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The first issue is scheduled to be published in Dec. 2018.
Call for Papers
CCS Chemistry is the flagship general journal for the cutting edge and fundamental research in the areas of chemica research facing global audiences published by Chinese Chemical Society. We call for excellent papers cover but not limited to synthetic chemistry, catalysis & surface chemistry, chemical theory and mechanism, chemical metrology, materials & energy chemistry, environmental chemistry, chemical biology, chemical engineering and industrial chemistry. Professional arrangement ensures that all papers can be reviewed and published online quickly and efficiently (one or two weeks).
Contact information:
Dr. Hao Linxiao, haolinxiao@iccas.ac.cn; +86-10-82449177-888
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2025, 36(10): 110369
doi: 10.1016/j.cclet.2024.110369
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
2025, 36(10): 111408
doi: 10.1016/j.cclet.2025.111408
Abstract:
2025, 36(10): 111504
doi: 10.1016/j.cclet.2025.111504
Abstract:
