Uniquely, synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies. In the presence of octadecylamine, the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute glum value up to 0.237. Exceptionally, followed by addition of para-phenylenediamine, the glum value was successively increased to 0.387 due to formation of bigger helical nanofibers. Compared with that of TPE helicate itself, the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed, which was very rare result for CPL-active materials. Surprisingly, the interaction of TPE helicate with xylylenediamine even gave a gel, which was transformed into suspension by shaking. Unexpectedly, the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other. Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large glum value.
2025, 36(5): 110760
doi: 10.1016/j.cclet.2024.110760
摘要:
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
Triphenylamine (TPA) is the most promising donor fragment for the construction of long-wavelength thermally activated delayed fluorescence (TADF) emitters owing to its suitable dihedral angle that could enhance radiative decay to compete with the serious non-radiative decay. However, the moderate electron-donating capacity of TPA seriously limits the selection of acceptor for constructing long-wavelength TADF emitters with narrow bandgaps. To address this issue, in this work, the peripheral benzene of TPA was replaced with 1,4-benzodioxane and anisole to obtain two new electron-donating units N-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-N-phenyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine (TPADBO, −5.02 eV) and 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPAMO, −5.00 eV), which possess much shallower highest occupied molecule orbital (HOMO) energy levels than the prototype TPA (−5.33 eV). Based on TPA and the modified TPA donor fragments, three TADF emitters were designed and synthesized, namely Py-TPA, Py-TPADBO and Py-TPAMO, with the same acceptor fragment 12-(2,6-diisopropylphenyl)pyrido[2′,3′:5,6]pyrazino[2,3-f][1,10]phenanthroline (Py). Among them, Py-TPAMO exhibits the highest photoluminescence quantum yield of 78.4% and the smallest singlet-triplet energy gap, which is because the introduction of anisole does not cause significant molecule deformation for the excited Py-TPAMO. And Py-TPAMO-based OLEDs successfully realize a maximum external quantum efficiency of 25.5% with the emission peak at 605 nm. This work provides a series of candidate of donor fragments for the development of efficient long-wavelength TADF emitters.
2025, 36(5): 110762
doi: 10.1016/j.cclet.2024.110762
摘要:
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
A series of “half-sandwich” bis(imino)pyridyl iron complexes with a substituted 8-(p-X-phenyl)naphthylamine (X = OMe, Me, CF3) was designed and synthesized by combining weak π-π interaction with steric and electronic tunings. The weak noncovalent π-π interaction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations. The roles of weak π-π interaction, steric bulk, and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail. The combination of π-π interaction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130 ℃.
2025, 36(5): 110765
doi: 10.1016/j.cclet.2024.110765
摘要:
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
Metal ions trigger Fenton/Fenton-like reactions, generating highly toxic hydroxyl radicals (•OH) for chemodynamic therapy (CDT), which is crucial in inducing lethal oxidative DNA damage and subsequent cell apoptosis. However, tumor cells can counteract this damage through repair pathways, particularly MutT homolog 1 (MTH1) protein attenuation of oxidative DNA damage. Suppression of MTH1 can enhance CDT efficacy, therefore, orderly integrating Fenton/Fenton-like agents with an MTH1 inhibitor is expected to significantly augment CDT effectiveness. Carrier-free CuTH@CD, self-assembled through the supramolecular orchestration of γ-cyclodextrin (γ-CD) with Cu2+ and the MTH1 inhibitor TH588, effectively overcoming tumor resistance by greatly amplifying oxidative damage capability. Without additional carriers and mediated by multiple supramolecular regulatory effects, CuTH@CD enables high drug loading content, stability, and uniform size distribution. Upon internalization by tumor cells, CuTH@CD invalidates repair pathways through Cu2+-mediated glutathione (GSH) depletion and TH588-mediated MTH1 inhibition. Meanwhile, both generated Cu+ ions and existing ones within the nanoassembly initiate a Fenton-like reaction, leading to the accumulation of •OH. This strategy enhances CDT efficiency with minimal side effects, improving oxidative damage potency and advancing self-delivery nanoplatforms for developing effective chemodynamic tumor therapies.
2025, 36(5): 109871
doi: 10.1016/j.cclet.2024.109871
摘要:
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
Green synthesis of drugs is of paramount importance for current public health and a prerequisite to new drugs exploiting. Nowadays, novel strategies of disease diagnosis and therapies are in blooming development as remarkable advances have been achieved which are all highly depended on drug development. Under the current requirements to high production capacity and novel synthesis methods of drugs, green synthesis based on strategies with different ways of empowering, advanced catalysts and unique reaction equipment are attracting huge attention and of great challenging. Higher quality products and environmentally friendly synthesis conditions are becoming more and more important for manufacturing process which has new requirements for catalyst materials and synthesis processes. Polyoxometalates (POMs) are class of transition metals-oxygen clusters with precise molecular structures and superior physicochemical properties which have made longstanding and important applications upon research community of functional materials, catalysis and medicine. In this review, the recent advances of polyoxometalates based strategies for green synthesis of drugs are summarized including POMs based catalysts, alternative reaction equipment based novel synthesis protocols. The significance of POMs to pharmaceutical and industrial field is highlighted and the related perspective for future development are well discussed.
2025, 36(5): 109898
doi: 10.1016/j.cclet.2024.109898
摘要:
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Two-dimensional (2D) transition metal sulfides (TMDs) are emerging and highly well received 2D materials, which are considered as an ideal 2D platform for studying various electronic properties and potential applications due to their chemical diversity. Converting 2D TMDs into one-dimensional (1D) TMDs nanotubes can not only retain some advantages of 2D nanosheets but also providing a unique direction to explore the novel properties of TMDs materials in the 1D limit. However, the controllable preparation of high-quality nanotubes remains a major challenge. It is very necessary to review the advanced development of one-dimensional transition metal dichalcogenide nanotubes from preparation to application. Here, we first summarize a series of bottom-up synthesis methods of 1D TMDs, such as template growth and metal catalyzed method. Then, top-down synthesis methods are summarized, which included self-curing and stacking of TMDs nanosheets. In addition, we discuss some key applications that utilize the properties of 1D-TMDs nanotubes in the areas of catalyst preparation, energy storage, and electronic devices. Last but not least, we prospect the preparation methods of high-quality 1D-TMDs nanotubes, which will lay a foundation for the synthesis of high-performance optoelectronic devices, catalysts, and energy storage components
Iridium-based catalysts for oxygen evolution reaction in proton exchange membrane water electrolysis
2025, 36(5): 109906
doi: 10.1016/j.cclet.2024.109906
摘要:
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
Proton exchange membrane water electrolysis (PEMWE) is a favorable technology for producing high-purity hydrogen under high current density using intermittent renewable energy. The performance of PEMWE is largely determined by the oxygen evolution reaction (OER), a sluggish four-electron reaction with a high reaction barrier. Nowadays, iridium (Ir)-based catalysts are the catalysts of choice for OER due to their excellent activity and durability in acidic solution. However, its high price and unsatisfactory electrochemical performance severely restrict the PEMWE’s practical application. In this review, we initiate by introducing the current OER reaction mechanisms, namely adsorbate evolution mechanism and lattice oxygen mechanism, with degradation mechanisms discussed. Optimized strategies in the preparation of advanced Ir-based catalysts are further introduced, with merits and potential problems also discussed. The parameters that determine the performance of PEMWE are then introduced, with unsolved issues and related outlooks summarized in the end.
2025, 36(5): 109938
doi: 10.1016/j.cclet.2024.109938
摘要:
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
Solid-state electrolytes (SSEs), as the core component within the next generation of key energy storage technologies - solid-state lithium batteries (SSLBs) - are significantly leading the development of future energy storage systems. Among the numerous types of SSEs, inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12 (LLZO) crystallized with the cubic Ia3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity, wide electrochemical voltage window, high shear modulus, and excellent chemical stability with electrodes. However, no SSEs possess all the properties necessary for SSLBs, thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement. Hence, this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration, Li vacancy concentration, Li carrier concentration and mobility, Li occupancy at available sites, lattice constant, triangle bottleneck size, oxygen vacancy defects, and Li-O bonding interactions. Furthermore, the general illustration of structures and fundamental features being crucial to chemical stability is examined, including Li concentration, Li-site occupation behavior, and Li-O bonding interactions. Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures, revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions. We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors, thus assisting in promoting the rapid development of alternative green and sustainable technologies.
2025, 36(5): 110059
doi: 10.1016/j.cclet.2024.110059
摘要:
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
Lateral flow immunoassay (LFIA), a rapid detection technique noted for simplicity and economy, has showcased indispensable applicability in diverse domains such as disease screening, food safety, and environmental monitoring. Nevertheless, challenges still exist in detecting ultra-low concentration analytes due to the inherent sensitivity limitations of LFIA. Recently, significant advances have been achieved by integrating enzyme activity probes and transforming LFIA into a highly sensitive tool for rapidly detecting trace analyte concentrations. Specifically, modifying natural enzymes or engineered nanozymes allows them to function as immune probes, directly catalyzing the production of signal molecules or indirectly initiating enzyme activity. Therefore, the signal intensity and detection sensitivity of LFIA are markedly elevated. The present review undertakes a comprehensive examination of pertinent research literature, offering a systematic analysis of recently proposed enzyme-based signal amplification strategies. By way of comparative assessment, the merits and demerits of current approaches are delineated, along with the identification of research avenues that still need to be explored. It is anticipated that this critical overview will garner considerable attention within the biomedical and materials science communities, providing valuable direction and insight toward the advancement of high-performance LFIA technologies.
2025, 36(5): 110072
doi: 10.1016/j.cclet.2024.110072
摘要:
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
Designing advanced hydrogels with controlled mechanical properties, drug delivery manner and multifunctional properties will be beneficial for biomedical applications. However, the further development of hydrogel is limited due to its poor mechanical property and structural diversity. Hydrogels combined with polymeric micelles to obtain micelle-hydrogel composites have been designed for synergistic enhancement of each original properties. Incorporation polymeric micelles into hydrogel networks can not only enhance the mechanical property of hydrogel, but also expand the functionality of hydrogel. Recent advances in polymeric micelle-hydrogel composites are herein reviewed with a focus on three typical micelle incorporation methods. In this review, we will also highlight some emerging biomedical applications in developing micelle-hydrogel composite with multiple functionalities. In addition, further development and application prospects of the micelle-hydrogels composites have also been addressed.
2025, 36(5): 110126
doi: 10.1016/j.cclet.2024.110126
摘要:
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
Chemical modification of native peptides and proteins is a versatile strategy to facilitate late-stage diversification for functional studies. Among the proteogenic amino acids, lysine is extensively involved in post-translational modifications and the binding of ligands to target proteins, making its selective modification attractive. However, lysine’s high natural abundance and solvent accessibility, as well as its relatively low reactivity to cysteine, necessitate addressing chemoselectivity and regioselectivity for the Lys modification of native proteins. Although Lys chemoselective modification methods have been well developed, achieving site-selective modification of a specific Lys residue remains a great challenge. In this review, we discussed the challenges of Lys selective modification, presented recent examples of Lys chemoselective modification, and summarized the currently known methods and strategies for Lys site-selective modification. We also included an outlook on potential solutions for Lys site-selective labeling and its potential applications in chemical biology and drug development.
2025, 36(5): 110226
doi: 10.1016/j.cclet.2024.110226
摘要:
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
The heritage preservation is of great intractability to the conservators as each kind of heritage material has unique and diverse requirements on temperature, humidity and air cleanliness. It is promising for metal-organic frameworks (MOFs), the multifunctional environment remediation materials, to be applied in heritage environmental protection. The advantages of MOFs lie in their multifunction like adsorption, photocatalysis, sterilization, as well as the controllable structure and properties that could be flexibly adjusted as demands, helping the heritage against various environmental threats. Thereby, the applications and the corresponding mechanisms of MOFs in cultural heritage preservation were reviewed in this work, including harmful gas adsorption, surface waterproofing, particulate matters (PM) removal, anti-bacterial and humidity control of environment. Finally, the selection principles and precautions of MOFs in heritage preservation were discussed, aiming to provide a forward-looking direction for the selection and application of MOFs.
2025, 36(5): 110277
doi: 10.1016/j.cclet.2024.110277
摘要:
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
As a versatile and environmentally benign oxidant, hydrogen peroxide (H2O2) is highly desired in sanitation, disinfection, environmental remediation, and the chemical industry. Compared with the conventional anthraquinone process, the electrosynthesis of H2O2 through the two-electron oxygen reduction reaction (2e− ORR) is an efficient, competitive, and promising avenue. Electrocatalysts and devices are two core factors in 2e− ORR, but the design principles of catalysts for different pH conditions and the development trends of relevant synthesis devices remain unclear. To this end, this review adopts a multiscale perspective to summarize recent advancements in the design principles, catalytic mechanisms, and application prospects of 2e− ORR catalysts, with a particular focus on the influence of pH conditions, aiming at providing guidance for the selective design of advanced 2e− ORR catalysts for highly-efficient H2O2 production. Moreover, in response to diverse on-site application demands, we elaborate on the evolution of H2O2 electrosynthesis devices, from rotating ring-disk electrodes and H-type cells to diverse flow-type cells. We elaborate on their characteristics and shortcomings, which can be beneficial for their further upgrades and customized applications. These insights may inspire the rational design of innovative catalysts and devices with high performance and wide serviceability for large-scale implementations.
2025, 36(5): 110284
doi: 10.1016/j.cclet.2024.110284
摘要:
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
Developing efficient, non-toxic, and low-cost emitters is a key issue in promoting the applications of electrochemiluminescence (ECL). Among varied ECL emitters, polymeric emitters are attracting dramatically increasing interest due to tunable structure, large surface area, brilliant transfer capability, and sustainable raw materials. In this review, we present a general overview of recent advances in developing polymeric luminophores, including their structural and synthetic methodologies. Methods rooted in straightforward unique structural modulation have been comprehensively summarized, aiming at enhancing the efficiency of ECL along with the underlying kinetic mechanisms. Moreover, as several conjugated polymers were just discovered in recent years, promising prospects and perspectives have also been deliberated. The insight of this review may provide a new avenue for helping develop advanced conjugated polymer ECL emitters and decode ECL applications.
2025, 36(5): 110423
doi: 10.1016/j.cclet.2024.110423
摘要:
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
As a novel two-dimensional (2D) material, MXenes are anticipated to have a significant impact on future aqueous energy storage and conversion technologies owing to their unique intrinsic laminar structure and exceptional physicochemical properties. Nevertheless, the fabrication and utilization of functional MXene-based devices face formidable challenges due to their susceptibility to oxidative degradation in aqueous solutions. This review begins with an outline of various preparation techniques for MXenes and their implications for structure and surface chemistry. Subsequently, the controversial oxidation mechanisms are discussed, followed by a summary of currently employed oxidation characterization techniques. Additionally, the factors influencing MXene oxidation are then introduced, encompassing chemical composition (types of M, X elements, layer numbers, terminations, and defects) as well as environment (atmosphere, temperature, light, potential, solution pH, free water and O2 content). The review then shifts its focus to strategies aiming to prevent or delay MXene oxidation, thereby expanding the applicability of MXenes in complex environments. Finally, the challenges and prospects within this rapidly-growing research field are presented to promote further advancements of MXenes in aqueous storage systems.
2025, 36(5): 110503
doi: 10.1016/j.cclet.2024.110503
摘要:
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
Homogeneous C–H and C–X borylation via transition-metal-catalysis have undergone rapid development in the past decades and become one of the most practical methods for the synthesis of organoboron compounds. However, the catalysts employed in homogeneous catalysis are generally expensive, sensitive, and difficult to separate from the reaction mixture and reuse. With the rapid development of heterogeneous catalysis, heterogeneous C–H and C–X borylation have emerged as highly efficient and sustainable approaches towards the synthesis of organoboron compounds. This review aims to highlight the recent advances in the synthesis of organoboron compounds employing heterogeneous C–H and C–X borylation strategies. We endeavor to shed light on new perspectives and inspire further research and applications in this emerging area.
2025, 36(5): 110521
doi: 10.1016/j.cclet.2024.110521
摘要:
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
The enantioselective separation of racemate, particularly those containing C(sp3)-H bonds knowns for their high bond dissociation energies and significant polarity, presents a significant challenge in pharmaceutical synthesis. Recent advances have witnessed the fusion of photocatalysis with hydrogen atom transfer (HAT) methodologies, marking a notable trend in synthesis of chiral molecules. This technique uses the excitation of a catalyst to activate substrates, enabling the selective isomerization of chiral centers containing C(sp3) configurations. This process distinctively facilitates the direct activation of the C(sp3)-H bond in targeted reagents. This review systematically discusses the photocatalytic isomerization of various chiral molecule featuring C(sp3)-H centers, capable of undergoing deracemization through two primary HAT mechanisms: direct and indirect pathways. From the perspective of synthetic organic chemistry, this field has progressed towards the development of isomerization strategies for molecules that incorporate an activating group at the α-position adjacent to the C(sp3) chiral center. Moreover, it covers methodologies applicable to molecules characterized by specific C-C and C-S bond configurations. The integration of photocatalysis with HAT technology thus provides valuable strategies for the synthesis of enantiopure compounds with enhanced selectivity and efficiency.
2025, 36(5): 110529
doi: 10.1016/j.cclet.2024.110529
摘要:
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
Utilizing transporter-mediated drug delivery to achieve effective oral absorption emerges as a promising strategy. Researchers have been concentrated on discovering solutions to the issues of low solubility and poor permeability of insoluble drugs, whereas, current reports have revealed that drug transporter proteins are abundantly expressed in the mucosa of intestinal epithelial cells, and that their mediated drug absorption effectively improved the bioavailability of orally administered drugs. There are two main categories based on the transporter mechanism, which include the family of ATP-binding cassette (ABC) transporters with efflux effects that reduce drug bioavailability and the family of solute carriers (SLC) transporters with uptake effects that promote drug absorption, respectively. Thus, we review studies of intestinal transporter-mediated delivery of drugs to enhance oral absorption, including the types of intestinal transporters, distribution characteristics, and strategies for enhancing oral absorption using transporter-mediated drug delivery systems are summarized, with the aim of providing important theoretical references for the development of intestinal-targeted delivery system.
2025, 36(5): 110618
doi: 10.1016/j.cclet.2024.110618
摘要:
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
Carbon dots (CDs) are an emerging class of zero-dimensional carbon nano optical materials that are as promising candidates for various applications. Through the exploration of scientific researchers, the optical band gap of CDs has been continuously regulated and red-shifted from the initial blue-violet light to longer wavelengths. In recent years, CDs with near-infrared (NIR) absorption/emission have been gradually reported. Because NIR light has deeper penetration and lower scattering and is invisible to the human eye, it has great application prospects in the fields of biological imaging and treatment, information encryption, optical communications, etc. Although there are a few reviews on deep red to NIR CDs, they only focus on the single biomedical direction. There is still a lack of comprehensive reviews focusing on NIR (≥700 nm) absorption and luminescent CDs and their multifunctional applications. Based on our research group’s findings on NIR CDs, this review summarizes recent advancements in their preparation strategies and applications, points out the current shortcomings and challenges, and anticipates future development trajectories.
2025, 36(5): 110628
doi: 10.1016/j.cclet.2024.110628
摘要:
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities, which attracted the attention of many chemists. Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy, mild reaction conditions and simplicity of operation. Allenolates, Morita−Baylis−Hillman (MBH) alcohols and their derivatives (MBHADs), electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations, which formed many phosphonium species such as β-phosphonium enolates, β-phosphonium dienolates and vinyl phosphonium ylides as intermediates. This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations. Thus, a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates, MBH alcohols and MBHADs, electron-deficient olefins and alkynes are presented in Chapters 2–6, respectively.
2025, 36(5): 110764
doi: 10.1016/j.cclet.2024.110764
摘要:
2025, 36(5): 110869
doi: 10.1016/j.cclet.2025.110869
摘要:
2025, 36(5): 110936
doi: 10.1016/j.cclet.2025.110936
摘要:
