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2025 Volume 36 Issue 1
2025, 36(1): 109530
doi: 10.1016/j.cclet.2024.109530
Abstract:
Multiple switchable physical channels within one material or device, encompassing optical, electrical, thermal, and mechanical pathways, can enable multifunctionality in mechanical-thermal-opto-electronic applications. Achieving integrated encryption and enhanced performance in storage and sensing presents a formidable challenge in the synthesis and functionality of new materials. In an effort to overcome the complexities associated with these multiple physical functions, this study investigates the large-size crystal of DPACdCl4 (DPA = diisopropylammonium), revealing significant features in rare multi-channel switches. This compound demonstrates the ability to switch between "OFF/0" and "ON/1" states in the mechanical-thermal-opto-electronic channels. Consequently, DPACdCl4 possesses four switchable physical channels, characterized by a higher phase transition temperature of 440.7 K and a competitive piezoelectric coefficient of 46 pC/N. Furthermore, solid-state NMR analysis indicates that thermally activated molecular vibrations significantly contribute to its multifunctional switching capabilities.
Multiple switchable physical channels within one material or device, encompassing optical, electrical, thermal, and mechanical pathways, can enable multifunctionality in mechanical-thermal-opto-electronic applications. Achieving integrated encryption and enhanced performance in storage and sensing presents a formidable challenge in the synthesis and functionality of new materials. In an effort to overcome the complexities associated with these multiple physical functions, this study investigates the large-size crystal of DPACdCl4 (DPA = diisopropylammonium), revealing significant features in rare multi-channel switches. This compound demonstrates the ability to switch between "OFF/0" and "ON/1" states in the mechanical-thermal-opto-electronic channels. Consequently, DPACdCl4 possesses four switchable physical channels, characterized by a higher phase transition temperature of 440.7 K and a competitive piezoelectric coefficient of 46 pC/N. Furthermore, solid-state NMR analysis indicates that thermally activated molecular vibrations significantly contribute to its multifunctional switching capabilities.
2025, 36(1): 109551
doi: 10.1016/j.cclet.2024.109551
Abstract:
α-MnO2 is a potential positive electrode material for aqueous zinc-ion batteries, but its electrochemical performance of zinc storage requires further improvement. In this paper, potassium ion-doped manganese dioxide nanoscrolls (KMnO2) with oxygen vacancy were synthesized by a one-step hydrothermal method. It was observed that the electrochemical specific capacity was 250.9 mAh/g at a current density of 0.2 C, which was better than the existing commercial α-MnO2. At a high current of 1 C, these batteries demonstrate improved cycle stability. Synchrotron radiation and other experiments as well as DFT theoretical calculations provided additional evidence that K doping was efficient in regulating the metal bond type and the mean charge regulation of covalent bonds with oxygen atoms in MnO2. When MnO and MnK bonds are present, KMnO2 showed outstanding adsorption of Zn2+ and further enhanced the Zn2+ embedding process. Simultaneously, oxygen defects caused by doping boosted the development of the nanoscroll structure, leading to an increase in active sites available for electrochemical reactions and subsequently enhancing the electrical conductivity of α-MnO2. This study exhibits the potential of optimizing materials based on manganese with the introduction of a potassium doping strategy, resulting in improved performance for aquatic zinc-ion batteries, and presents novel perspectives for related research.
α-MnO2 is a potential positive electrode material for aqueous zinc-ion batteries, but its electrochemical performance of zinc storage requires further improvement. In this paper, potassium ion-doped manganese dioxide nanoscrolls (KMnO2) with oxygen vacancy were synthesized by a one-step hydrothermal method. It was observed that the electrochemical specific capacity was 250.9 mAh/g at a current density of 0.2 C, which was better than the existing commercial α-MnO2. At a high current of 1 C, these batteries demonstrate improved cycle stability. Synchrotron radiation and other experiments as well as DFT theoretical calculations provided additional evidence that K doping was efficient in regulating the metal bond type and the mean charge regulation of covalent bonds with oxygen atoms in MnO2. When MnO and MnK bonds are present, KMnO2 showed outstanding adsorption of Zn2+ and further enhanced the Zn2+ embedding process. Simultaneously, oxygen defects caused by doping boosted the development of the nanoscroll structure, leading to an increase in active sites available for electrochemical reactions and subsequently enhancing the electrical conductivity of α-MnO2. This study exhibits the potential of optimizing materials based on manganese with the introduction of a potassium doping strategy, resulting in improved performance for aquatic zinc-ion batteries, and presents novel perspectives for related research.
2025, 36(1): 109555
doi: 10.1016/j.cclet.2024.109555
Abstract:
Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency, e.g., electrocatalytic CO2 reduction reaction (CO2RR). Herein, we employ freestanding porous carbon fibers (PCNF) as an efficacious and stable support for the uniformly distributed SnO2 nanoparticles (SnO2PCNF), thereby capitalizing on the synergistic support effect that arises from their strong interaction. On one hand, the interaction between the SnO2 nanoparticles and the carbon support optimizes the electronic configuration of the active centers. This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy, consequently lowering the energy barrier associated with CO2 reduction. As a result, the SnO2PCNF realizes a remarkable CO2RR performance with excellent selectivity towards formate (98.1%). On the other hand, the porous carbon fibers enable the uniform and stable dispersion of SnO2 nanoparticles, and this superior porous structure of carbon supports can also facilitate the exposure of the SnO2 nanoparticles on the reaction interface to a great extent. Consequently, adequate contact between active sites, reactants, and electrolytes can significantly increase the metal utilization, eventually bringing forth a remarkable 7.09 A/mg mass activity. This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.
Leveraging the interplay between the metal component and the supporting material represents a cornerstone strategy for augmenting electrocatalytic efficiency, e.g., electrocatalytic CO2 reduction reaction (CO2RR). Herein, we employ freestanding porous carbon fibers (PCNF) as an efficacious and stable support for the uniformly distributed SnO2 nanoparticles (SnO2PCNF), thereby capitalizing on the synergistic support effect that arises from their strong interaction. On one hand, the interaction between the SnO2 nanoparticles and the carbon support optimizes the electronic configuration of the active centers. This interaction leads to a noteworthy shift of the d-band center toward stronger intermediate adsorption energy, consequently lowering the energy barrier associated with CO2 reduction. As a result, the SnO2PCNF realizes a remarkable CO2RR performance with excellent selectivity towards formate (98.1%). On the other hand, the porous carbon fibers enable the uniform and stable dispersion of SnO2 nanoparticles, and this superior porous structure of carbon supports can also facilitate the exposure of the SnO2 nanoparticles on the reaction interface to a great extent. Consequently, adequate contact between active sites, reactants, and electrolytes can significantly increase the metal utilization, eventually bringing forth a remarkable 7.09 A/mg mass activity. This work might provide a useful idea for improving the utilization rate of metals in numerous electrocatalytic reactions.
Diluent modified weakly solvating electrolyte for fast-charging high-voltage lithium metal batteries
2025, 36(1): 109556
doi: 10.1016/j.cclet.2024.109556
Abstract:
Weakly solvating electrolyte (WSE) demonstrates superior compatibility with lithium (Li) metal batteries (LMBs). However, its application in fast-charging high-voltage LMBs is challenging. Here, we propose a diluent modified WSE for fast-charging high-voltage LMBs, which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) into the tetrahydropyran (THP) based WSE. A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP, which accelerates the de-solvation kinetics of Li+. Besides, more anions are involved in solvation structure in the presence of TTE, yielding inorganic-rich interphases with improved stability. Li (30 µm)LiNi0.5 Co0.2Mn0.3O2 (4.1 mAh/cm2) batteries with the TTE modified WSE retain over 64% capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V, much better than that with pure THP based WSE. This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
Weakly solvating electrolyte (WSE) demonstrates superior compatibility with lithium (Li) metal batteries (LMBs). However, its application in fast-charging high-voltage LMBs is challenging. Here, we propose a diluent modified WSE for fast-charging high-voltage LMBs, which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE) into the tetrahydropyran (THP) based WSE. A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP, which accelerates the de-solvation kinetics of Li+. Besides, more anions are involved in solvation structure in the presence of TTE, yielding inorganic-rich interphases with improved stability. Li (30 µm)LiNi0.5 Co0.2Mn0.3O2 (4.1 mAh/cm2) batteries with the TTE modified WSE retain over 64% capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V, much better than that with pure THP based WSE. This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
2025, 36(1): 109559
doi: 10.1016/j.cclet.2024.109559
Abstract:
Customized design of well-defined cathode structures with abundant adsorption sites and rapid diffusion dynamics, holds great promise in filling capacity gap of carbonaceous cathodes towards high-performance Zn-ion hybrid supercapacitors (ZHC). Herein, we fabricate a series of dynamics-oriented hierarchical porous carbons derived from the unique organic-inorganic interpenetrating polymer networks. The interpenetrating polymer networks are obtained through physically knitting polyferric chloride (PFC) network into the highly crosslinked resorcinol-formaldehyde (RF) network. Instead of covalent bonding, physical interpenetrating force in such RF-PFC networks efficiently relieves the RF skeleton shrinkage upon pyrolysis. Meanwhile, the in-situ PFC network sacrifices as a structure-directing agent to suppress the macrophase separation, and correspondingly 3D hierarchical porous structure with plentiful ion-diffusion channels (pore volume of 1.35 cm3/g) is generated in the representative HPC4 via nanospace occupation and swelling effect. Further removal of Fe fillers leaves behind a large accessible specific surface area of 1550 m2/g for enhanced Zn-ion adsorption. When used as the cathode for ZHC, HPC4 demonstrates a remarkable electrochemical performance with a specific capacity of 215.1 mAh/g at 0.5 A/g and a high Zn2+ ion diffusion coefficient of 11.1 × 10−18 cm2/s. The ZHC device yields 117.0 Wh/kg energy output at a power density of 272.1 W/kg, coupled with good cycle lifespan (100,000 cycles@10 A/g). This work inspires innovative insights to accelerate Zn diffusion dynamics by structure elaboration towards high-capacity cathode materials.
Customized design of well-defined cathode structures with abundant adsorption sites and rapid diffusion dynamics, holds great promise in filling capacity gap of carbonaceous cathodes towards high-performance Zn-ion hybrid supercapacitors (ZHC). Herein, we fabricate a series of dynamics-oriented hierarchical porous carbons derived from the unique organic-inorganic interpenetrating polymer networks. The interpenetrating polymer networks are obtained through physically knitting polyferric chloride (PFC) network into the highly crosslinked resorcinol-formaldehyde (RF) network. Instead of covalent bonding, physical interpenetrating force in such RF-PFC networks efficiently relieves the RF skeleton shrinkage upon pyrolysis. Meanwhile, the in-situ PFC network sacrifices as a structure-directing agent to suppress the macrophase separation, and correspondingly 3D hierarchical porous structure with plentiful ion-diffusion channels (pore volume of 1.35 cm3/g) is generated in the representative HPC4 via nanospace occupation and swelling effect. Further removal of Fe fillers leaves behind a large accessible specific surface area of 1550 m2/g for enhanced Zn-ion adsorption. When used as the cathode for ZHC, HPC4 demonstrates a remarkable electrochemical performance with a specific capacity of 215.1 mAh/g at 0.5 A/g and a high Zn2+ ion diffusion coefficient of 11.1 × 10−18 cm2/s. The ZHC device yields 117.0 Wh/kg energy output at a power density of 272.1 W/kg, coupled with good cycle lifespan (100,000 cycles@10 A/g). This work inspires innovative insights to accelerate Zn diffusion dynamics by structure elaboration towards high-capacity cathode materials.
2025, 36(1): 109566
doi: 10.1016/j.cclet.2024.109566
Abstract:
Hydrogen, as a cheap, clean, and cost-effective secondary energy source, performs an essential role in optimizing today’s energy structure. Magnesium hydride (MgH2) represents an attractive hydrogen carrier for storage and transportation, however, the kinetic behavior and operating temperature remain undesirable. In this work, a dual-phase multi-site alloy (MsA) anchored on carbon substrates was designed, and its superior catalytic effects on the hydrogen storage properties of MgH2 were reported. Mechanism analysis identified that multi-site FeNi3/NiCu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH2−MsA systems. Concretely, the unique multi-metallic site structure attached to the surface of MgH2 provided substantial reversible channels and accessible active sites conducive to the adsorption, activation, and nucleation of H atoms. In addition, the coupling system formed by FeNi3 and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH2 and H atoms. Hence, the onset dehydrogenation temperature of MgH2 + 5 wt% MsA was reduced to 195 ℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 kJ/mol. 5.08 wt% H2 could be released at 250 ℃ in 20 min, reaching a high dehydrogenation rate of 0.254 wt% H2/min, yet that for MgH2 at a higher temperature of 335 ℃ was only 0.145 wt% H2/min. Then, the dehydrogenated MgH2−MsA sample could absorb hydrogen from room temperature (30 ℃) and charge 3.93 wt% H2 at 100 ℃ within 20 min under 3.0 MPa H2 pressure. Benefiting from carbon substrates, the 5 wt% MsA doped-MgH2 could still maintain 6.36 wt% hydrogen capacity after 20 cycles. In conclusion, this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.
Hydrogen, as a cheap, clean, and cost-effective secondary energy source, performs an essential role in optimizing today’s energy structure. Magnesium hydride (MgH2) represents an attractive hydrogen carrier for storage and transportation, however, the kinetic behavior and operating temperature remain undesirable. In this work, a dual-phase multi-site alloy (MsA) anchored on carbon substrates was designed, and its superior catalytic effects on the hydrogen storage properties of MgH2 were reported. Mechanism analysis identified that multi-site FeNi3/NiCu nanoalloys synergistically served as intrinsic drivers for the striking de/hydrogenation performance of the MgH2−MsA systems. Concretely, the unique multi-metallic site structure attached to the surface of MgH2 provided substantial reversible channels and accessible active sites conducive to the adsorption, activation, and nucleation of H atoms. In addition, the coupling system formed by FeNi3 and NiCu dual-phase alloys further enhanced the reactivity between Mg/MgH2 and H atoms. Hence, the onset dehydrogenation temperature of MgH2 + 5 wt% MsA was reduced to 195 ℃ and the hydrogen desorption apparent activation energy was reduced to 83.6 kJ/mol. 5.08 wt% H2 could be released at 250 ℃ in 20 min, reaching a high dehydrogenation rate of 0.254 wt% H2/min, yet that for MgH2 at a higher temperature of 335 ℃ was only 0.145 wt% H2/min. Then, the dehydrogenated MgH2−MsA sample could absorb hydrogen from room temperature (30 ℃) and charge 3.93 wt% H2 at 100 ℃ within 20 min under 3.0 MPa H2 pressure. Benefiting from carbon substrates, the 5 wt% MsA doped-MgH2 could still maintain 6.36 wt% hydrogen capacity after 20 cycles. In conclusion, this work provides experimental rationale and new insights for the design of efficient catalysts for magnesium-based solid-state hydrogen storage materials.
2025, 36(1): 109568
doi: 10.1016/j.cclet.2024.109568
Abstract:
All-solid-state Li batteries (ASSLBs) using solid electrolytes (SEs) have gained significant attention in recent years considering the safety issue and their high energy density. Despite these advantages, the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites. Elemental doping is an effective and direct method to enhance the performance of SEs. Here, we report an Al-F co-doping strategy to improve the overall properties including ion conductivity, high voltage stability, and cathode and anode compatibility. Particularly, the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases, thereby constructing a relatively stable interface and promoting uniform Li deposition. The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series. ASSLBs assembled with these optimized electrolytes gain good electrochemical performance, demonstrating the universality of Al-F co-doping towards advanced SEs.
All-solid-state Li batteries (ASSLBs) using solid electrolytes (SEs) have gained significant attention in recent years considering the safety issue and their high energy density. Despite these advantages, the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites. Elemental doping is an effective and direct method to enhance the performance of SEs. Here, we report an Al-F co-doping strategy to improve the overall properties including ion conductivity, high voltage stability, and cathode and anode compatibility. Particularly, the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases, thereby constructing a relatively stable interface and promoting uniform Li deposition. The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series. ASSLBs assembled with these optimized electrolytes gain good electrochemical performance, demonstrating the universality of Al-F co-doping towards advanced SEs.
2025, 36(1): 109569
doi: 10.1016/j.cclet.2024.109569
Abstract:
The oxygen reduction reaction (ORR) is a crucial process in Zn-air systems, and the catalyst plays a significant role in this reaction. However, reported catalysts often suffer from poor durability and stability during the ORR process. Herein, we synthesized La-Fe bimetallic nanoparticles encapsulated in a N-doped porous carbon dodecahedron (La-Fe/NC) originated from ZIF-8 by a simple direct carbonization. The La-Fe/NC catalyst had a numerous mesopores and dendritic outer layer generated by carbon nanotubes (CNTs), forming a high conductivity network that helped to optimize electron transfer and mass transport in the ORR process. The effect of different doping transition metals and metal ratios on the ORR activity of Zn-air batteries was investigated. In alkaline media, the La-Fe/NC showed the highest ORR catalytic activity, with a half-wave potential (E1/2) of 0.879 V (vs. RHE, Pt/C 0.845 V). After 5000 cycles, the E1/2 of the La-Fe/NC catalyst only decreased by 7 mV, and its performance in stability tests and methanol tolerance tests was superior to Pt/C. When used as the air electrode in a Zn-air battery, the La-Fe/NC catalyst demonstrated an excellent specific capacity of 755 mAh/g and a peak power density of 179.8 mW/cm2. The results provide important insights for the development of high-performance Zn-air batteries and new directions for the design of ORR catalysts.
The oxygen reduction reaction (ORR) is a crucial process in Zn-air systems, and the catalyst plays a significant role in this reaction. However, reported catalysts often suffer from poor durability and stability during the ORR process. Herein, we synthesized La-Fe bimetallic nanoparticles encapsulated in a N-doped porous carbon dodecahedron (La-Fe/NC) originated from ZIF-8 by a simple direct carbonization. The La-Fe/NC catalyst had a numerous mesopores and dendritic outer layer generated by carbon nanotubes (CNTs), forming a high conductivity network that helped to optimize electron transfer and mass transport in the ORR process. The effect of different doping transition metals and metal ratios on the ORR activity of Zn-air batteries was investigated. In alkaline media, the La-Fe/NC showed the highest ORR catalytic activity, with a half-wave potential (E1/2) of 0.879 V (vs. RHE, Pt/C 0.845 V). After 5000 cycles, the E1/2 of the La-Fe/NC catalyst only decreased by 7 mV, and its performance in stability tests and methanol tolerance tests was superior to Pt/C. When used as the air electrode in a Zn-air battery, the La-Fe/NC catalyst demonstrated an excellent specific capacity of 755 mAh/g and a peak power density of 179.8 mW/cm2. The results provide important insights for the development of high-performance Zn-air batteries and new directions for the design of ORR catalysts.
2025, 36(1): 109588
doi: 10.1016/j.cclet.2024.109588
Abstract:
Designing highly active electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution and reduction reactions (OER and ORR) is pivotal to renewable energy technology. Herein, based on density functional theory (DFT) calculations, we systematically investigate the catalytic activity of iron-nitrogen-carbon based covalent organic frameworks (COF) monolayers with axially coordinated ligands (denotes as FeN4-X@COF, X refers to axial ligand, X = -SCN, -I, -H, -SH, -NO2, -Br, -ClO, -Cl, -HCO3, -NO, -ClO2, -OH, -CN and -F). The calculated results demonstrate that all the catalysts possess good thermodynamic and electrochemical stabilities. The different ligands axially ligated to the Fe active center could induce changes in the charge of the Fe center, which further regulates the interaction strength between intermediates and catalysts that governs the catalytic activity. Importantly, FeN4-SH@COF and FeN4OH@COF are efficient bifunctional catalysts for HER and OER, FeN4OH@COF and FeN4-I@COF are promising bifunctional catalysts for OER and ORR. These findings not only reveal promising bifunctional HER/OER and OER/ORR catalysts but also provide theoretical guidance for designing optimum iron-nitrogen-carbon based catalysts.
Designing highly active electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution and reduction reactions (OER and ORR) is pivotal to renewable energy technology. Herein, based on density functional theory (DFT) calculations, we systematically investigate the catalytic activity of iron-nitrogen-carbon based covalent organic frameworks (COF) monolayers with axially coordinated ligands (denotes as FeN4-X@COF, X refers to axial ligand, X = -SCN, -I, -H, -SH, -NO2, -Br, -ClO, -Cl, -HCO3, -NO, -ClO2, -OH, -CN and -F). The calculated results demonstrate that all the catalysts possess good thermodynamic and electrochemical stabilities. The different ligands axially ligated to the Fe active center could induce changes in the charge of the Fe center, which further regulates the interaction strength between intermediates and catalysts that governs the catalytic activity. Importantly, FeN4-SH@COF and FeN4OH@COF are efficient bifunctional catalysts for HER and OER, FeN4OH@COF and FeN4-I@COF are promising bifunctional catalysts for OER and ORR. These findings not only reveal promising bifunctional HER/OER and OER/ORR catalysts but also provide theoretical guidance for designing optimum iron-nitrogen-carbon based catalysts.
2025, 36(1): 109590
doi: 10.1016/j.cclet.2024.109590
Abstract:
The metal ion batteries have gained widespread attention for wearable electronics due to their competitive energy density and long cycling life. Exploring the advanced anode materials is significant for next generation energy storage systems. However, severe electrode volume changes and sluggish redox kinetics are the critical problems for lithium/potassium ion batteries (LIBs/PIBs) towards large-scale applications. Herein, we prepare a novel anode material, which consists of reduced graphene oxide wrapping one-dimensional (1D) N-doped porous carbon nanotube with cobalt phosphoselenide (CoPSe) nanoparticles embedded inside them (rGO@CoPSe/NC). Benefited from the dual carbon decorations and ultrafine nanoparticles structure, it achieves a reversible capacity of 245 mAh/g at 5 A/g after 2000 cycles for LIBs and 215 mAh/g at 1 A/g after 500 cycles for PIBs. The pseudocapacitance and GITT measurements are used to investigate the electrochemical kinetics of rGO@CoPSe/NC for LIBs. In addition, the lithium ion full cell also shows good electrochemical performance when paired with high capacity LiNi0.8Co0.1Mn0.1O2 cathode. This work provides a feasible electrode design strategy for high-efficiency metal ion batteries based on multidimensional nanoarchitecture engineering and composition tailoring.
The metal ion batteries have gained widespread attention for wearable electronics due to their competitive energy density and long cycling life. Exploring the advanced anode materials is significant for next generation energy storage systems. However, severe electrode volume changes and sluggish redox kinetics are the critical problems for lithium/potassium ion batteries (LIBs/PIBs) towards large-scale applications. Herein, we prepare a novel anode material, which consists of reduced graphene oxide wrapping one-dimensional (1D) N-doped porous carbon nanotube with cobalt phosphoselenide (CoPSe) nanoparticles embedded inside them (rGO@CoPSe/NC). Benefited from the dual carbon decorations and ultrafine nanoparticles structure, it achieves a reversible capacity of 245 mAh/g at 5 A/g after 2000 cycles for LIBs and 215 mAh/g at 1 A/g after 500 cycles for PIBs. The pseudocapacitance and GITT measurements are used to investigate the electrochemical kinetics of rGO@CoPSe/NC for LIBs. In addition, the lithium ion full cell also shows good electrochemical performance when paired with high capacity LiNi0.8Co0.1Mn0.1O2 cathode. This work provides a feasible electrode design strategy for high-efficiency metal ion batteries based on multidimensional nanoarchitecture engineering and composition tailoring.
2025, 36(1): 109596
doi: 10.1016/j.cclet.2024.109596
Abstract:
Pure near-infrared (NIR) phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine. We have designed and synthesized two new B-embedded pure near-infrared (NIR)-emitting iridium complexes (Ir(Bpiq)2acac and Ir(Bpiq)2dpm) with peaks greater than 720 nm. More importantly, they exhibit very narrow phosphorescent emission with full width at half maximum (FWHM) of only about 50 nm (0.12 eV), resulting in a high NIR content (> 90%) in their spectrum. In view of better optical property and solubility, the complex Ir(Bpiq)2dpm was used as the emitting layer of a solution-processed OLED device, and achieved good maximum external quantum efficiency (EQE) (2.8%) peaking at 728 nm. This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.
Pure near-infrared (NIR) phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine. We have designed and synthesized two new B-embedded pure near-infrared (NIR)-emitting iridium complexes (Ir(Bpiq)2acac and Ir(Bpiq)2dpm) with peaks greater than 720 nm. More importantly, they exhibit very narrow phosphorescent emission with full width at half maximum (FWHM) of only about 50 nm (0.12 eV), resulting in a high NIR content (> 90%) in their spectrum. In view of better optical property and solubility, the complex Ir(Bpiq)2dpm was used as the emitting layer of a solution-processed OLED device, and achieved good maximum external quantum efficiency (EQE) (2.8%) peaking at 728 nm. This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.
2025, 36(1): 109597
doi: 10.1016/j.cclet.2024.109597
Abstract:
Exploring transition metal sulfide electrocatalysts with high-efficiency for hydrogen evolution reaction (HER) is essential to produce H2 fuel through water splitting. Herein, novel nickel tungsten sulfide heterojunction (NiS-WS2) with a nanowoven ball-like structure were directed synthetized by a facile hydrothermal method. The hierarchical NiS-WS2 exhibited excellent HER activity with a relatively small overpotential of 142 and 137 mV at 10 mA/cm2 in 0.5 mol/L H2SO4 and 1 mol/L KOH, which is much better than that of single NiS and WS2. The impressive performance of NiS-WS2 heterojunction is owed to the collective synergy of special morphological and more exposed active sites between the crystal interfacial of NiS and WS2. In addition, the hierarchical NiS-WS2 can facilitate the transport of charge/mass by optimized electronic structure, which further improves the HER activity of electrocatalysts. These outcomes provide a simple method to prospect towards the design and application of heterostructures as efficient electrocatalysts, shedding some light on the development of functional materials in energy chemistry.
Exploring transition metal sulfide electrocatalysts with high-efficiency for hydrogen evolution reaction (HER) is essential to produce H2 fuel through water splitting. Herein, novel nickel tungsten sulfide heterojunction (NiS-WS2) with a nanowoven ball-like structure were directed synthetized by a facile hydrothermal method. The hierarchical NiS-WS2 exhibited excellent HER activity with a relatively small overpotential of 142 and 137 mV at 10 mA/cm2 in 0.5 mol/L H2SO4 and 1 mol/L KOH, which is much better than that of single NiS and WS2. The impressive performance of NiS-WS2 heterojunction is owed to the collective synergy of special morphological and more exposed active sites between the crystal interfacial of NiS and WS2. In addition, the hierarchical NiS-WS2 can facilitate the transport of charge/mass by optimized electronic structure, which further improves the HER activity of electrocatalysts. These outcomes provide a simple method to prospect towards the design and application of heterostructures as efficient electrocatalysts, shedding some light on the development of functional materials in energy chemistry.
2025, 36(1): 109650
doi: 10.1016/j.cclet.2024.109650
Abstract:
Phosphorus-based anode is a promising anode for sodium-ion batteries (SIBs) due to its high specific capacity, however, suffers from poor electronic conductivity and unfavorable electrochemical reversibility. Incorporating metals such as copper (Cu) into phosphorus has been demonstrated to not only improve the electronic conductivity but also accommodate the volume change during cycling, yet the underline sodiation mechanism is not clear. Herein, take a copper phosphide and reduced graphene oxide (CuP2/C) composite as an example, which delivers a high reversible capacity of > 900 mAh/g. Interestingly, it is revealed that the native oxidation PO components of the CuP2/C composite show higher electrochemical reversibility than the bulk CuP2, based on a quantitative analysis of high-resolution solid-state 31P NMR, ex-situ XPS and synchrotron X-ray diffraction characterization techniques. The sodiation products Na3PO4 and Na4P2O7 derived from PO could react with Na-P alloys and regenerate to PO during charge process, which probably accounts for the high reversible capacity of the CuP2/C anode. The findings also illustrate that the phosphorus transforms into nanocrystalline Na3P and NaP alloys, which laterally shows crystallization-amorphization evolution process during cycling.
Phosphorus-based anode is a promising anode for sodium-ion batteries (SIBs) due to its high specific capacity, however, suffers from poor electronic conductivity and unfavorable electrochemical reversibility. Incorporating metals such as copper (Cu) into phosphorus has been demonstrated to not only improve the electronic conductivity but also accommodate the volume change during cycling, yet the underline sodiation mechanism is not clear. Herein, take a copper phosphide and reduced graphene oxide (CuP2/C) composite as an example, which delivers a high reversible capacity of > 900 mAh/g. Interestingly, it is revealed that the native oxidation PO components of the CuP2/C composite show higher electrochemical reversibility than the bulk CuP2, based on a quantitative analysis of high-resolution solid-state 31P NMR, ex-situ XPS and synchrotron X-ray diffraction characterization techniques. The sodiation products Na3PO4 and Na4P2O7 derived from PO could react with Na-P alloys and regenerate to PO during charge process, which probably accounts for the high reversible capacity of the CuP2/C anode. The findings also illustrate that the phosphorus transforms into nanocrystalline Na3P and NaP alloys, which laterally shows crystallization-amorphization evolution process during cycling.
2025, 36(1): 109669
doi: 10.1016/j.cclet.2024.109669
Abstract:
High-efficient rubber antioxidants for enhanced heat resistance without compromising mechanical properties remain an enormous and long-term challenge for the rubber industry. Herein, we employed the in-situ growth of Ce-doped Co-metal-organic framework (CeCo-MOF) in dendritic mesoporous organosilica nanoparticles (DMONs@CeCo-MOF, denoted as DCCM) to prepare a novel antioxidant that exhibit outstanding thermal stability. Dendritic mesoporous organosilica nanoparticles (DMONs) effectively alleviated the incompatibility of CeCo-MOF in the polymer matrix, and the effective scavenging of free radicals was attributed to the various oxidation states of metal ions in CeCo-MOF. Surprising, by adding only 0.5 phr (parts per hundred of rubber) of DMONs@CeCo-MOF to silicone rubber, (SR), the retention rate of tensile strength increased from 37.3% to 61.6% after aging 72 h at 250 ℃, and the retention rate of elongation at break of DCCM/SR1 composites reached 68%, which was 5.43 times of SR. The strategy of anchoring MOFs on the surface of silica also provides a viable method for preparing effective compound functionalized rubber antioxidant.
High-efficient rubber antioxidants for enhanced heat resistance without compromising mechanical properties remain an enormous and long-term challenge for the rubber industry. Herein, we employed the in-situ growth of Ce-doped Co-metal-organic framework (CeCo-MOF) in dendritic mesoporous organosilica nanoparticles (DMONs@CeCo-MOF, denoted as DCCM) to prepare a novel antioxidant that exhibit outstanding thermal stability. Dendritic mesoporous organosilica nanoparticles (DMONs) effectively alleviated the incompatibility of CeCo-MOF in the polymer matrix, and the effective scavenging of free radicals was attributed to the various oxidation states of metal ions in CeCo-MOF. Surprising, by adding only 0.5 phr (parts per hundred of rubber) of DMONs@CeCo-MOF to silicone rubber, (SR), the retention rate of tensile strength increased from 37.3% to 61.6% after aging 72 h at 250 ℃, and the retention rate of elongation at break of DCCM/SR1 composites reached 68%, which was 5.43 times of SR. The strategy of anchoring MOFs on the surface of silica also provides a viable method for preparing effective compound functionalized rubber antioxidant.
2025, 36(1): 109731
doi: 10.1016/j.cclet.2024.109731
Abstract:
Selective separation of amino acids and proteins is crucial in various areas of research, including proteomics, protein structure and function studies, protein purification and drug development, and biosensing and biodetection. A nanocomposite film is formed by combining layer-by-layer self-assembled gold nanospheres (AuNPs) driven by cucurbit[7]uril (CB[7]) and polymethyl methacrylate (PMMA) film. Due to the host-guest interactions, the selective transmission of L-tryptophan in the nanocomposite film is confirmed by the current-voltage measurements using a picoammeter. Furthermore, by adjusting the particle size of AuNPs to increase channel size, lysozyme containing multiple tryptophan residues can selectively pass through the nanocomposite film, indicating the high versatility and adaptability of the nanocomposite film. This study will provide a new direction for the selective separation of amino acids and proteins.
Selective separation of amino acids and proteins is crucial in various areas of research, including proteomics, protein structure and function studies, protein purification and drug development, and biosensing and biodetection. A nanocomposite film is formed by combining layer-by-layer self-assembled gold nanospheres (AuNPs) driven by cucurbit[7]uril (CB[7]) and polymethyl methacrylate (PMMA) film. Due to the host-guest interactions, the selective transmission of L-tryptophan in the nanocomposite film is confirmed by the current-voltage measurements using a picoammeter. Furthermore, by adjusting the particle size of AuNPs to increase channel size, lysozyme containing multiple tryptophan residues can selectively pass through the nanocomposite film, indicating the high versatility and adaptability of the nanocomposite film. This study will provide a new direction for the selective separation of amino acids and proteins.
2025, 36(1): 109733
doi: 10.1016/j.cclet.2024.109733
Abstract:
The self-assembled nanoparticles (SAN) formed during the decoction process of traditional Chinese medicine (TCM) exhibit non-uniform particle sizes and a tendency for aggregation. Our group found that the pH-driven method can improve the self-assembly phenomenon of Herpetospermum caudigerum Wall., and the SAN exhibited uniform particle size and demonstrated good stability. In this paper, we analyzed the interactions between the main active compound, herpetrione (Her), and its main carrier, Herpetospermum caudigerum Wall. polysaccharide (HCWP), along with their self-assembly mechanisms under different pH values. The binding constants of Her and HCWP increase with rising pH, leading to the formation of Her-HCWP SAN with a smaller particle size, higher zeta potential, and improved thermal stability. While the contributions of hydrogen bonding and electrostatic attraction to the formation of Her-HCWP SAN increase with rising pH, the hydrophobic force consistently plays a dominant role. This study enhances our scientific understanding of the self-assembly phenomenon of TCM improved by pH driven method.
The self-assembled nanoparticles (SAN) formed during the decoction process of traditional Chinese medicine (TCM) exhibit non-uniform particle sizes and a tendency for aggregation. Our group found that the pH-driven method can improve the self-assembly phenomenon of Herpetospermum caudigerum Wall., and the SAN exhibited uniform particle size and demonstrated good stability. In this paper, we analyzed the interactions between the main active compound, herpetrione (Her), and its main carrier, Herpetospermum caudigerum Wall. polysaccharide (HCWP), along with their self-assembly mechanisms under different pH values. The binding constants of Her and HCWP increase with rising pH, leading to the formation of Her-HCWP SAN with a smaller particle size, higher zeta potential, and improved thermal stability. While the contributions of hydrogen bonding and electrostatic attraction to the formation of Her-HCWP SAN increase with rising pH, the hydrophobic force consistently plays a dominant role. This study enhances our scientific understanding of the self-assembly phenomenon of TCM improved by pH driven method.
2025, 36(1): 109744
doi: 10.1016/j.cclet.2024.109744
Abstract:
A supramolecular assembly composed of perylene diimide derivative (PDI-nm) and nor-seco-cucurbit[10]uril (ns-Q[10]) was designed. The excellent host-guest interaction between PDI-nm and ns-Q[10] prevented the aggregation-caused quenching (ACQ) effect of PDI-nm, resulting in a luminescent assembly. The addition of spermine to the PDI-nm/ns-Q[10] assembly restored the ACQ of PDI-nm due to the competitive binding of spermine to ns-Q[10], which released PDI-nm. The assembly based on this principle showed ultra-high sensitivity for the detection of spermine with a detection limit as low as 7.84 × 10−7 mol/L in aqueous solution and 3.69 × 10−7 mol/L in plasma solution. Moreover, an artificial light-harvesting system based on this assembly was proposed, benefiting from its good luminescent performance. Nile red (NiR) functioned as an acceptor loaded into assembly, and a highly efficient energy transfer process occurred from PDI-nm/ns-Q[10] to NiR, with an efficiency up to 87%.
A supramolecular assembly composed of perylene diimide derivative (PDI-nm) and nor-seco-cucurbit[10]uril (ns-Q[10]) was designed. The excellent host-guest interaction between PDI-nm and ns-Q[10] prevented the aggregation-caused quenching (ACQ) effect of PDI-nm, resulting in a luminescent assembly. The addition of spermine to the PDI-nm/ns-Q[10] assembly restored the ACQ of PDI-nm due to the competitive binding of spermine to ns-Q[10], which released PDI-nm. The assembly based on this principle showed ultra-high sensitivity for the detection of spermine with a detection limit as low as 7.84 × 10−7 mol/L in aqueous solution and 3.69 × 10−7 mol/L in plasma solution. Moreover, an artificial light-harvesting system based on this assembly was proposed, benefiting from its good luminescent performance. Nile red (NiR) functioned as an acceptor loaded into assembly, and a highly efficient energy transfer process occurred from PDI-nm/ns-Q[10] to NiR, with an efficiency up to 87%.
2025, 36(1): 109747
doi: 10.1016/j.cclet.2024.109747
Abstract:
Triflumezopyrim (TFM) is a novel mesoionic pyrido[1,2-α]pyrimidinones insecticide, which acts on nicotinic acetylcholine receptors (nAChRs) and has no cross-resistance with other insecticides. Herein, we firstly developed a new continuous flow approach to synthesis 2-[3-(trifluoromethyl)phenyl]malonic acid, a key intermate of TFM, coupling with esterification, condensation, and hydrolysis. All three-step reactions were optimized and transformed into a continuous synthesis mode by three micro reaction units. Compared with the batch mode, the total reaction time and overall separation yield were improved from more than 12 h and 60% to 18 min and 73.38%, respectively. The solvent consumption and waste emission were significantly reduced, which also provides an eco-friendly and efficient potential tool for the development and production of mesoionic pyrido[1,2-α]pyrimidinones insecticide.
Triflumezopyrim (TFM) is a novel mesoionic pyrido[1,2-α]pyrimidinones insecticide, which acts on nicotinic acetylcholine receptors (nAChRs) and has no cross-resistance with other insecticides. Herein, we firstly developed a new continuous flow approach to synthesis 2-[3-(trifluoromethyl)phenyl]malonic acid, a key intermate of TFM, coupling with esterification, condensation, and hydrolysis. All three-step reactions were optimized and transformed into a continuous synthesis mode by three micro reaction units. Compared with the batch mode, the total reaction time and overall separation yield were improved from more than 12 h and 60% to 18 min and 73.38%, respectively. The solvent consumption and waste emission were significantly reduced, which also provides an eco-friendly and efficient potential tool for the development and production of mesoionic pyrido[1,2-α]pyrimidinones insecticide.
2025, 36(1): 109748
doi: 10.1016/j.cclet.2024.109748
Abstract:
Ag2CO3-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source. The reaction involves β-fragmentation of primary alkoxy radicals, followed by the fluorination of the resulting C-centered radical intermediates. The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope, thus opening up a new entrance to the synthesis of fluorinated constructs including α-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives. The divergent functionalization of the obtained α-fluoroimides enables an efficient access to amine derivatives through C–F bond activation under the action of BF3·OEt2.
Ag2CO3-promoted dehydroxymethylative fluorination of aliphatic alcohols has been achieved with Selectfluor as both oxidant and fluorine source. The reaction involves β-fragmentation of primary alkoxy radicals, followed by the fluorination of the resulting C-centered radical intermediates. The transformation proceeds under mild reaction conditions and exhibits a broad substrate scope, thus opening up a new entrance to the synthesis of fluorinated constructs including α-fluoroimides and 1-fluoroalkyl benzoates as well as secondary and tertiary alkyl fluorides like versatile 2-fluoro-2-alkyl 1,3-propandiol derivatives. The divergent functionalization of the obtained α-fluoroimides enables an efficient access to amine derivatives through C–F bond activation under the action of BF3·OEt2.
2025, 36(1): 109752
doi: 10.1016/j.cclet.2024.109752
Abstract:
Osteoarthritis (OA) is the most prevalent joint disease and icariin is a promising drug for its treatment. However, the clinical use of icariin is hindered by poor water solubility, low bioavailability, and non-specific release and biological distribution. Herein, sulfonated azocalix[4]arene (SAC4A) with enhanced water solubility, recognition capacity, and designed responsiveness was used to improve the efficiency of icariin for OA therapy. SAC4A, a macrocycle with well-defined molecular weight and structure, could encapsulate and enhance water solubility of various drugs. In addition, SAC4A enables hypoxia-responsive release of loaded drug. Compared with icariin treatment, supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats, including more regular bone morphology and structure, and lower degree of cartilage damage. Moreover, the supramolecular formulation demonstrated various advantages, including easy preparation, hypoxia-triggered release, and small size that conducive to drug penetration.
Osteoarthritis (OA) is the most prevalent joint disease and icariin is a promising drug for its treatment. However, the clinical use of icariin is hindered by poor water solubility, low bioavailability, and non-specific release and biological distribution. Herein, sulfonated azocalix[4]arene (SAC4A) with enhanced water solubility, recognition capacity, and designed responsiveness was used to improve the efficiency of icariin for OA therapy. SAC4A, a macrocycle with well-defined molecular weight and structure, could encapsulate and enhance water solubility of various drugs. In addition, SAC4A enables hypoxia-responsive release of loaded drug. Compared with icariin treatment, supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats, including more regular bone morphology and structure, and lower degree of cartilage damage. Moreover, the supramolecular formulation demonstrated various advantages, including easy preparation, hypoxia-triggered release, and small size that conducive to drug penetration.
2025, 36(1): 109755
doi: 10.1016/j.cclet.2024.109755
Abstract:
A transition-metal- and oxidant-free amination/cyclization reaction to access 1,2,4-triazolo[1,5-a]pyridines was realized in water by using amino diphenylphosphinate as amino source. A broad array of readily accessible N-(pyridyl)amides could be converted into the products featuring a diverse set of functional groups. The sustainable methodology was successfully applied to the late-stage functionalization of natural products and drugs.
A transition-metal- and oxidant-free amination/cyclization reaction to access 1,2,4-triazolo[1,5-a]pyridines was realized in water by using amino diphenylphosphinate as amino source. A broad array of readily accessible N-(pyridyl)amides could be converted into the products featuring a diverse set of functional groups. The sustainable methodology was successfully applied to the late-stage functionalization of natural products and drugs.
2025, 36(1): 109760
doi: 10.1016/j.cclet.2024.109760
Abstract:
Controlled synthesis of two-dimensional covalent organic frameworks (2D COFs), including stoichiometric and sub-stoichiometric variations, is a topic of growing interest due to its potential in gas separation applications. In this study, we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of [4 + 4] type COFs. These included a stoichiometric [4 + 4] type COF and two sub-stoichiometric [4 + 2] type COFs, featuring unreacted amino or formyl groups. The resulting COFs exhibit different gas adsorption and separation properties. Specifically, sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C2H2, C2H4, and CO2 to stoichiometric COF-DAPy. In contrast, sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C2H2/C2H4 and C2H2/CO2 separation, with the C2H2/C2H4 selectivity being the highest among reported COFs, attributed to increased pore polarity resulting from the presence of formyl groups. This study not only offers an additional example of sub-stoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials, particularly in the field of gas adsorption and separation.
Controlled synthesis of two-dimensional covalent organic frameworks (2D COFs), including stoichiometric and sub-stoichiometric variations, is a topic of growing interest due to its potential in gas separation applications. In this study, we successfully synthesized three distinct 2D COFs by carefully adjusting solvent compositions and monomer ratios during the synthesis of [4 + 4] type COFs. These included a stoichiometric [4 + 4] type COF and two sub-stoichiometric [4 + 2] type COFs, featuring unreacted amino or formyl groups. The resulting COFs exhibit different gas adsorption and separation properties. Specifically, sub-stoichiometric COF-DA with residual amino groups shows comparable adsorption capacity for C2H2, C2H4, and CO2 to stoichiometric COF-DAPy. In contrast, sub-stoichiometric COF-Py with residual formyl groups displays enhanced adsorption selectivity for C2H2/C2H4 and C2H2/CO2 separation, with the C2H2/C2H4 selectivity being the highest among reported COFs, attributed to increased pore polarity resulting from the presence of formyl groups. This study not only offers an additional example of sub-stoichiometric COF synthesis but also advocates for further exploration of sub-stoichiometric COF materials, particularly in the field of gas adsorption and separation.
2025, 36(1): 109763
doi: 10.1016/j.cclet.2024.109763
Abstract:
Immunotherapy offers significant potential but is often hampered by the immunosuppressive environment in oral squamous cell carcinoma (OSCC). To address this, we propose an enhanced immunotherapeutic strategy that revitalizes the tumor immune microenvironment (TIME) in OSCC by integrating upconversion-based photodynamic therapy (PDT) with chemotherapy. Using a red blood cell membrane-inspired biomimetic nanoplatform, our approach concurrently delivers chlorin e6@upconversion nanoparticles (Ce6@UCNP) and doxorubicin (DOX). By leveraging fluorescence resonance energy transfer (FRET) for 980 nm to 660 nm upconversion excitation, we address challenges such as limited tissue penetration and tissue damage, as well as nanoplatform issues including immunogenicity and targeting inaccuracy Our integrated approach enhances PDT and chemotherapy with the goal of transforming immunologically "cold" tumors into "hot" ones through a cascaded therapy, thereby revitalizing the tumor immune microenvironment in OSCC.
Immunotherapy offers significant potential but is often hampered by the immunosuppressive environment in oral squamous cell carcinoma (OSCC). To address this, we propose an enhanced immunotherapeutic strategy that revitalizes the tumor immune microenvironment (TIME) in OSCC by integrating upconversion-based photodynamic therapy (PDT) with chemotherapy. Using a red blood cell membrane-inspired biomimetic nanoplatform, our approach concurrently delivers chlorin e6@upconversion nanoparticles (Ce6@UCNP) and doxorubicin (DOX). By leveraging fluorescence resonance energy transfer (FRET) for 980 nm to 660 nm upconversion excitation, we address challenges such as limited tissue penetration and tissue damage, as well as nanoplatform issues including immunogenicity and targeting inaccuracy Our integrated approach enhances PDT and chemotherapy with the goal of transforming immunologically "cold" tumors into "hot" ones through a cascaded therapy, thereby revitalizing the tumor immune microenvironment in OSCC.
2025, 36(1): 109778
doi: 10.1016/j.cclet.2024.109778
Abstract:
Intracellular redox homeostasis is of indispensable importance in pathophysiology. In order to maintain the balance of the redox state within the cell, reactive oxygen species (ROS) and reactive sulfur species (RSS) react and transform with each other, and their levels also directly reflect the degree of oxidative stress and disease. Hypochlorous acid (HClO) and cysteine (Cys) usually co-exist in organisms, interacting with each other in many important physiological processes and synergistically maintaining the dynamic redox balance in the body. To understand the relevance and pathophysiological effects of these two signaling molecules in oxidative stress, unique fluorescence imaging tools are required. Herein, we designed and developed a dual-channel fluorescent probe HP, for the individual and continuous detection of HClO and Cys. This probe could simultaneously monitor the changes in the concentrations of HClO and Cys in cells, and was characterized by a fast response, high sensitivity and high selectivity, especially compared with glutathione (GSH) and homocysteine (Hcy), the probe had a good specificity for Cys. Importantly, probe HP successfully observed dynamic changes in HClO- and Cys-mediated redox status in the oxygen-glucose deprivation/reperfusion (OGD/R) model of HeLa cells and dynamically monitored fluctuations in endogenous HClO levels in lipopolysaccharides (LPS)-induced peritonitis mice.
Intracellular redox homeostasis is of indispensable importance in pathophysiology. In order to maintain the balance of the redox state within the cell, reactive oxygen species (ROS) and reactive sulfur species (RSS) react and transform with each other, and their levels also directly reflect the degree of oxidative stress and disease. Hypochlorous acid (HClO) and cysteine (Cys) usually co-exist in organisms, interacting with each other in many important physiological processes and synergistically maintaining the dynamic redox balance in the body. To understand the relevance and pathophysiological effects of these two signaling molecules in oxidative stress, unique fluorescence imaging tools are required. Herein, we designed and developed a dual-channel fluorescent probe HP, for the individual and continuous detection of HClO and Cys. This probe could simultaneously monitor the changes in the concentrations of HClO and Cys in cells, and was characterized by a fast response, high sensitivity and high selectivity, especially compared with glutathione (GSH) and homocysteine (Hcy), the probe had a good specificity for Cys. Importantly, probe HP successfully observed dynamic changes in HClO- and Cys-mediated redox status in the oxygen-glucose deprivation/reperfusion (OGD/R) model of HeLa cells and dynamically monitored fluctuations in endogenous HClO levels in lipopolysaccharides (LPS)-induced peritonitis mice.
2025, 36(1): 109781
doi: 10.1016/j.cclet.2024.109781
Abstract:
Herein, we report the dynamic kinetic resolution asymmetric acylation of γ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts, and a series of ketals were obtained in high yields (up to 95%) and excellent enantioselectivities (up to 99%). In terms of synthetic utility, the reaction can be performed on a gram scale, and the product can be converted into potential biological nucleoside analog.
Herein, we report the dynamic kinetic resolution asymmetric acylation of γ-hydroxy-γ-perfluoroalkyl butenolides/phthalides catalyzed by amino acid-derived bifunctional organocatalysts, and a series of ketals were obtained in high yields (up to 95%) and excellent enantioselectivities (up to 99%). In terms of synthetic utility, the reaction can be performed on a gram scale, and the product can be converted into potential biological nucleoside analog.
2025, 36(1): 109785
doi: 10.1016/j.cclet.2024.109785
Abstract:
Aflatoxins B1 (AFB1) contamination in agro-food holds great threaten to human and animal health. Conventional test strips for rapid AFB1 visualized monitoring remains challenged by improvement of sensitivity and matrix interference resistance. In this case, we developed a portable electrochemiluminescence (ECL) imaging test strip with dual-signal outputs for AFB1 quantification in corn samples. Ru-PEI@SiO2@Au nanospheres were synthesized for bonding with anti-AFB1 antibody and then colorimetrical signal-reported on test line through the capillary flow at strips. Meanwhile, ECL imaging signal of the constructed carbon-ink-based working electrode on polyvinyl chloride substrate of strips was exported under an applied potential of 1.25 V. The whole ECL test strips not only endowed convenient colorimetric responses but guaranteed quick-witted ECL image distinguishment even at extremely low AFB1 content. The detection limit of this ECL imaging-integrated mode was 10-fold lower than that of only colorimetric mode. Furthermore, satisfactory selectivity, reliability and practicability of the as-proposed ECL test strips were demonstrated. This work offered a promising platform for on-site, accurate and sensitive detection of pollutants in foods.
Aflatoxins B1 (AFB1) contamination in agro-food holds great threaten to human and animal health. Conventional test strips for rapid AFB1 visualized monitoring remains challenged by improvement of sensitivity and matrix interference resistance. In this case, we developed a portable electrochemiluminescence (ECL) imaging test strip with dual-signal outputs for AFB1 quantification in corn samples. Ru-PEI@SiO2@Au nanospheres were synthesized for bonding with anti-AFB1 antibody and then colorimetrical signal-reported on test line through the capillary flow at strips. Meanwhile, ECL imaging signal of the constructed carbon-ink-based working electrode on polyvinyl chloride substrate of strips was exported under an applied potential of 1.25 V. The whole ECL test strips not only endowed convenient colorimetric responses but guaranteed quick-witted ECL image distinguishment even at extremely low AFB1 content. The detection limit of this ECL imaging-integrated mode was 10-fold lower than that of only colorimetric mode. Furthermore, satisfactory selectivity, reliability and practicability of the as-proposed ECL test strips were demonstrated. This work offered a promising platform for on-site, accurate and sensitive detection of pollutants in foods.
"Superimposed" spectral characteristics of fluorophores arising from cross-conjugation hybridization
2025, 36(1): 109786
doi: 10.1016/j.cclet.2024.109786
Abstract:
The demand for enhanced optical properties in advanced fluorescence technologies has driven research into the structure-property relationship of fluorophores. In this paper, we use naphthalene fluorophores NaDC-Aze and PhDO-Aze as a case study to emphasize the pivotal role of cross conjugation in tuning the optical structure-property relationship. NaDC-Aze and PhDO-Aze, formed by hybridizing two distinct conjugated systems in a single naphthalene molecule, exhibit spectral characteristics from both conjugated systems. Experimental data and theoretical calculations demonstrate the coexistence of two electron-delocalization systems in a cross-conjugation manner in both NaDC-Aze and PhDO-Aze. The cross-conjugation fluorophores exhibit high brightness, large Stokes shift, and a broad absorption wavelength range by combining distinct spectral properties from its parent fluorophores. These spectral properties will be advantageous for certain applications (i.e., panchromatic absorption in organic solar cells, and fluorophores compatible with a wide range of excitation wavelengths).
The demand for enhanced optical properties in advanced fluorescence technologies has driven research into the structure-property relationship of fluorophores. In this paper, we use naphthalene fluorophores NaDC-Aze and PhDO-Aze as a case study to emphasize the pivotal role of cross conjugation in tuning the optical structure-property relationship. NaDC-Aze and PhDO-Aze, formed by hybridizing two distinct conjugated systems in a single naphthalene molecule, exhibit spectral characteristics from both conjugated systems. Experimental data and theoretical calculations demonstrate the coexistence of two electron-delocalization systems in a cross-conjugation manner in both NaDC-Aze and PhDO-Aze. The cross-conjugation fluorophores exhibit high brightness, large Stokes shift, and a broad absorption wavelength range by combining distinct spectral properties from its parent fluorophores. These spectral properties will be advantageous for certain applications (i.e., panchromatic absorption in organic solar cells, and fluorophores compatible with a wide range of excitation wavelengths).
2025, 36(1): 109790
doi: 10.1016/j.cclet.2024.109790
Abstract:
An N-heterocyclic carbene (NHC) catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported and δ-lactones tolerated with stereogenic centers at β- and γ-positions are obtained in moderate to high yields and with high enantioselectivities. Further computational studies explain that the radical cross-coupling step is the key to determining the enantioselectivity. Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control. DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.
An N-heterocyclic carbene (NHC) catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported and δ-lactones tolerated with stereogenic centers at β- and γ-positions are obtained in moderate to high yields and with high enantioselectivities. Further computational studies explain that the radical cross-coupling step is the key to determining the enantioselectivity. Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control. DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.
2025, 36(1): 109798
doi: 10.1016/j.cclet.2024.109798
Abstract:
PBQ [1-(4-chlorophenyl)-3-(pyridin-3-yl)urea], an enormous potent molluscicide, showed excellent Pomacea canaliculata (P. canaliculata) control activity and low toxicity for other aquatic organisms, but its snail-killing mechanisms are still not fully understood. We employed an optical method to elucidate PBQ action via a novel fluorescent viscosity probe, NCV. As the viscosity in the test solutions increased, compared with that in pure ethanol, a 54-fold fluorescence intensity enhancement of NCV was observed in 310 cP of 90% glycerol. Furthermore, NCV successfully exhibited a selective fluorescence response towards monensin-induced cellular viscosity changes in HepG2 cells. The liver, stomach, and foot plantar of the tested snails were frozen and sectioned for fluorescent imaging experiments after the treatment with different PBQ concentrations over various times. A significant fluorescent increase in the snail's liver was observed upon exposure to 0.75 mg/L PBQ for 72 h, which highlighted an increase in viscosity. Hematoxylin and eosin (HE) staining further supported PBQ-induced liver damage with a viscosity increase in P. canaliculata. Our study provides a new rapid optical visualization method to study the killing mechanisms of PBQ and may help discover new chemicals that control snail populations.
PBQ [1-(4-chlorophenyl)-3-(pyridin-3-yl)urea], an enormous potent molluscicide, showed excellent Pomacea canaliculata (P. canaliculata) control activity and low toxicity for other aquatic organisms, but its snail-killing mechanisms are still not fully understood. We employed an optical method to elucidate PBQ action via a novel fluorescent viscosity probe, NCV. As the viscosity in the test solutions increased, compared with that in pure ethanol, a 54-fold fluorescence intensity enhancement of NCV was observed in 310 cP of 90% glycerol. Furthermore, NCV successfully exhibited a selective fluorescence response towards monensin-induced cellular viscosity changes in HepG2 cells. The liver, stomach, and foot plantar of the tested snails were frozen and sectioned for fluorescent imaging experiments after the treatment with different PBQ concentrations over various times. A significant fluorescent increase in the snail's liver was observed upon exposure to 0.75 mg/L PBQ for 72 h, which highlighted an increase in viscosity. Hematoxylin and eosin (HE) staining further supported PBQ-induced liver damage with a viscosity increase in P. canaliculata. Our study provides a new rapid optical visualization method to study the killing mechanisms of PBQ and may help discover new chemicals that control snail populations.
2025, 36(1): 109799
doi: 10.1016/j.cclet.2024.109799
Abstract:
The first-ever synthesis of the unknown furo[2′,3′:4,5]pyrimido[1,2-b]indazole skeleton was demonstrated based on the undiscovered tetra-functionalization of enaminones, with simple substrates and reaction conditions. The key to realizing this process lies in the multiple trapping of the in situ generated ketenimine cation by the 3-aminoindazole, which results in the formation of four new chemical bonds and two new rings in one pot. Moreover, the products of this new reaction were found to exhibit aggregation-induced emission (AIE) without modification.
The first-ever synthesis of the unknown furo[2′,3′:4,5]pyrimido[1,2-b]indazole skeleton was demonstrated based on the undiscovered tetra-functionalization of enaminones, with simple substrates and reaction conditions. The key to realizing this process lies in the multiple trapping of the in situ generated ketenimine cation by the 3-aminoindazole, which results in the formation of four new chemical bonds and two new rings in one pot. Moreover, the products of this new reaction were found to exhibit aggregation-induced emission (AIE) without modification.
2025, 36(1): 109811
doi: 10.1016/j.cclet.2024.109811
Abstract:
Pyrrolobenzoxazines are a rare terpene-amino acid family of natural products with potent biological activities. Here, we reported the full biosynthetic pathway of paeciloxazine (1), a typical pyrrolobenzoxazine, with significant insecticidal activity. Base on heterologous expression, chemical complement experiment, and in vitro biochemical assays, we demonstrated the sesquiterpene portion of 1 derived from discontinuously oxidations of amorphdiene, in which P450 monooxygenase PaxH catalyzed a cascade of hydroxylation and epoxidation, while two flavin dependent monooxygenases are involved in the transformation of the esterified tryptophan into a pyrrolobenzoxazine core. Furthermore, a total of 15 compounds were generated through heterologous expression, of which 13, 17 and 20 showed potential antiepileptic activity. This study fully elucidated the biosynthetic pathway of paeciloxazine (1) and showed the diversity and complexity of constructing natural products by organisms.
Pyrrolobenzoxazines are a rare terpene-amino acid family of natural products with potent biological activities. Here, we reported the full biosynthetic pathway of paeciloxazine (1), a typical pyrrolobenzoxazine, with significant insecticidal activity. Base on heterologous expression, chemical complement experiment, and in vitro biochemical assays, we demonstrated the sesquiterpene portion of 1 derived from discontinuously oxidations of amorphdiene, in which P450 monooxygenase PaxH catalyzed a cascade of hydroxylation and epoxidation, while two flavin dependent monooxygenases are involved in the transformation of the esterified tryptophan into a pyrrolobenzoxazine core. Furthermore, a total of 15 compounds were generated through heterologous expression, of which 13, 17 and 20 showed potential antiepileptic activity. This study fully elucidated the biosynthetic pathway of paeciloxazine (1) and showed the diversity and complexity of constructing natural products by organisms.
2025, 36(1): 109817
doi: 10.1016/j.cclet.2024.109817
Abstract:
Carbonyl compounds are abundant in nature and represent a substantial portion of biomass resources. Despite significant recent progress in homo-coupling of carbonyl compounds, achieving their deoxy-functionalization homo-coupling remains a highly intricate challenge. Herein, we report an entirely novel reaction paradigm: the trifluoromethylative homo-coupling of carbonyl compounds via hydrazones, which enables the formation of three C(sp3)–C(sp3) bonds in a single step. This method provides a new pathway for synthesizing trifluoromethylative coupling product which has unique applications in both fields of medical and material sciences. Mechanistic investigations have unveiled that the formation of a trifluoromethyl-substituted benzyl radical plays a pivotal role as a key intermediate in this reaction.
Carbonyl compounds are abundant in nature and represent a substantial portion of biomass resources. Despite significant recent progress in homo-coupling of carbonyl compounds, achieving their deoxy-functionalization homo-coupling remains a highly intricate challenge. Herein, we report an entirely novel reaction paradigm: the trifluoromethylative homo-coupling of carbonyl compounds via hydrazones, which enables the formation of three C(sp3)–C(sp3) bonds in a single step. This method provides a new pathway for synthesizing trifluoromethylative coupling product which has unique applications in both fields of medical and material sciences. Mechanistic investigations have unveiled that the formation of a trifluoromethyl-substituted benzyl radical plays a pivotal role as a key intermediate in this reaction.
2025, 36(1): 109818
doi: 10.1016/j.cclet.2024.109818
Abstract:
The preparation, functionalization, and investigations in host-guest properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods. Herein, a novel type of pillararene derivative, namely desymmetrized pillar[8]arene (DP[8]A), has been successfully synthesized via a facile two-step strategy with high yield. Compared with its pillar[8]arene counterpart, DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings. Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A, which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance. Density functional theory (DFT) calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity. Water-soluble carboxylate-modified DP[8]A, that is, CDP[8]A, was also prepared to investigate the host-guest properties in aqueous solution with methyl viologen (MV), where the binding constant and morphologies of the formed host-guest complexes have been studied. In all, this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.
The preparation, functionalization, and investigations in host-guest properties of high-level pillararene macrocycles have long been a big challenge because of the lack of efficient synthetic methods. Herein, a novel type of pillararene derivative, namely desymmetrized pillar[8]arene (DP[8]A), has been successfully synthesized via a facile two-step strategy with high yield. Compared with its pillar[8]arene counterpart, DP[8]A is composed of four alkoxy-substituted benzene units and four bare benzene rings. Single crystal analysis has been performed in order to unveil the molecular conformation and packing mode of DP[8]A, which indicated that DP[8]A possesses a unique chair-like structure and much smaller steric hindrance. Density functional theory (DFT) calculations and electrostatic potential map suggested the inhomogeneous electronic distribution in the DP[8]A cavity. Water-soluble carboxylate-modified DP[8]A, that is, CDP[8]A, was also prepared to investigate the host-guest properties in aqueous solution with methyl viologen (MV), where the binding constant and morphologies of the formed host-guest complexes have been studied. In all, this new version of eight-membered pillararene derivative might potentially serve as a powerful macrocycle candidate for further applications in supramolecular chemistry.
2025, 36(1): 109834
doi: 10.1016/j.cclet.2024.109834
Abstract:
Fluorescence lateral flow immunoassay (LFA) has emerged as a powerful tool for rapid screening of various biomarkers owing to its simplicity, sensitivity and flexibility. It is noteworthy that fluorescent probe mainly determines the analytical performance of LFA. Due to the emission and excitation wavelengths are located in the visible region, most fluorophores are inevitably subject to light scattering and background autofluorescence. Herein, we reported a novel LFA sensor based on the second near-infrared (NIR-Ⅱ) fluorescent probe with excellent anti-interference capability. The designed NIR-Ⅱ probe was the Nd3+ and Yb3+ doped rare earth nanoparticles (RENPs) by employing Nd3+ as energy donor and Yb3+ as energy acceptor, which of the donor-acceptor energy transfer (ET) efficiency reached up to 80.7%. Meanwhile, relying on the convenient and effective encapsulation strategy of poly(lactic-co-glycolic acid) (PLGA) microspheres to RENPs, the surface functionalized NIR-Ⅱ probe (RE@PLGA) was obtained for subsequent bioconjugation. Benefiting from the optical advantages of NIR-Ⅱ probe, this proposed NIR-Ⅱ LFA displayed a good linear relationship ranging from 7 ng/mL to 200 ng/mL for the detection of α-fetoprotein (AFP), an important biomarker of hepatocellular carcinoma (HCC). The limit of detection (LOD) was determined as low as 3.0 ng/mL, which was of 8.3 times lower than clinical cutoff value. It is promising that LFA sensor based on this efficient RENPs probe provides new opportunities for high sensitive detection of various biomarkers in biological samples.
Fluorescence lateral flow immunoassay (LFA) has emerged as a powerful tool for rapid screening of various biomarkers owing to its simplicity, sensitivity and flexibility. It is noteworthy that fluorescent probe mainly determines the analytical performance of LFA. Due to the emission and excitation wavelengths are located in the visible region, most fluorophores are inevitably subject to light scattering and background autofluorescence. Herein, we reported a novel LFA sensor based on the second near-infrared (NIR-Ⅱ) fluorescent probe with excellent anti-interference capability. The designed NIR-Ⅱ probe was the Nd3+ and Yb3+ doped rare earth nanoparticles (RENPs) by employing Nd3+ as energy donor and Yb3+ as energy acceptor, which of the donor-acceptor energy transfer (ET) efficiency reached up to 80.7%. Meanwhile, relying on the convenient and effective encapsulation strategy of poly(lactic-co-glycolic acid) (PLGA) microspheres to RENPs, the surface functionalized NIR-Ⅱ probe (RE@PLGA) was obtained for subsequent bioconjugation. Benefiting from the optical advantages of NIR-Ⅱ probe, this proposed NIR-Ⅱ LFA displayed a good linear relationship ranging from 7 ng/mL to 200 ng/mL for the detection of α-fetoprotein (AFP), an important biomarker of hepatocellular carcinoma (HCC). The limit of detection (LOD) was determined as low as 3.0 ng/mL, which was of 8.3 times lower than clinical cutoff value. It is promising that LFA sensor based on this efficient RENPs probe provides new opportunities for high sensitive detection of various biomarkers in biological samples.
2025, 36(1): 109839
doi: 10.1016/j.cclet.2024.109839
Abstract:
Heterodimerization in RTKs is of vital importance in the RTK signaling and cell functions. Heterodimerization between RTKs can result in diversity of downstream signals, increasing the ability of cells to respond to external experiments. Traditional RTKs heterodimerization always occur in the same families and is lack of agonists to activate the heterodimeric RTKs signaling pathway. Herein, we developed the DNA agonist based on bivalent aptamers for the heterodimerized RTKs of different families, AF/AM-1, which could simultaneously activate FGFR1 and c-Met signaling. It is the first agonist that realizing the heterodimerization and activation of FGFR1 and c-Met, two different RTK families. The activation of FGFR1/c-Met heterodimer result in the down-stream signals transduction, such as the phosphorylation of Akt and Erk, inducing the cell migration and proliferation. The DNA agonist for RTK heterodimer of different families would have potential applications in the fields of biomedicine.
Heterodimerization in RTKs is of vital importance in the RTK signaling and cell functions. Heterodimerization between RTKs can result in diversity of downstream signals, increasing the ability of cells to respond to external experiments. Traditional RTKs heterodimerization always occur in the same families and is lack of agonists to activate the heterodimeric RTKs signaling pathway. Herein, we developed the DNA agonist based on bivalent aptamers for the heterodimerized RTKs of different families, AF/AM-1, which could simultaneously activate FGFR1 and c-Met signaling. It is the first agonist that realizing the heterodimerization and activation of FGFR1 and c-Met, two different RTK families. The activation of FGFR1/c-Met heterodimer result in the down-stream signals transduction, such as the phosphorylation of Akt and Erk, inducing the cell migration and proliferation. The DNA agonist for RTK heterodimer of different families would have potential applications in the fields of biomedicine.
2025, 36(1): 109840
doi: 10.1016/j.cclet.2024.109840
Abstract:
Vascular disrupting agents (VDAs) can destroy tumor vasculature and lead to tumor ischemia and hypoxia, resulting in tumor necrosis. However, VDAs are easy to induce the upregulation of genes that are associated with cancer cell drug resistance and angiogenesis in tumor cells. Hypoxia-activated chemotherapy will be an ideal supplement to VDAs therapy since it can help to fully utilize the ischemia and hypoxia induced by VDAs to realize a synergistic antitumor therapeutic outcome. Here, we design a liposome whose surface is modified with a tumor-homing peptide Cys-Arg-Glu-Lys-Ala (CREKA, which can specifically target tumor vessels and stroma) and whose aqueous cavity and lipid bilayer are loaded by a hypoxia-activatable drug banoxantrone dihydrochloride (AQ4N) and a VDA combretastatin A4 (CA4), respectively. CA4 can selectively target vascular endothelial cells and destroy the tumor blood vessels, which will cause the rapid inhibition of blood flow in tumor and enhance the hypoxia in the tumor region. As a consequence, AQ4N can exert its boosted cytotoxicity under the enhanced hypoxic environment. The as-prepared liposome with a uniform particle size exhibits good stability and high cancer cell killing efficacy in vitro. In addition, in vivo experiments confirm the excellent tumor-targeting/accumulation, tumor vasculature-damaging, and tumor inhibition effects of the liposome. This work develops a liposomal which can achieve safe and effective tumor suppression without external stimulus excitation by only single injection, and is expected to benefit the future development of effective antitumor liposomal drugs.
Vascular disrupting agents (VDAs) can destroy tumor vasculature and lead to tumor ischemia and hypoxia, resulting in tumor necrosis. However, VDAs are easy to induce the upregulation of genes that are associated with cancer cell drug resistance and angiogenesis in tumor cells. Hypoxia-activated chemotherapy will be an ideal supplement to VDAs therapy since it can help to fully utilize the ischemia and hypoxia induced by VDAs to realize a synergistic antitumor therapeutic outcome. Here, we design a liposome whose surface is modified with a tumor-homing peptide Cys-Arg-Glu-Lys-Ala (CREKA, which can specifically target tumor vessels and stroma) and whose aqueous cavity and lipid bilayer are loaded by a hypoxia-activatable drug banoxantrone dihydrochloride (AQ4N) and a VDA combretastatin A4 (CA4), respectively. CA4 can selectively target vascular endothelial cells and destroy the tumor blood vessels, which will cause the rapid inhibition of blood flow in tumor and enhance the hypoxia in the tumor region. As a consequence, AQ4N can exert its boosted cytotoxicity under the enhanced hypoxic environment. The as-prepared liposome with a uniform particle size exhibits good stability and high cancer cell killing efficacy in vitro. In addition, in vivo experiments confirm the excellent tumor-targeting/accumulation, tumor vasculature-damaging, and tumor inhibition effects of the liposome. This work develops a liposomal which can achieve safe and effective tumor suppression without external stimulus excitation by only single injection, and is expected to benefit the future development of effective antitumor liposomal drugs.
2025, 36(1): 109842
doi: 10.1016/j.cclet.2024.109842
Abstract:
Axially chiral binaphthol have achieved great success in asymmetric catalysis. Compared to α-binaphthol, axially chiral aryl-β-naphthol are far less reported. Here, we report a method of asymmetric catalysis to construct β-naphthol with up to 99% yield, 95.5:4.5 enantiomeric ratio, using alkynyl esters as precursors and chiral phosphonic acid (CPA)/Lewis acid as catalysts. Key steps involve oxygen transfer and de novo arene formation to set up the chiral axis. Moreover, this methodology provides a versatile platform for structurally divergent synthesis of atroposelective β-naphthol analogs, which are widely found in bioactive molecules and asymmetric catalysts.
Axially chiral binaphthol have achieved great success in asymmetric catalysis. Compared to α-binaphthol, axially chiral aryl-β-naphthol are far less reported. Here, we report a method of asymmetric catalysis to construct β-naphthol with up to 99% yield, 95.5:4.5 enantiomeric ratio, using alkynyl esters as precursors and chiral phosphonic acid (CPA)/Lewis acid as catalysts. Key steps involve oxygen transfer and de novo arene formation to set up the chiral axis. Moreover, this methodology provides a versatile platform for structurally divergent synthesis of atroposelective β-naphthol analogs, which are widely found in bioactive molecules and asymmetric catalysts.
2025, 36(1): 109844
doi: 10.1016/j.cclet.2024.109844
Abstract:
Macrophages undergo dynamic transitions between M1 and M2 states, exerting profound influences on both inflammatory and regenerative processes. The biocompatible and wound-healing properties of decellularized amniotic membrane (dAM) make it a subject of exploration for its potential impact on the anti-inflammatory response of macrophages. Experimental findings unequivocally demonstrate that dAM promotes anti-inflammatory M2 polarization of macrophage, with its cytokine-rich content posited as a potential mediator. The application of RNA sequencing unveils differential gene expression, implicating the hypoxia inducible factor-1α (HIF-1α) signaling pathway in this intricate interplay. Subsequent investigation further demonstrates that dAM facilitates anti-inflammatory M2 polarization of macrophage through the upregulation of epidermal growth factor (EGF), which, in turn, activates the phosphatidylinositol 3-kinase (PI3K)/protein kinase B (AKT) pathway and stabilizes HIF-1α. This cascade results in a noteworthy augmentation of anti-inflammatory gene expression. This study significantly contributes to advancing our comprehension of dAM's immunomodulatory role in tissue repair, thereby suggesting promising therapeutic potential.
Macrophages undergo dynamic transitions between M1 and M2 states, exerting profound influences on both inflammatory and regenerative processes. The biocompatible and wound-healing properties of decellularized amniotic membrane (dAM) make it a subject of exploration for its potential impact on the anti-inflammatory response of macrophages. Experimental findings unequivocally demonstrate that dAM promotes anti-inflammatory M2 polarization of macrophage, with its cytokine-rich content posited as a potential mediator. The application of RNA sequencing unveils differential gene expression, implicating the hypoxia inducible factor-1α (HIF-1α) signaling pathway in this intricate interplay. Subsequent investigation further demonstrates that dAM facilitates anti-inflammatory M2 polarization of macrophage through the upregulation of epidermal growth factor (EGF), which, in turn, activates the phosphatidylinositol 3-kinase (PI3K)/protein kinase B (AKT) pathway and stabilizes HIF-1α. This cascade results in a noteworthy augmentation of anti-inflammatory gene expression. This study significantly contributes to advancing our comprehension of dAM's immunomodulatory role in tissue repair, thereby suggesting promising therapeutic potential.
2025, 36(1): 109848
doi: 10.1016/j.cclet.2024.109848
Abstract:
Nanomaterials provide an ideal platform for biomolecular display due to their dimensions approach the molecular scale, facilitating binding behavior akin to that observed in solution-based processes. DNA nanoprobes hold great promise as miniature detectives capable of detecting miRNAs within cells. However, current nanoprobes face a challenge in achieving the required precision for accurate miRNA detection, particularly within the intricate confines of the cellular microenvironment, due to interference with biological autofluorescence, off-target effects, and a lack of spatiotemporal control. Here, we have designed a dual-stimuli responsive DNA tracker, synergistically utilizing specific intracellular cues and external triggers, which enables spatiotemporal-controlled and precise detection and imaging of miRNAs "on demand". The tracker, which combines zeolitic imidazolate framework-67 (ZIF-67) and unique hairpin DNA structures, effectively anchored onto the ZIF-67 through electrostatic interactions, remains in a dormant state until activated by abundant cellular ATP, resulting in the release of the hairpin structures that include a PC linker incorporated into the loop region. Subsequent irradiation triggers specific recognition of the target miRNA. The newly developed HP-PC-BT@ZIF-67 tracker demonstrates precise spatiotemporal miRNA detection and exhibits excellent biocompatibility, enabling specific miRNA recognition "on demand" within cancer cells. This research presents a reliable miRNA imaging platform in the intricate cellular environment, opening up the possibilities for precise biomedical analysis and disease diagnosis.
Nanomaterials provide an ideal platform for biomolecular display due to their dimensions approach the molecular scale, facilitating binding behavior akin to that observed in solution-based processes. DNA nanoprobes hold great promise as miniature detectives capable of detecting miRNAs within cells. However, current nanoprobes face a challenge in achieving the required precision for accurate miRNA detection, particularly within the intricate confines of the cellular microenvironment, due to interference with biological autofluorescence, off-target effects, and a lack of spatiotemporal control. Here, we have designed a dual-stimuli responsive DNA tracker, synergistically utilizing specific intracellular cues and external triggers, which enables spatiotemporal-controlled and precise detection and imaging of miRNAs "on demand". The tracker, which combines zeolitic imidazolate framework-67 (ZIF-67) and unique hairpin DNA structures, effectively anchored onto the ZIF-67 through electrostatic interactions, remains in a dormant state until activated by abundant cellular ATP, resulting in the release of the hairpin structures that include a PC linker incorporated into the loop region. Subsequent irradiation triggers specific recognition of the target miRNA. The newly developed HP-PC-BT@ZIF-67 tracker demonstrates precise spatiotemporal miRNA detection and exhibits excellent biocompatibility, enabling specific miRNA recognition "on demand" within cancer cells. This research presents a reliable miRNA imaging platform in the intricate cellular environment, opening up the possibilities for precise biomedical analysis and disease diagnosis.
2025, 36(1): 109857
doi: 10.1016/j.cclet.2024.109857
Abstract:
Early diagnosis and accurate boundary delineation are the key steps of tumor precision medicine. Circulating tumor cells (CTCs) detection of liquid biopsy can provide abundant information for early diagnosis of cancer. High detection specificity and good enrichment features are two key factors for CTCs accurate identification in peripheral blood sample. For this purpose, iron oxide (IO)-based surface-enhanced Raman scattering (SERS) bioprobes with good biocompatibility, high detection sensitivity, remarkable detection specificity, and good enrichment efficiency, were developed for detecting different types of CTCs. Magnetic SERS bioprobes combined with programmed death ligand-1 (PD-L1) antibody are regarded as an effective way to boost the targeting ability and detection specificity, benefiting for accurately capturing and identifying rare CTCs. Four types of CTCs with different PD-L1 expression were accurately distinguished among white blood cells via high-resolution SERS mapping images and stable Raman signals. Subsequently, CTCs blood samples obtained from the triple negative breast cancer patients were also successfully recognized compared to that of health people, indicating IO@AR@PDA-aPD-L1 SERS bioprobe possessed great potential for CTCs detection in liquid biopsy. Additionally, IO-based bioprobe exhibited excellent dual-modal imaging abilities of high-resolution SERS imaging mode and microimaging magnetic resonance imaging mode. These two highly complementary imaging modes endowed IO-based bioprobes unrivalled capacity in tumor boundary differentiation, supporting tumor accurate resection and precise surgery. To our best knowledge, this is the first time that biocompatible IO-based SERS bioprobes without noble metal element were reported not only for CTCs accurate detection, but also for precise tumor boundary delineation, showing great advantages in tumor diagnosis and treatment.
Early diagnosis and accurate boundary delineation are the key steps of tumor precision medicine. Circulating tumor cells (CTCs) detection of liquid biopsy can provide abundant information for early diagnosis of cancer. High detection specificity and good enrichment features are two key factors for CTCs accurate identification in peripheral blood sample. For this purpose, iron oxide (IO)-based surface-enhanced Raman scattering (SERS) bioprobes with good biocompatibility, high detection sensitivity, remarkable detection specificity, and good enrichment efficiency, were developed for detecting different types of CTCs. Magnetic SERS bioprobes combined with programmed death ligand-1 (PD-L1) antibody are regarded as an effective way to boost the targeting ability and detection specificity, benefiting for accurately capturing and identifying rare CTCs. Four types of CTCs with different PD-L1 expression were accurately distinguished among white blood cells via high-resolution SERS mapping images and stable Raman signals. Subsequently, CTCs blood samples obtained from the triple negative breast cancer patients were also successfully recognized compared to that of health people, indicating IO@AR@PDA-aPD-L1 SERS bioprobe possessed great potential for CTCs detection in liquid biopsy. Additionally, IO-based bioprobe exhibited excellent dual-modal imaging abilities of high-resolution SERS imaging mode and microimaging magnetic resonance imaging mode. These two highly complementary imaging modes endowed IO-based bioprobes unrivalled capacity in tumor boundary differentiation, supporting tumor accurate resection and precise surgery. To our best knowledge, this is the first time that biocompatible IO-based SERS bioprobes without noble metal element were reported not only for CTCs accurate detection, but also for precise tumor boundary delineation, showing great advantages in tumor diagnosis and treatment.
2025, 36(1): 109882
doi: 10.1016/j.cclet.2024.109882
Abstract:
The contamination of water resources by phenolic compounds (PCs) presents a significant environmental hazard, necessitating the development of novel materials and methodologies for effective mitigation. In this study, a metallic copper-doped zeolitic imidazolate framework was pyrolyzed and designated as Cu-NC-20 for the activation of peroxymonosulfate (PMS) to degrade phenol (PE). Cu-NC-20 could effectively address the issue of metal agglomeration while simultaneously diminishing copper dissolution during the activation of PMS reactions. The Cu-NC-20 catalyst exhibited a rapid degradation rate for PE across a broad pH range (3–9) and demonstrated high tolerance towards coexisting ions. According to scavenger experiments and electron paramagnetic resonance analysis, singlet oxygen (1O2) and high-valent copper-oxo (Cu(Ⅲ)) were the predominant reactive oxygen species, indicating that the system was nonradical-dominated during the degradation process. The quantitative structure-activity relationship (QSAR) between the oxidation rate constants of various substituted phenols and Hammett constants was established. It indicated that the Cu-NC-20/PMS system had the optimal oxidation rate constant with σ− correlation and exhibited a typical electrophilic reaction pattern. This study provides a comprehensive understanding of the heterogeneous activation process for the selective removal of phenolic compounds.
The contamination of water resources by phenolic compounds (PCs) presents a significant environmental hazard, necessitating the development of novel materials and methodologies for effective mitigation. In this study, a metallic copper-doped zeolitic imidazolate framework was pyrolyzed and designated as Cu-NC-20 for the activation of peroxymonosulfate (PMS) to degrade phenol (PE). Cu-NC-20 could effectively address the issue of metal agglomeration while simultaneously diminishing copper dissolution during the activation of PMS reactions. The Cu-NC-20 catalyst exhibited a rapid degradation rate for PE across a broad pH range (3–9) and demonstrated high tolerance towards coexisting ions. According to scavenger experiments and electron paramagnetic resonance analysis, singlet oxygen (1O2) and high-valent copper-oxo (Cu(Ⅲ)) were the predominant reactive oxygen species, indicating that the system was nonradical-dominated during the degradation process. The quantitative structure-activity relationship (QSAR) between the oxidation rate constants of various substituted phenols and Hammett constants was established. It indicated that the Cu-NC-20/PMS system had the optimal oxidation rate constant with σ− correlation and exhibited a typical electrophilic reaction pattern. This study provides a comprehensive understanding of the heterogeneous activation process for the selective removal of phenolic compounds.
2025, 36(1): 109883
doi: 10.1016/j.cclet.2024.109883
Abstract:
Membrane distillation (MD) has gained extensive attention for treating highly saline wastewater. However, membrane scaling during the MD process has hindered the rapid development of this technology. Current approaches to mitigate scaling in membrane distillation focus primarily on achieving enhanced hydrophobicity and even superhydrophobicity via utilizing fluorinated fibrous membrane or introducing perfluorosilane modification. Considering the environmental hazards posed by fluorinated compounds, it is highly desirable to develop non-fluorinated membranes with enhanced anti-scaling properties for effective membrane distillation. In this study, we present a non-fluorinated liquid-like MD membrane with exceptional anti-scaling performance. This membrane was facilely fabricated by grafting linear polydimethylsiloxane (LPDMS) onto a hydrophilic polyether sulfone (PES) membrane pre-coated with the intermediate layers of polydopamine and silica (denoted as LPDMS-PES). Remarkably, LPDMS-PES manifested a drastically improved scaling resistance in continuous MD tests than its perfluorinated counterpart, i.e., 1H,1H,2H,2H-perfluorooctyltrichlorosilane-modified PES membrane (PFOS-PES), in both heterogeneous nucleation-dominated and crystal deposition-dominated scaling processes, despite the latter having a smaller surface energy. LPDMS-PES demonstrated a reduction of crystal accumulation of approximately 85% for NaCl and 73% for CaSO4 in the heterogeneous nucleation-dominated scaling process compared to PFOS-PES. Additionally, in the crystal deposition-dominated scaling process LPDMS-PES exhibited a reduction of about 70% in scale accumulation. These results explicitly evidenced the great potential of the liquid-like membrane to minimize scaling in membrane distillation by inhibiting both scale nucleation and adhesion onto the membrane. We believe the findings of this study have important implications for the design of high-performance MD membranes, particularly in the quest for environmentally sustainable alternatives to perfluorinated materials.
Membrane distillation (MD) has gained extensive attention for treating highly saline wastewater. However, membrane scaling during the MD process has hindered the rapid development of this technology. Current approaches to mitigate scaling in membrane distillation focus primarily on achieving enhanced hydrophobicity and even superhydrophobicity via utilizing fluorinated fibrous membrane or introducing perfluorosilane modification. Considering the environmental hazards posed by fluorinated compounds, it is highly desirable to develop non-fluorinated membranes with enhanced anti-scaling properties for effective membrane distillation. In this study, we present a non-fluorinated liquid-like MD membrane with exceptional anti-scaling performance. This membrane was facilely fabricated by grafting linear polydimethylsiloxane (LPDMS) onto a hydrophilic polyether sulfone (PES) membrane pre-coated with the intermediate layers of polydopamine and silica (denoted as LPDMS-PES). Remarkably, LPDMS-PES manifested a drastically improved scaling resistance in continuous MD tests than its perfluorinated counterpart, i.e., 1H,1H,2H,2H-perfluorooctyltrichlorosilane-modified PES membrane (PFOS-PES), in both heterogeneous nucleation-dominated and crystal deposition-dominated scaling processes, despite the latter having a smaller surface energy. LPDMS-PES demonstrated a reduction of crystal accumulation of approximately 85% for NaCl and 73% for CaSO4 in the heterogeneous nucleation-dominated scaling process compared to PFOS-PES. Additionally, in the crystal deposition-dominated scaling process LPDMS-PES exhibited a reduction of about 70% in scale accumulation. These results explicitly evidenced the great potential of the liquid-like membrane to minimize scaling in membrane distillation by inhibiting both scale nucleation and adhesion onto the membrane. We believe the findings of this study have important implications for the design of high-performance MD membranes, particularly in the quest for environmentally sustainable alternatives to perfluorinated materials.
2025, 36(1): 109884
doi: 10.1016/j.cclet.2024.109884
Abstract:
Deep learning neural network incorporating surface enhancement Raman scattering technique (SERS) is becoming as a powerful tool for the precise classifications and diagnosis of bacterial infections. However, the large amount of sample requirement and time-consuming sample collection severely hinder its applications. We herein propose a spectral concatenation strategy for residual neural network using non-specific and specific SERS spectra for the training data augmentation, which is accessible to acquiring larger training dataset with same number of SERS spectra or same size of training dataset with fewer SERS spectra, compared with pure non-specific SERS spectra. With this strategy, the training loss exhibit rapid convergence, and an average accuracy up to 100% in bacteria classifications was achieved with 50 SERS spectra for each kind of bacterium; even reduced to 20 SERS spectra per kind of bacterium, classification accuracy is still > 95%, demonstrating marked advantage over the results without spectra concatenation. This method can markedly improve the classification accuracy under fewer samples and reduce the data collection workload, and can evidently enhance the performance when used in different machine learning models with high generalization ability. Therefore, this strategy is beneficial for rapid and accurate bacteria classifications with residual neural network.
Deep learning neural network incorporating surface enhancement Raman scattering technique (SERS) is becoming as a powerful tool for the precise classifications and diagnosis of bacterial infections. However, the large amount of sample requirement and time-consuming sample collection severely hinder its applications. We herein propose a spectral concatenation strategy for residual neural network using non-specific and specific SERS spectra for the training data augmentation, which is accessible to acquiring larger training dataset with same number of SERS spectra or same size of training dataset with fewer SERS spectra, compared with pure non-specific SERS spectra. With this strategy, the training loss exhibit rapid convergence, and an average accuracy up to 100% in bacteria classifications was achieved with 50 SERS spectra for each kind of bacterium; even reduced to 20 SERS spectra per kind of bacterium, classification accuracy is still > 95%, demonstrating marked advantage over the results without spectra concatenation. This method can markedly improve the classification accuracy under fewer samples and reduce the data collection workload, and can evidently enhance the performance when used in different machine learning models with high generalization ability. Therefore, this strategy is beneficial for rapid and accurate bacteria classifications with residual neural network.
2025, 36(1): 109885
doi: 10.1016/j.cclet.2024.109885
Abstract:
Inactivation of carbon-based transition metal catalysts, which was caused by electron loss, limited their application in advanced oxidation processes. Therefore, Co and TiO2 double-loaded carbon nanofiber material (Co@CNFs-TiO2) was synthesized in this study. Photocatalytic and chemical catalytic systems were synergized efficiently. Tetracycline was eliminated within 15 min. The degradation rate remained above 90% after five cycles, and the 50% promotion proved the high stability of Co@CNFs-TiO2. The main reactive oxygen species in this system were sulfate radicals, whereas Co and TiO2 represented the active sites of the catalytic reaction. Electrons generated from TiO2 during the photocatalytic process were transferred to Co, which promoted the Co(Ⅲ)/Co(Ⅱ) cycle and maintained Co in a low-valence state, thereby stimulating the generation of sulfate radicals. In this study, the effective regulation of reactive oxygen species in the reaction system was realized. The results provided a guidance for in situ electron replenishment and regeneration of carbon-based transition metal catalysts, which will expand the practical application of advanced oxidation processes.
Inactivation of carbon-based transition metal catalysts, which was caused by electron loss, limited their application in advanced oxidation processes. Therefore, Co and TiO2 double-loaded carbon nanofiber material (Co@CNFs-TiO2) was synthesized in this study. Photocatalytic and chemical catalytic systems were synergized efficiently. Tetracycline was eliminated within 15 min. The degradation rate remained above 90% after five cycles, and the 50% promotion proved the high stability of Co@CNFs-TiO2. The main reactive oxygen species in this system were sulfate radicals, whereas Co and TiO2 represented the active sites of the catalytic reaction. Electrons generated from TiO2 during the photocatalytic process were transferred to Co, which promoted the Co(Ⅲ)/Co(Ⅱ) cycle and maintained Co in a low-valence state, thereby stimulating the generation of sulfate radicals. In this study, the effective regulation of reactive oxygen species in the reaction system was realized. The results provided a guidance for in situ electron replenishment and regeneration of carbon-based transition metal catalysts, which will expand the practical application of advanced oxidation processes.
2025, 36(1): 109889
doi: 10.1016/j.cclet.2024.109889
Abstract:
An ionic liquid assisted hydrogel modified silica was synthesized using a one-pot polymerization and physical coating technique and subsequently applied to mixed-mode liquid chromatography. Analytical techniques, including Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and elemental analysis, etc., confirmed the successful prepared of this innovative stationary phase. The unique combination of amide, long alkyl chain, and imidazole ring in the hydrogel coating enables the stationary phase to function effectively in hydrophilic/reversed-phase/ion exchange liquid chromatography. Notably, the stationary phase exhibited superior separation performance owing to the synergistic effect of the ionic liquid and hydrogel. This was particularly evident when analyzing various analytes such as organic acids, nucleosides/bases, polycyclic aromatic hydrocarbons (PAHs) and anions. Furthermore, under our operating conditions, an excellent column efficiency of 53, 642.9 plates/m was achieved for theobromine. In summary, we have proposed a straightforward strategy to enhance the separation performance of hydrogel coatings in liquid chromatography, thereby broadening the potential applications of hydrogels in the field of separation.
An ionic liquid assisted hydrogel modified silica was synthesized using a one-pot polymerization and physical coating technique and subsequently applied to mixed-mode liquid chromatography. Analytical techniques, including Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and elemental analysis, etc., confirmed the successful prepared of this innovative stationary phase. The unique combination of amide, long alkyl chain, and imidazole ring in the hydrogel coating enables the stationary phase to function effectively in hydrophilic/reversed-phase/ion exchange liquid chromatography. Notably, the stationary phase exhibited superior separation performance owing to the synergistic effect of the ionic liquid and hydrogel. This was particularly evident when analyzing various analytes such as organic acids, nucleosides/bases, polycyclic aromatic hydrocarbons (PAHs) and anions. Furthermore, under our operating conditions, an excellent column efficiency of 53, 642.9 plates/m was achieved for theobromine. In summary, we have proposed a straightforward strategy to enhance the separation performance of hydrogel coatings in liquid chromatography, thereby broadening the potential applications of hydrogels in the field of separation.
2025, 36(1): 109896
doi: 10.1016/j.cclet.2024.109896
Abstract:
Selenium is one of the important trace elements in the human body. Its deficiency will directly affect human health. With people's attention to health, the content of selenium in food has gradually attracted attention. However, detecting selenium compounds in complex samples remains a challenge. In this work, we built an online heating-reaction device. This device combines the electrospray extraction ionization mass spectrometry (EESI-MS) with the heating reaction device, which can simultaneously detect various selenium compounds in complex liquid samples. Under acidic conditions, the sample was heated and catalyzed by a heating reaction device, so that the SeO32− and O-phenylenediamine (OPD) could generate 1,3-dihydro-2,1,3-benzoselenadiazole. Based on the above reactions, we can detect organic selenium, inorganic selenium and other compounds in liquid samples by organic mass spectrometry. In this experiment, we determined the content of three forms of selenium: selenomethionine (SeMet), l-selenocystine (SeCys(2)), and sodium selenite. The calibration curves for SeMet, SeCys(2), and sodium selenite showed strong linearity within a range of 0.50–50.00 µg/L. The limits of detection (LOD) for the three compounds were 0.22, 0.27, and 0.41 µg/L, respectively. The limits of quantification (LOQ) were 0.68, 0.81, and 1.23 µg/L, respectively. Spiked recoveries at three levels ranged from 98.8% to 106.1%. In addition, this method can simultaneously detect three selenium compounds and three other specific chemical components in tea infusion samples, providing a rapid and efficient method for identifying tea quality.
Selenium is one of the important trace elements in the human body. Its deficiency will directly affect human health. With people's attention to health, the content of selenium in food has gradually attracted attention. However, detecting selenium compounds in complex samples remains a challenge. In this work, we built an online heating-reaction device. This device combines the electrospray extraction ionization mass spectrometry (EESI-MS) with the heating reaction device, which can simultaneously detect various selenium compounds in complex liquid samples. Under acidic conditions, the sample was heated and catalyzed by a heating reaction device, so that the SeO32− and O-phenylenediamine (OPD) could generate 1,3-dihydro-2,1,3-benzoselenadiazole. Based on the above reactions, we can detect organic selenium, inorganic selenium and other compounds in liquid samples by organic mass spectrometry. In this experiment, we determined the content of three forms of selenium: selenomethionine (SeMet), l-selenocystine (SeCys(2)), and sodium selenite. The calibration curves for SeMet, SeCys(2), and sodium selenite showed strong linearity within a range of 0.50–50.00 µg/L. The limits of detection (LOD) for the three compounds were 0.22, 0.27, and 0.41 µg/L, respectively. The limits of quantification (LOQ) were 0.68, 0.81, and 1.23 µg/L, respectively. Spiked recoveries at three levels ranged from 98.8% to 106.1%. In addition, this method can simultaneously detect three selenium compounds and three other specific chemical components in tea infusion samples, providing a rapid and efficient method for identifying tea quality.
2025, 36(1): 109928
doi: 10.1016/j.cclet.2024.109928
Abstract:
Catalytic oxidation of soot is of great importance for emission control on diesel vehicles. In this work, a highly active Cs/Co/Ce-Sn catalyst was investigated for soot oxidation, and it was unexpectedly found that high-temperature calcination greatly improved the activity of the catalyst. When the calcination temperature was increased from 500 ℃ to 750 ℃, T50 decreased from 456.9 ℃ to 389.8 ℃ in a NO/O2/H2O/N2 atmosphere. Characterization results revealed that high-temperature calcination can promote the ability to transfer negative charge density from Cs to other metal cations in Cs/Co/Ce-Sn, which will facilitate the production of more oxygen defects and the generation of more surface-active oxygen species. Surface-active oxygen species are beneficial to the oxidation of NO to NO2, leading to the high yield of NO2 exploitation. Therefore, the Cs/Co/Ce-Sn catalyst calcined at 750 ℃ demonstrated higher activity than that calcined at 500 ℃. This work provides a pathway to prepare high efficiency catalysts for the removal of soot and significant insight into the effects of calcination on soot oxidation catalysts.
Catalytic oxidation of soot is of great importance for emission control on diesel vehicles. In this work, a highly active Cs/Co/Ce-Sn catalyst was investigated for soot oxidation, and it was unexpectedly found that high-temperature calcination greatly improved the activity of the catalyst. When the calcination temperature was increased from 500 ℃ to 750 ℃, T50 decreased from 456.9 ℃ to 389.8 ℃ in a NO/O2/H2O/N2 atmosphere. Characterization results revealed that high-temperature calcination can promote the ability to transfer negative charge density from Cs to other metal cations in Cs/Co/Ce-Sn, which will facilitate the production of more oxygen defects and the generation of more surface-active oxygen species. Surface-active oxygen species are beneficial to the oxidation of NO to NO2, leading to the high yield of NO2 exploitation. Therefore, the Cs/Co/Ce-Sn catalyst calcined at 750 ℃ demonstrated higher activity than that calcined at 500 ℃. This work provides a pathway to prepare high efficiency catalysts for the removal of soot and significant insight into the effects of calcination on soot oxidation catalysts.
2025, 36(1): 109934
doi: 10.1016/j.cclet.2024.109934
Abstract:
Zirconium-based metal-organic cages (Zr-MOCs) typically exhibit high stability, but their structural and application reports are scarce due to stringent crystallization conditions. We have successfully fluorinated the classical Zr-MOCs (ZrT-3) for the first time, obtaining the fluorinated MOCs (ZrT-3-F). Notably, ZrT-3-F not only inherits the high stability of its parent structure, but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time. The reaction can reach a conversion rate of 99% in 6 h, and the selectivity reaches 95%, which far exceeds the non-fluorinated ZrT-3. This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential, such as catalysis.
Zirconium-based metal-organic cages (Zr-MOCs) typically exhibit high stability, but their structural and application reports are scarce due to stringent crystallization conditions. We have successfully fluorinated the classical Zr-MOCs (ZrT-3) for the first time, obtaining the fluorinated MOCs (ZrT-3-F). Notably, ZrT-3-F not only inherits the high stability of its parent structure, but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time. The reaction can reach a conversion rate of 99% in 6 h, and the selectivity reaches 95%, which far exceeds the non-fluorinated ZrT-3. This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential, such as catalysis.
2025, 36(1): 109985
doi: 10.1016/j.cclet.2024.109985
Abstract:
Metal-organic frameworks (MOFs) with superior physicochemical properties have great potential for applications in chromatographic separation. However, currently popular methods for the synthesis of MOF-based silica composite materials usually require the use of harmful organic solvents and long-term high-temperature sealing reactions. In order to respond to the needs of green chromatography, it is urgent to develop a new green organic-solvent-free strategy for the synthesis of MOF@SiO2 composites. MIP-202 is a zirconium-MOF constructed from zirconium ion and l-aspartic acid, which features green synthesis as well as good hydrolytic stability and chemical stability. In this paper, SiO2-NH2 was first prepared in a hydrophilic deep eutectic solvent, and then an amino acid-based MOF material (MIP-202) was modified on the surface of the SiO2-NH2 in an aqueous solution to obtain a MIP-202@SiO2 composite material. The multi-mode separation performance of MIP-202@SiO2 as a promising liquid chromatographic stationary phase was particularly evaluated and the separation mechanisms were discussed. The MIP-202@SiO2 column exhibited excellent separation ability for aromatic positional isomers. In addition, chiral enantiomers and hydrophilic analytes were also satisfactorily detected and separated. This work provides a new approach for the facile synthesis of MOF-based liquid chromatographic separation material by using green deep eutectic solvent and water as the reaction media.
Metal-organic frameworks (MOFs) with superior physicochemical properties have great potential for applications in chromatographic separation. However, currently popular methods for the synthesis of MOF-based silica composite materials usually require the use of harmful organic solvents and long-term high-temperature sealing reactions. In order to respond to the needs of green chromatography, it is urgent to develop a new green organic-solvent-free strategy for the synthesis of MOF@SiO2 composites. MIP-202 is a zirconium-MOF constructed from zirconium ion and l-aspartic acid, which features green synthesis as well as good hydrolytic stability and chemical stability. In this paper, SiO2-NH2 was first prepared in a hydrophilic deep eutectic solvent, and then an amino acid-based MOF material (MIP-202) was modified on the surface of the SiO2-NH2 in an aqueous solution to obtain a MIP-202@SiO2 composite material. The multi-mode separation performance of MIP-202@SiO2 as a promising liquid chromatographic stationary phase was particularly evaluated and the separation mechanisms were discussed. The MIP-202@SiO2 column exhibited excellent separation ability for aromatic positional isomers. In addition, chiral enantiomers and hydrophilic analytes were also satisfactorily detected and separated. This work provides a new approach for the facile synthesis of MOF-based liquid chromatographic separation material by using green deep eutectic solvent and water as the reaction media.
2025, 36(1): 110047
doi: 10.1016/j.cclet.2024.110047
Abstract:
Recently circularly polarized luminescence (CPL) materials have attracted significant interest. Introducing reversible dynamic property to these materials has been a key focus in cutting-edge fields, such as in high-level information encryption. Here, we provided a novel and general strategy involving handedness-selective filtration and ground-state chiral self-recovery (CSR) in double film system to address this issue. Based on this strategy, we achieved CPL switch through the reversible modulation of ground-state chirality including absorption and scattering circular dichroism (CD) signals over the full UV-visible wavelength range (365-700 nm) in a single azobenzene polymer (PAzo) film. More importantly, by flexibly changing the type of fluorescent films, it is convenient to achieve general excited-state CSR, that is reversible switching of full-color including ideal white (CIE coordinate (0.33, 0.33)), as well as room-temperature phosphorescent CPL. All these CPL signals without almost any intensity decay after three cycles of on-and-off switching. Experimental results indicated that the trans-cis isomerization and ordered rearrangement of azobenzene units in PAzo film were the fundamental reasons for realizing CPL switching. Finally, based on this system we achieved dynamic visual encryption and decryption process including multiple decryption methods. This study provides an effective method for constructing a universally applicable chiroptical switch in excited state.
Recently circularly polarized luminescence (CPL) materials have attracted significant interest. Introducing reversible dynamic property to these materials has been a key focus in cutting-edge fields, such as in high-level information encryption. Here, we provided a novel and general strategy involving handedness-selective filtration and ground-state chiral self-recovery (CSR) in double film system to address this issue. Based on this strategy, we achieved CPL switch through the reversible modulation of ground-state chirality including absorption and scattering circular dichroism (CD) signals over the full UV-visible wavelength range (365-700 nm) in a single azobenzene polymer (PAzo) film. More importantly, by flexibly changing the type of fluorescent films, it is convenient to achieve general excited-state CSR, that is reversible switching of full-color including ideal white (CIE coordinate (0.33, 0.33)), as well as room-temperature phosphorescent CPL. All these CPL signals without almost any intensity decay after three cycles of on-and-off switching. Experimental results indicated that the trans-cis isomerization and ordered rearrangement of azobenzene units in PAzo film were the fundamental reasons for realizing CPL switching. Finally, based on this system we achieved dynamic visual encryption and decryption process including multiple decryption methods. This study provides an effective method for constructing a universally applicable chiroptical switch in excited state.
2025, 36(1): 110083
doi: 10.1016/j.cclet.2024.110083
Abstract:
Chloroform is a common and excellent solvent for preparing high-efficient organic solar cells (OSCs), however, it is toxic and poisonable chemical. In comparisons, deuterated chloroform (DC) is less toxic and costly, and particularly, it is non-poisonable chemical. In this paper, we use DC to replace ultra-dry chloroform (UC) as the processing solvent for preparation of active layers of organic solar cells. First, we selected PM6:BTP-eC9 as the basic binary and counted 100 solar cells' data, from which comparable device performance were obtained with use of DC and UC. Interestingly, DC showed better reproducibility, superior storage under a nitrogen atmosphere and a little better performance than UC. Both DC and UC gave rise of comparable hole and electron mobilities and similar charge recombination losses. Second, we based PM6:Y6 and D18-Cl: Y6 as the binaries and similar effects were obtained from both UC and DC when counting 30 devices for each binary. Third, the universality of the use of DC for preparing high-efficient OSCs were again checked with several binary and ternary systems. In all, this study demonstrate that DC can replace UC for use in the field of OSCs.
Chloroform is a common and excellent solvent for preparing high-efficient organic solar cells (OSCs), however, it is toxic and poisonable chemical. In comparisons, deuterated chloroform (DC) is less toxic and costly, and particularly, it is non-poisonable chemical. In this paper, we use DC to replace ultra-dry chloroform (UC) as the processing solvent for preparation of active layers of organic solar cells. First, we selected PM6:BTP-eC9 as the basic binary and counted 100 solar cells' data, from which comparable device performance were obtained with use of DC and UC. Interestingly, DC showed better reproducibility, superior storage under a nitrogen atmosphere and a little better performance than UC. Both DC and UC gave rise of comparable hole and electron mobilities and similar charge recombination losses. Second, we based PM6:Y6 and D18-Cl: Y6 as the binaries and similar effects were obtained from both UC and DC when counting 30 devices for each binary. Third, the universality of the use of DC for preparing high-efficient OSCs were again checked with several binary and ternary systems. In all, this study demonstrate that DC can replace UC for use in the field of OSCs.
2025, 36(1): 110099
doi: 10.1016/j.cclet.2024.110099
Abstract:
Metal complexes hold significant promise in tumor diagnosis and treatment. However, their potential applications in photodynamic therapy (PDT) are hindered by issues such as poor photostability, low yield of reactive oxygen species (ROS), and aggregation-induced ROS quenching. To address these challenges, we present a molecular self-assembly strategy utilizing aggregation-induced emission (AIE) conjugates for metal complexes. As a proof of concept, we synthesized a mitochondrial-targeting cyclometalated Ir(III) photosensitizer Ir-TPE. This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups. Ir-TPE readily self-assembles into nanoaggregates in aqueous solution, leading to a significant production of ROS upon light irradiation. Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria, resulting in mitochondrial DNA damage. This damage can lead to ferroptosis and autophagy, two forms of cell death that are highly cytotoxic to cancer cells. The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS, leading to a more pronounced cytotoxic effect. In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication. This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.
Metal complexes hold significant promise in tumor diagnosis and treatment. However, their potential applications in photodynamic therapy (PDT) are hindered by issues such as poor photostability, low yield of reactive oxygen species (ROS), and aggregation-induced ROS quenching. To address these challenges, we present a molecular self-assembly strategy utilizing aggregation-induced emission (AIE) conjugates for metal complexes. As a proof of concept, we synthesized a mitochondrial-targeting cyclometalated Ir(III) photosensitizer Ir-TPE. This approach significantly enhances the photodynamic effect while mitigating the dark toxicity associated with AIE groups. Ir-TPE readily self-assembles into nanoaggregates in aqueous solution, leading to a significant production of ROS upon light irradiation. Photoirradiated Ir-TPE triggers multiple modes of death by excessively accumulating ROS in the mitochondria, resulting in mitochondrial DNA damage. This damage can lead to ferroptosis and autophagy, two forms of cell death that are highly cytotoxic to cancer cells. The aggregation-enhanced photodynamic effect of Ir-TPE significantly enhances the production of ROS, leading to a more pronounced cytotoxic effect. In vitro and in vivo experiments demonstrate this aggregation-enhanced PDT approach achieves effective in situ tumor eradication. This study not only addresses the limitations of metal complexes in terms of low ROS production due to aggregation but also highlights the potential of this strategy for enhancing ROS production in PDT.
2025, 36(1): 110123
doi: 10.1016/j.cclet.2024.110123
Abstract:
In our work, polymorphism strategy has been successfully applied to tune up chromism and luminescence properties of viologen-based materials. Two polymorphs of viologen-based complexes of α-CdBr2(PHSQ)2(H2O)2 (1) and β-CdBr2(PHSQ)2(H2O)2 (2) (PHSQ = N-(4-sulfophenyl)-4,4′-bipyridinium) were synthesized by changing the solvent. They can both respond to UV light and electricity in the manner of chromism visible to the naked eye and the coloration states have good reversibility, through which an inkless erasable printing model has been established. But the coloration contrast of 1 is higher compared to 2. Meanwhile, they both exhibit photoluminescence properties and the intensity of 1 is twice that of 2, which is accompanied by photoquenching upon continuous UV light irradiation. The only divergence of disordered/ordered O atoms in the two crystalline compounds leads to significantly different chromic and luminescent properties. Further explorations simultaneously demonstrate that the different chromic performance between 1 and 2 should attribute to the alteration of stimulus-induced (light/ electricity) electron transfer channels caused by the ordered/disordered O atoms in the complexes, which is achieved through CH···O and OH···O interactions to change crystal arrangement and structural rigidity, thus affect luminescent properties.
In our work, polymorphism strategy has been successfully applied to tune up chromism and luminescence properties of viologen-based materials. Two polymorphs of viologen-based complexes of α-CdBr2(PHSQ)2(H2O)2 (1) and β-CdBr2(PHSQ)2(H2O)2 (2) (PHSQ = N-(4-sulfophenyl)-4,4′-bipyridinium) were synthesized by changing the solvent. They can both respond to UV light and electricity in the manner of chromism visible to the naked eye and the coloration states have good reversibility, through which an inkless erasable printing model has been established. But the coloration contrast of 1 is higher compared to 2. Meanwhile, they both exhibit photoluminescence properties and the intensity of 1 is twice that of 2, which is accompanied by photoquenching upon continuous UV light irradiation. The only divergence of disordered/ordered O atoms in the two crystalline compounds leads to significantly different chromic and luminescent properties. Further explorations simultaneously demonstrate that the different chromic performance between 1 and 2 should attribute to the alteration of stimulus-induced (light/ electricity) electron transfer channels caused by the ordered/disordered O atoms in the complexes, which is achieved through CH···O and OH···O interactions to change crystal arrangement and structural rigidity, thus affect luminescent properties.
2025, 36(1): 110169
doi: 10.1016/j.cclet.2024.110169
Abstract:
Quantitative determination of tetracycline (TC) in environment and foods is of great importance, as excessive residues might have negative effects on human health and environmental risks. Herein, a self-powered molecularly imprinted photoelectrochemical (PEC) sensor based on the ZnO/C photoanode and the Fe-doped CuBi2O4 (CBFO) photocathode is developed for the sensitive detection of TC. The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode. Furthermore, molecularly imprinted polymers (MIPs) at photocathode can selectivity identify the TC templates and thus improve the specificity. Under the optimal conditions, the sensor has a linear range of 10‒2–1.0 × 105 nmol/L, and a limit of detection (LOD) of 0.007 nmol/L (S/N = 3). More crucially, the milk sample detection is carried out using the as-prepared sensor, and the outcome is satisfactory. The research gives us a novel sensing platform for quick and accurate antibiotic (like TC) in environment and food monitoring.
Quantitative determination of tetracycline (TC) in environment and foods is of great importance, as excessive residues might have negative effects on human health and environmental risks. Herein, a self-powered molecularly imprinted photoelectrochemical (PEC) sensor based on the ZnO/C photoanode and the Fe-doped CuBi2O4 (CBFO) photocathode is developed for the sensitive detection of TC. The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode. Furthermore, molecularly imprinted polymers (MIPs) at photocathode can selectivity identify the TC templates and thus improve the specificity. Under the optimal conditions, the sensor has a linear range of 10‒2–1.0 × 105 nmol/L, and a limit of detection (LOD) of 0.007 nmol/L (S/N = 3). More crucially, the milk sample detection is carried out using the as-prepared sensor, and the outcome is satisfactory. The research gives us a novel sensing platform for quick and accurate antibiotic (like TC) in environment and food monitoring.
2025, 36(1): 110174
doi: 10.1016/j.cclet.2024.110174
Abstract:
Diradicaloid polycyclic hydrocarbons (PHs) own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics. Herein, we disclose precise fusion of B/O-heterocycles onto PHs for control over their electronic structures and diradical properties. We designed and synthesized four B/O-containing diradicaloid isomers that feature the fluoreno[3,2-b]fluorene and fluoreno[2,1-a]fluorene π-skeletons, respectively. The precise B/O-heterocycle fusion modes along with the changed conjugation patterns lead to their modulated electronic structures and properties, such as diradical and aromatic structures, energy levels and band gaps, as well as magnetic, electrochemical and photophysical properties. Notably, the mode A may decrease the open-shell extent, whereas the mode B can enhance the diradical nature, leading to their well-tuned diradical characters in the range of 0.46‒0.70. Moreover, the mode A stabilizes the LUMOs and the mode B obviously increases the HOMO levels, which are remarkably contributed by the B and O atoms, respectively, further giving rise to the decreased band gaps and redshifted absorptions. This study clearly illustrates the electronic effects of B/O-heterocycle fusion on PHs and gains insight into B/O-type organic diradicaloids. These findings will provide an important guideline for the design of more fascinating heteroatom-containing diradicaloids.
Diradicaloid polycyclic hydrocarbons (PHs) own unique open-shell electronic structures and exhibit potential utility in the fields of organic electronics and spintronics. Herein, we disclose precise fusion of B/O-heterocycles onto PHs for control over their electronic structures and diradical properties. We designed and synthesized four B/O-containing diradicaloid isomers that feature the fluoreno[3,2-b]fluorene and fluoreno[2,1-a]fluorene π-skeletons, respectively. The precise B/O-heterocycle fusion modes along with the changed conjugation patterns lead to their modulated electronic structures and properties, such as diradical and aromatic structures, energy levels and band gaps, as well as magnetic, electrochemical and photophysical properties. Notably, the mode A may decrease the open-shell extent, whereas the mode B can enhance the diradical nature, leading to their well-tuned diradical characters in the range of 0.46‒0.70. Moreover, the mode A stabilizes the LUMOs and the mode B obviously increases the HOMO levels, which are remarkably contributed by the B and O atoms, respectively, further giving rise to the decreased band gaps and redshifted absorptions. This study clearly illustrates the electronic effects of B/O-heterocycle fusion on PHs and gains insight into B/O-type organic diradicaloids. These findings will provide an important guideline for the design of more fascinating heteroatom-containing diradicaloids.
2025, 36(1): 110175
doi: 10.1016/j.cclet.2024.110175
Abstract:
Copper (Cu) is widely used in the electrochemical carbon dioxide reduction reaction (ECO2RR) for efficient methane (CH4) product. However, the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions. In this work, we prepared Ce-doped MOF-199 precursor (Ce/HKUST-1) and further obtained nanoparticle electrocatalyst Ce/CuOx-NPs by cyclic voltammetry (CV) pretreatment. The Faradic efficiency of methane () maintains above 62% within a broad potential window of 350 mV and the maximum reaches 67.4% with a partial current density of 293 mA/cm2 at −1.6 V vs. a reversible hydrogen electrode. Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium (Ce) not only promoted the generation of key intermediate *CO but also lowered energy barrier of the *CO to *CHO step. This study provides a novel and efficient catalyst for methane production in ECO2RR and offers profound insights into constructing high performance Cu-based catalysts.
Copper (Cu) is widely used in the electrochemical carbon dioxide reduction reaction (ECO2RR) for efficient methane (CH4) product. However, the morphology and valence of Cu-based catalysts are usually unstable under reaction conditions. In this work, we prepared Ce-doped MOF-199 precursor (Ce/HKUST-1) and further obtained nanoparticle electrocatalyst Ce/CuOx-NPs by cyclic voltammetry (CV) pretreatment. The Faradic efficiency of methane () maintains above 62% within a broad potential window of 350 mV and the maximum reaches 67.4% with a partial current density of 293 mA/cm2 at −1.6 V vs. a reversible hydrogen electrode. Catalyst characterization and theoretical calculations revealed that the unique electronic structure and large ionic radius of Cerium (Ce) not only promoted the generation of key intermediate *CO but also lowered energy barrier of the *CO to *CHO step. This study provides a novel and efficient catalyst for methane production in ECO2RR and offers profound insights into constructing high performance Cu-based catalysts.
2025, 36(1): 110204
doi: 10.1016/j.cclet.2024.110204
Abstract:
Membrane electrode assembly (MEA) is widely considered to be the most promising type of electrolyzer for the practical application of electrochemical CO2 reduction reaction (CO2RR). In MEAs, a square-shaped cross-section in the flow channel is normally adopted, the configuration optimization of which could potentially enhance the performance of the electrolyzer. This paper describes the numerical simulation study on the impact of the flow-channel cross-section shapes in the MEA electrolyzer for CO2RR. The results show that wide flow channels with low heights are beneficial to the CO2RR by providing a uniform flow field of CO2, especially at high current densities. Moreover, the larger the electrolyzer, the more significant the effect is. This study provides a theoretical basis for the design of high-performance MEA electrolyzers for CO2RR.
Membrane electrode assembly (MEA) is widely considered to be the most promising type of electrolyzer for the practical application of electrochemical CO2 reduction reaction (CO2RR). In MEAs, a square-shaped cross-section in the flow channel is normally adopted, the configuration optimization of which could potentially enhance the performance of the electrolyzer. This paper describes the numerical simulation study on the impact of the flow-channel cross-section shapes in the MEA electrolyzer for CO2RR. The results show that wide flow channels with low heights are beneficial to the CO2RR by providing a uniform flow field of CO2, especially at high current densities. Moreover, the larger the electrolyzer, the more significant the effect is. This study provides a theoretical basis for the design of high-performance MEA electrolyzers for CO2RR.
2025, 36(1): 110222
doi: 10.1016/j.cclet.2024.110222
Abstract:
Highly toxic phosgene, diethyl chlorophosphate (DCP) and volatile acyl chlorides endanger our life and public security. To achieve facile sensing and discrimination of multiple target analytes, herein, we presented a single fluorescent probe (BDP-CHD) for high-throughput screening of phosgene, DCP and volatile acyl chlorides. The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene (BODIPY) with bright green fluorescence. By contrast, DCP, diphosgene and acyl chlorides can covalently assembled with the probe, giving rise to strong blue fluorescence. The probe has demonstrated high-throughput detection capability, high sensitivity, fast response (within 3 s) and parts per trillion (ppt) level detection limit. Furthermore, a portable platform based on BDP-CHD was constructed, which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis (LDA). Moreover, a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes. Therefore, this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene, DCP and volatile acyl chlorides. The proposed "one for more" strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.
Highly toxic phosgene, diethyl chlorophosphate (DCP) and volatile acyl chlorides endanger our life and public security. To achieve facile sensing and discrimination of multiple target analytes, herein, we presented a single fluorescent probe (BDP-CHD) for high-throughput screening of phosgene, DCP and volatile acyl chlorides. The probe underwent a covalent cascade reaction with phosgene to form boron dipyrromethene (BODIPY) with bright green fluorescence. By contrast, DCP, diphosgene and acyl chlorides can covalently assembled with the probe, giving rise to strong blue fluorescence. The probe has demonstrated high-throughput detection capability, high sensitivity, fast response (within 3 s) and parts per trillion (ppt) level detection limit. Furthermore, a portable platform based on BDP-CHD was constructed, which has achieved high-throughput discrimination of 16 analytes through linear discriminant analysis (LDA). Moreover, a smartphone adaptable RGB recognition pattern was established for the quantitative detection of multi-analytes. Therefore, this portable fluorescence sensing platform can serve as a versatile tool for rapid and high-throughput detection of toxic phosgene, DCP and volatile acyl chlorides. The proposed "one for more" strategy simplifies multi-target discrimination procedures and holds great promise for various sensing applications.
2025, 36(1): 110223
doi: 10.1016/j.cclet.2024.110223
Abstract:
The dysbiosis of oral microbiota contributes to diseases such as periodontitis and certain cancers by triggering the host inflammatory response. Developing methods for the immediate and sensitive identification of oral microorganism is crucial for the rapid diagnosis and early interventions of associated diseases. Traditional methods for microbial detection primarily include the plate culturing, polymerase chain reaction and enzyme-linked immunosorbent assay, which are either time-consuming or laborious. Herein, we reported a persistent luminescence-encoded multiple-channel optical sensing array and achieved the rapid and accurate identification of oral-derived microorganisms. Our results demonstrate that electrostatic attractions and hydrophobic-hydrophobic interactions dominate the binding of the persistent luminescent nanoprobes to oral microorganisms and the microbial identification process can be finished within 30 min. Specifically, a total of 7 oral-derived microorganisms demonstrate their own response patterns and were differentiated by linear discriminant analysis (LDA) with the accuracy up to 100% both in the solution and artificial saliva samples. Moreover, the persistent luminescence encoded array sensor could also discern the microorganism mixtures with the accuracy up to 100%. The proposed persistent luminescence encoding sensor arrays in this work might offer new ideas for rapid and accurate oral-derived microorganism detection, and provide new ways for disease diagnosis associated with microbial metabolism.
The dysbiosis of oral microbiota contributes to diseases such as periodontitis and certain cancers by triggering the host inflammatory response. Developing methods for the immediate and sensitive identification of oral microorganism is crucial for the rapid diagnosis and early interventions of associated diseases. Traditional methods for microbial detection primarily include the plate culturing, polymerase chain reaction and enzyme-linked immunosorbent assay, which are either time-consuming or laborious. Herein, we reported a persistent luminescence-encoded multiple-channel optical sensing array and achieved the rapid and accurate identification of oral-derived microorganisms. Our results demonstrate that electrostatic attractions and hydrophobic-hydrophobic interactions dominate the binding of the persistent luminescent nanoprobes to oral microorganisms and the microbial identification process can be finished within 30 min. Specifically, a total of 7 oral-derived microorganisms demonstrate their own response patterns and were differentiated by linear discriminant analysis (LDA) with the accuracy up to 100% both in the solution and artificial saliva samples. Moreover, the persistent luminescence encoded array sensor could also discern the microorganism mixtures with the accuracy up to 100%. The proposed persistent luminescence encoding sensor arrays in this work might offer new ideas for rapid and accurate oral-derived microorganism detection, and provide new ways for disease diagnosis associated with microbial metabolism.
2025, 36(1): 110232
doi: 10.1016/j.cclet.2024.110232
Abstract:
Rational design of viable routes to obtain efficient and stable oxygen evolution reaction (OER) electrocatalysts remains challenging, especially under industrial conditions. Here, we provide a solvent-steam assisted corrosion engineering strategy to directly fabricate high-entropy NiFe-LDH with spatially resolved structural order. Ammonium fluoride in methanol steam enables the formation of nanosheets while Fe3+ effectively enhances their adhesion to the semi-sacrificial nickel-iron foam (NFF), thereby conjuring up a NiFe-LDH@NFF catalyst that exhibits remarkable adaptability to robust electrochemical activation yet with excellent stability. Comprehensive measurements reveal the in-situ formation of high-valance metal oxyhydroxide and the enhancement of adsorption-desorption process. Under the industrial condition (6 mol/L KOH, 60 ℃), the NiFe-LDH@NFF exhibits excellent activity of 50 mA/cm2 at 1.55 V and high durability of over 120 h at 200 mA/cm2. We anticipate that the steam assisted strategy could promote the development of efficient non-precious electrocatalysts for hydrogen energy.
Rational design of viable routes to obtain efficient and stable oxygen evolution reaction (OER) electrocatalysts remains challenging, especially under industrial conditions. Here, we provide a solvent-steam assisted corrosion engineering strategy to directly fabricate high-entropy NiFe-LDH with spatially resolved structural order. Ammonium fluoride in methanol steam enables the formation of nanosheets while Fe3+ effectively enhances their adhesion to the semi-sacrificial nickel-iron foam (NFF), thereby conjuring up a NiFe-LDH@NFF catalyst that exhibits remarkable adaptability to robust electrochemical activation yet with excellent stability. Comprehensive measurements reveal the in-situ formation of high-valance metal oxyhydroxide and the enhancement of adsorption-desorption process. Under the industrial condition (6 mol/L KOH, 60 ℃), the NiFe-LDH@NFF exhibits excellent activity of 50 mA/cm2 at 1.55 V and high durability of over 120 h at 200 mA/cm2. We anticipate that the steam assisted strategy could promote the development of efficient non-precious electrocatalysts for hydrogen energy.
2025, 36(1): 110233
doi: 10.1016/j.cclet.2024.110233
Abstract:
Benzotriazole (BTA)-based A2-A1-D-A1-A2 type wide-bandgap (WBG) non-fullerene acceptors (NFAs) have shown promising potential in indoor photovoltaic, and in-depth investigation of their structure-property relationship is of great significance. Herein, we explored the chlorination effect of the side chain on the terminals. We introduced Cl atoms into the benzyl side chains in parent BTA5 to synthesize two NFAs, BTA5-Cl with mono-chlorinated benzyl groups and BTA5-2Cl containing bi-chlorinated benzyl groups. We chose D18-Cl with deep-energy levels and strong crystallinity to pair with these three acceptors, affording high photovoltage and photocurrent. With the stepwise chlorination, the open-circuit voltage (VOC) values decrease from 1.28, 1.22, to 1.20 V, while the corresponding power conversion efficiencies (PCEs) improve from 5.07%, 9.15%, to 10.96%. Compared with BTA5-based OSCs, introducing Cl atoms downshifts the energy levels and slightly increases the non-radiative energy loss (0.14 < 0.17 < 0.19 eV), resulting in a sequential decrease in VOC. However, more chlorine atom replacements produce more effective exciton dissociation, higher charge transfer, and balanced carrier mobility in the blend films, ultimately achieving better PCEs. This work indicates that chlorination of the benzyl group on the terminals can improve the device's performance, implying good application potential in indoor photovoltaics.
Benzotriazole (BTA)-based A2-A1-D-A1-A2 type wide-bandgap (WBG) non-fullerene acceptors (NFAs) have shown promising potential in indoor photovoltaic, and in-depth investigation of their structure-property relationship is of great significance. Herein, we explored the chlorination effect of the side chain on the terminals. We introduced Cl atoms into the benzyl side chains in parent BTA5 to synthesize two NFAs, BTA5-Cl with mono-chlorinated benzyl groups and BTA5-2Cl containing bi-chlorinated benzyl groups. We chose D18-Cl with deep-energy levels and strong crystallinity to pair with these three acceptors, affording high photovoltage and photocurrent. With the stepwise chlorination, the open-circuit voltage (VOC) values decrease from 1.28, 1.22, to 1.20 V, while the corresponding power conversion efficiencies (PCEs) improve from 5.07%, 9.15%, to 10.96%. Compared with BTA5-based OSCs, introducing Cl atoms downshifts the energy levels and slightly increases the non-radiative energy loss (0.14 < 0.17 < 0.19 eV), resulting in a sequential decrease in VOC. However, more chlorine atom replacements produce more effective exciton dissociation, higher charge transfer, and balanced carrier mobility in the blend films, ultimately achieving better PCEs. This work indicates that chlorination of the benzyl group on the terminals can improve the device's performance, implying good application potential in indoor photovoltaics.
2025, 36(1): 110235
doi: 10.1016/j.cclet.2024.110235
Abstract:
The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center. Therefore, the electronic conductivity is a vital parameter for oxygen reduction reaction (ORR). Covalent triazine frameworks (CTFs) have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks. However, the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application. Herein, CTFs were constructed by introducing F and N co-modification for efficient 2e− ORR. Compared with the pristine CTF, the co-presence of F, N could increase the conductivity obviously by 1000-fold. As a result, F-N-CTF exhibits enhanced catalytic performance of H2O2 generation and selectivity towards reaction pathways. This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e− ORR.
The high conductivity of electrocatalyst can eliminate the Schottky energy barrier at the interface of heterogeneous phases during an electrocatalytic reaction and accelerate the rapid electron transfer to the catalytic active center. Therefore, the electronic conductivity is a vital parameter for oxygen reduction reaction (ORR). Covalent triazine frameworks (CTFs) have shown great potential application as electrocatalysts in ORR with a merit of the diverse building blocks. However, the intrinsic low conductivity and high impedance of CTFs could be significant setbacks in electrocatalytic application. Herein, CTFs were constructed by introducing F and N co-modification for efficient 2e− ORR. Compared with the pristine CTF, the co-presence of F, N could increase the conductivity obviously by 1000-fold. As a result, F-N-CTF exhibits enhanced catalytic performance of H2O2 generation and selectivity towards reaction pathways. This work reveals the importance of conductivity optimization for CTFs and provides guidance for designing high conductivity non-metallic organic semiconductor catalysts for 2e− ORR.
2025, 36(1): 110236
doi: 10.1016/j.cclet.2024.110236
Abstract:
The synthesis of polyurethanes (PUs) from the reaction of low molecular weight poly(ethylene carbonate) diol (PECD) is rarely investigated. This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4′-diphenylmethane diisocyanate (MDI) with PECD that was derived from the copolymerization of carbon dioxide (CO2) and ethylene oxide (EO). The tensile strength, the elongation at break and 300% constant tensile strength of the PECD-PU were up to 66 ± 2 MPa, 880% ± 50% and 13 MPa, respectively, higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters. The PECD-PU with high CO2 carbonate content exhibited good solvent resistance and chemical stability. Of importance, the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO2, i.e., the carbonate unit in PECD. This work provides comprehensive properties of PECD-derived PUs, indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.
The synthesis of polyurethanes (PUs) from the reaction of low molecular weight poly(ethylene carbonate) diol (PECD) is rarely investigated. This work reports a novel PU with excellent mechanical properties from the solution polymerization of 4,4′-diphenylmethane diisocyanate (MDI) with PECD that was derived from the copolymerization of carbon dioxide (CO2) and ethylene oxide (EO). The tensile strength, the elongation at break and 300% constant tensile strength of the PECD-PU were up to 66 ± 2 MPa, 880% ± 50% and 13 MPa, respectively, higher than the control PUs from the reaction of MDI with commercial polyethers or polyesters. The PECD-PU with high CO2 carbonate content exhibited good solvent resistance and chemical stability. Of importance, the mechanical properties and chemical resistance of PECD-PU were significantly enhanced with the increasing content of CO2, i.e., the carbonate unit in PECD. This work provides comprehensive properties of PECD-derived PUs, indicating that PECD is a competitive precursor for the preparation of PU and has broad application prospects.
2025, 36(1): 110279
doi: 10.1016/j.cclet.2024.110279
Abstract:
Atomically precise metal nanoclusters (NCs) have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner, quantum confinement effects, light-harvesting capability and multitude of active sites. Nonetheless, wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan, uncontrollable charge transport pathway, and light-induced poor stability, impeding the construction of robust and stable metal NC-based photosystems. Herein, we report the fabrication of stable alloy (Au1-xPtx) NCs photosystem, for which tailor-made negatively charged l-glutathione (GSH)-capped Au1-xPtx NCs as the building blocks are controllably deposited on the BiVO4 (BVO) by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes (Au1-xPtx/BVO). The self-assembled Au1-xPtx/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Aux/BVO photoanodes, which is caused by the Pt atom doping into the Aux NCs for elevating photosensitivity and boosting the stability. The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation, improving the photostability and accelerating the surface charge transfer kinetics. Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.
Atomically precise metal nanoclusters (NCs) have been deemed as a new generation of metal nanomaterials in the field of solar energy conversion due to their unique atomic stacking manner, quantum confinement effects, light-harvesting capability and multitude of active sites. Nonetheless, wide-spread application of monometallic NCs is blocked by the ultrashort carrier lifespan, uncontrollable charge transport pathway, and light-induced poor stability, impeding the construction of robust and stable metal NC-based photosystems. Herein, we report the fabrication of stable alloy (Au1-xPtx) NCs photosystem, for which tailor-made negatively charged l-glutathione (GSH)-capped Au1-xPtx NCs as the building blocks are controllably deposited on the BiVO4 (BVO) by a self-assembly approach for steering enhanced light absorption and interfacial charge transfer over alloy NCs-based photoanodes (Au1-xPtx/BVO). The self-assembled Au1-xPtx/BVO composite photoanode exhibits the significantly enhanced photoelectrochemical water oxidation performances compared with pristine BVO and Aux/BVO photoanodes, which is caused by the Pt atom doping into the Aux NCs for elevating photosensitivity and boosting the stability. The synergy of Au and Pt atoms in alloy NCs protects the gold core from rapid oxidation, improving the photostability and accelerating the surface charge transfer kinetics. Our work would significantly inspire ongoing interest in unlocking the charge transport characteristics of atomically precise alloy NCs for solar energy conversion.
2025, 36(1): 110288
doi: 10.1016/j.cclet.2024.110288
Abstract:
Photocatalytic overall pure water splitting is a promising method for generating green hydrogen energy under mild conditions. However, this process is often hindered by sluggish electron-hole separation and transport. To address this, a step-scheme (S-scheme) B-doped N-deficient C3N4/O-doped C3N5 (BN-C3N4/O-C3N5) heterojunction with interfacial B-O bonds has been constructed. Utilizing Pt and Co(OH)2 as co-catalysts, BN-C3N4/O-C3N5 S-scheme heterojunction demonstrates significantly enhanced photocatalytic activity for overall pure water splitting under visible light, achieving H2 and O2 evolution rates of 40.12 and 19.62 µmol/h, respectively. Systematic characterizations and experiments revealed the performance-enhancing effects of the enhanced built-in electric field and the interfacial B-O bonding. Firstly, the strengthened built-in electric field provides sufficient force for rapid interfacial electron transport. Secondly, by reducing the transport energy barrier and transfer distance, the interfacial B-O bonds facilitate rapid recombination of electrons and holes with relatively low redox potential via the S-scheme charge-transfer route, leaving the high-potential electrons and holes available for H+ reduction and OH− oxidation reactions. Overall, the photocatalytic efficiency of BN-C3N4/O-C3N5 S-scheme heterojunction was significantly improved, making it a promising approach for green hydrogen production through overall pure water splitting.
Photocatalytic overall pure water splitting is a promising method for generating green hydrogen energy under mild conditions. However, this process is often hindered by sluggish electron-hole separation and transport. To address this, a step-scheme (S-scheme) B-doped N-deficient C3N4/O-doped C3N5 (BN-C3N4/O-C3N5) heterojunction with interfacial B-O bonds has been constructed. Utilizing Pt and Co(OH)2 as co-catalysts, BN-C3N4/O-C3N5 S-scheme heterojunction demonstrates significantly enhanced photocatalytic activity for overall pure water splitting under visible light, achieving H2 and O2 evolution rates of 40.12 and 19.62 µmol/h, respectively. Systematic characterizations and experiments revealed the performance-enhancing effects of the enhanced built-in electric field and the interfacial B-O bonding. Firstly, the strengthened built-in electric field provides sufficient force for rapid interfacial electron transport. Secondly, by reducing the transport energy barrier and transfer distance, the interfacial B-O bonds facilitate rapid recombination of electrons and holes with relatively low redox potential via the S-scheme charge-transfer route, leaving the high-potential electrons and holes available for H+ reduction and OH− oxidation reactions. Overall, the photocatalytic efficiency of BN-C3N4/O-C3N5 S-scheme heterojunction was significantly improved, making it a promising approach for green hydrogen production through overall pure water splitting.
2025, 36(1): 110289
doi: 10.1016/j.cclet.2024.110289
Abstract:
Precise tumor targeting and therapy is a major trend in cancer treatment. Herein, we designed a tumor acidic microenvironment activatable drug loaded DNA nanostructure, in which, we made a clever use of the sequences of AS1411 and i-motif, which can partially hybridize, and designed a simple while robust DNA d-strand nanostructure, in which, i-motif sequence was designed to regulate the binding ability of the AS1411 aptamer to target tumor. In the normal physiological environment, i-motif inhibits the targeting ability of AS1411. In the acidic tumor microenvironment, i-motif forms a quadruplex conformation and dissociates from AS1411, restoring the targeting ability of AS1411. Only when acidic condition and tumor cell receptor are present, this nanostructure can be internalized by the tumor cells. Moreover, the structure change of this nanostructure can realize the release of loaded drug. This drug loaded A-I-Duplex DNA structure showed cancer cell and spheroid targeting and inhibition ability, which is promising in the clinical cancer therapy.
Precise tumor targeting and therapy is a major trend in cancer treatment. Herein, we designed a tumor acidic microenvironment activatable drug loaded DNA nanostructure, in which, we made a clever use of the sequences of AS1411 and i-motif, which can partially hybridize, and designed a simple while robust DNA d-strand nanostructure, in which, i-motif sequence was designed to regulate the binding ability of the AS1411 aptamer to target tumor. In the normal physiological environment, i-motif inhibits the targeting ability of AS1411. In the acidic tumor microenvironment, i-motif forms a quadruplex conformation and dissociates from AS1411, restoring the targeting ability of AS1411. Only when acidic condition and tumor cell receptor are present, this nanostructure can be internalized by the tumor cells. Moreover, the structure change of this nanostructure can realize the release of loaded drug. This drug loaded A-I-Duplex DNA structure showed cancer cell and spheroid targeting and inhibition ability, which is promising in the clinical cancer therapy.
2025, 36(1): 110299
doi: 10.1016/j.cclet.2024.110299
Abstract:
In this work, we developed plasmonic photocatalyst composed of CuPd alloy nanoparticles supported on TiN, the optimized Cu3Pd2/TiN catalyst shows excellent conversion (> 96%) and selectivity (> 99%) for Heck reaction at 50 ℃ under visible light irradiation. By in-situ spectroscopic investigations, we find that visible light excitation could achieve stable metallic Cu species on the surface of CuPd alloy nanoparticles, thereby eliminating the inevitable surface oxides of Cu based catalyst. The in-situ formed metallic Cu species under irradiation take advantage of the strong interactions of Cu with visible light, and manifest in the localized surface plasmon resonances (LSPR) photoexcitation. Visible light excitation could further promote the charge transfer between catalytic Pd component and the support TiN, resulting in electron-rich Pd sites on CuPd/TiN. Moreover, light excitation on CuPd/TiN generates strong chemisorption of iodobenzene and styrene, favoring the activation of reactants for Heck reaction. DFT calculations suggest that electron-rich CuPd sites ideally lower the activation energy barrier for the coupling reaction. This work provides valuable insights for mechanistic understanding of plasmonic photocatalysis.
In this work, we developed plasmonic photocatalyst composed of CuPd alloy nanoparticles supported on TiN, the optimized Cu3Pd2/TiN catalyst shows excellent conversion (> 96%) and selectivity (> 99%) for Heck reaction at 50 ℃ under visible light irradiation. By in-situ spectroscopic investigations, we find that visible light excitation could achieve stable metallic Cu species on the surface of CuPd alloy nanoparticles, thereby eliminating the inevitable surface oxides of Cu based catalyst. The in-situ formed metallic Cu species under irradiation take advantage of the strong interactions of Cu with visible light, and manifest in the localized surface plasmon resonances (LSPR) photoexcitation. Visible light excitation could further promote the charge transfer between catalytic Pd component and the support TiN, resulting in electron-rich Pd sites on CuPd/TiN. Moreover, light excitation on CuPd/TiN generates strong chemisorption of iodobenzene and styrene, favoring the activation of reactants for Heck reaction. DFT calculations suggest that electron-rich CuPd sites ideally lower the activation energy barrier for the coupling reaction. This work provides valuable insights for mechanistic understanding of plasmonic photocatalysis.
2025, 36(1): 110313
doi: 10.1016/j.cclet.2024.110313
Abstract:
In-situ enhanced bioreduction by functional materials is a cost-effective technology to remove chlorinated hydrocarbons in groundwater. Herein, a novel polydopamine (PDA)-modified biochar (BC)-based composite containing nanoscale zero-valent iron (nZVI) and poly-l-lactic acid (PLLA) (PB-PDA-Fe) was synthesized to enhance the removal of 1,1,1-trichloroethane (1,1,1-TCA) in simulated groundwater with actual site sediments. Its impact on functional microbial community structure in system was also investigated. The typical characterizations revealed uniform dispersion of PLA and nZVI particles on the BC surface, being smoother after PDA coating. The composite exhibited a significantly higher performance on 1,1,1-TCA removal (82.38%, initial concentration 100 mg/L) than Fe-PDA and PB-PDA treatments. The diversity and richness of the microbial community in the composite treatment consistently decreased during incubation due to a synergistic effect between PLLA-BC and nZVI. Desulfitobaterium, Pedobacter, Sphaerochaeta, Shewanella, and Clostridium were identified as enriched genera by the composite through DNA-stable isotope probing (DNA-SIP), playing a crucial role in the bioreductive dechlorination process. All the above results demonstrate that this novel composite selectively enhances the activity of microorganisms with extracellular respiration functions to efficiently dechlorinate 1,1,1-TCA. These findings could contribute to understanding the responsive microbial community by carbon-iron composites and expedite the application of in-situ enhanced bioreduction for effective remediation of chlorinated hydrocarbon-contaminated groundwater.
In-situ enhanced bioreduction by functional materials is a cost-effective technology to remove chlorinated hydrocarbons in groundwater. Herein, a novel polydopamine (PDA)-modified biochar (BC)-based composite containing nanoscale zero-valent iron (nZVI) and poly-l-lactic acid (PLLA) (PB-PDA-Fe) was synthesized to enhance the removal of 1,1,1-trichloroethane (1,1,1-TCA) in simulated groundwater with actual site sediments. Its impact on functional microbial community structure in system was also investigated. The typical characterizations revealed uniform dispersion of PLA and nZVI particles on the BC surface, being smoother after PDA coating. The composite exhibited a significantly higher performance on 1,1,1-TCA removal (82.38%, initial concentration 100 mg/L) than Fe-PDA and PB-PDA treatments. The diversity and richness of the microbial community in the composite treatment consistently decreased during incubation due to a synergistic effect between PLLA-BC and nZVI. Desulfitobaterium, Pedobacter, Sphaerochaeta, Shewanella, and Clostridium were identified as enriched genera by the composite through DNA-stable isotope probing (DNA-SIP), playing a crucial role in the bioreductive dechlorination process. All the above results demonstrate that this novel composite selectively enhances the activity of microorganisms with extracellular respiration functions to efficiently dechlorinate 1,1,1-TCA. These findings could contribute to understanding the responsive microbial community by carbon-iron composites and expedite the application of in-situ enhanced bioreduction for effective remediation of chlorinated hydrocarbon-contaminated groundwater.
2025, 36(1): 110314
doi: 10.1016/j.cclet.2024.110314
Abstract:
Disulfidptosis, a novel mechanism of programmed cell death through the disruption of tumor metabolic symbiosis (TMS), has showed tremendous potential in cancer therapy. However, the efficacy of disulfidptosis is limited by poor permeability of drugs in solid tumors. Herein, hydrogen sulfide (H2S) and near-infrared (NIR) light-driven nanomotors (denoted as HGPP) have been constructed to efficiently penetrate tumors and induce disulfidptosis. HGPP demonstrate glutathione (GSH)-responsive release of H2S, which combined with NIR light-induced photothermal effect drive HGPP movement to facilitate deep tumor penetration. The released H2S induces tumor acidosis and disrupts TMS, where disulfide accumulation following cell starvation leads to disulfidptosis. In addition, HGPP induce hepatoma specific cellular uptake and catalyze the conversion of glucose and oxygen to produce hydrogen peroxide (H2O2), leading to glucose starvation. Overall, this study has developed a multifunctional Janus nanomotor that provides a novel strategy for disulfidptosis-based solid tumor therapy.
Disulfidptosis, a novel mechanism of programmed cell death through the disruption of tumor metabolic symbiosis (TMS), has showed tremendous potential in cancer therapy. However, the efficacy of disulfidptosis is limited by poor permeability of drugs in solid tumors. Herein, hydrogen sulfide (H2S) and near-infrared (NIR) light-driven nanomotors (denoted as HGPP) have been constructed to efficiently penetrate tumors and induce disulfidptosis. HGPP demonstrate glutathione (GSH)-responsive release of H2S, which combined with NIR light-induced photothermal effect drive HGPP movement to facilitate deep tumor penetration. The released H2S induces tumor acidosis and disrupts TMS, where disulfide accumulation following cell starvation leads to disulfidptosis. In addition, HGPP induce hepatoma specific cellular uptake and catalyze the conversion of glucose and oxygen to produce hydrogen peroxide (H2O2), leading to glucose starvation. Overall, this study has developed a multifunctional Janus nanomotor that provides a novel strategy for disulfidptosis-based solid tumor therapy.
2025, 36(1): 110351
doi: 10.1016/j.cclet.2024.110351
Abstract:
Gastric Carcinoma (GC) is a highly fatal malignant tumor with a poor prognosis. Its elevated mortality rates are primarily due to its proclivity for late-stage metastasis. Exploring the metabolic interactions between tumor microenvironment and the systemic bloodstream could help to clearly understand the mechanisms and identify precise biomarkers of tumor growth, proliferation, and metastasis. In this study, an integrative approach that combines plasma metabolomics with mass spectrometry imaging of tumor tissue was developed to investigate the global metabolic landscape of GC tumorigenesis and metastasis. The results showed that the oxidized glutathione to glutathione ratio (GSSH/GSH) became increased in non-distal metastatic GC (M0), which means an accumulation of oxidative stress in tumor tissues. Furthermore, it was found that the peroxidation of polyunsaturated fatty acids, such as 9,10-EpOMe, 9-HOTrE, etc., were accelerated in both plasma and tumor tissues of distal metastatic GC (M1). These changes were further confirmed the potential effect of CYP2E1 and GGT1 in metastatic potential of GC by mass spectrometry imaging (MSI) and immunohistochemistry (IHC). Collectively, our findings reveal the integrated multidimensional metabolomics approach is a clinical useful method to unravel the blood-tumor metabolic crosstalk, illuminate reprogrammed metabolic networks, and provide reliable circulating biomarkers.
Gastric Carcinoma (GC) is a highly fatal malignant tumor with a poor prognosis. Its elevated mortality rates are primarily due to its proclivity for late-stage metastasis. Exploring the metabolic interactions between tumor microenvironment and the systemic bloodstream could help to clearly understand the mechanisms and identify precise biomarkers of tumor growth, proliferation, and metastasis. In this study, an integrative approach that combines plasma metabolomics with mass spectrometry imaging of tumor tissue was developed to investigate the global metabolic landscape of GC tumorigenesis and metastasis. The results showed that the oxidized glutathione to glutathione ratio (GSSH/GSH) became increased in non-distal metastatic GC (M0), which means an accumulation of oxidative stress in tumor tissues. Furthermore, it was found that the peroxidation of polyunsaturated fatty acids, such as 9,10-EpOMe, 9-HOTrE, etc., were accelerated in both plasma and tumor tissues of distal metastatic GC (M1). These changes were further confirmed the potential effect of CYP2E1 and GGT1 in metastatic potential of GC by mass spectrometry imaging (MSI) and immunohistochemistry (IHC). Collectively, our findings reveal the integrated multidimensional metabolomics approach is a clinical useful method to unravel the blood-tumor metabolic crosstalk, illuminate reprogrammed metabolic networks, and provide reliable circulating biomarkers.
2025, 36(1): 110385
doi: 10.1016/j.cclet.2024.110385
Abstract:
Ethylene carbonate (EC) is the conventional and promising solvent to achieve high energy lithium metal battery. However, the innate low energy level of lowest unoccupied molecular orbital (LUMO) in EC makes it incompatible with lithium metal, causing uncontrolled lithium growth and low Coulombic efficiency (CE). Herein, we introduced bis(2,2,2-trifluoroethyl) carbonate (TFEC), a carbonate with a strong electron-withdrawing effect (-CF3), which enhances the stability of EC at electrode interface by reducing ion-dipole interactions between Li+ and EC. As the interaction between Li and EC weakens, TFEC and more PF6− anions coordinate with Li+, promoting the formation of contact ion pairs (CIPs) and aggregates (AGGs), thereby increasing the inorganic composition within the solid electrolyte interphase. Additionally, the distinct solvated sheath structure favors the decomposition of fluorinated solvents and PF6− anions, forming inorganic-rich electrode-electrolyte interfaces (SEI and CEI), thereby ensuring high stability for both the Li anode and high-voltage cathode. Hence, when applied in the full-cell LiLiMn0.8Fe0.2PO4, it displays consistent cycling performance, exhibiting minimal capacity decay with a retention rate of 62.5% after 800 cycles, substantially surpassing that of cells using base electrolytes (29.8%).
Ethylene carbonate (EC) is the conventional and promising solvent to achieve high energy lithium metal battery. However, the innate low energy level of lowest unoccupied molecular orbital (LUMO) in EC makes it incompatible with lithium metal, causing uncontrolled lithium growth and low Coulombic efficiency (CE). Herein, we introduced bis(2,2,2-trifluoroethyl) carbonate (TFEC), a carbonate with a strong electron-withdrawing effect (-CF3), which enhances the stability of EC at electrode interface by reducing ion-dipole interactions between Li+ and EC. As the interaction between Li and EC weakens, TFEC and more PF6− anions coordinate with Li+, promoting the formation of contact ion pairs (CIPs) and aggregates (AGGs), thereby increasing the inorganic composition within the solid electrolyte interphase. Additionally, the distinct solvated sheath structure favors the decomposition of fluorinated solvents and PF6− anions, forming inorganic-rich electrode-electrolyte interfaces (SEI and CEI), thereby ensuring high stability for both the Li anode and high-voltage cathode. Hence, when applied in the full-cell LiLiMn0.8Fe0.2PO4, it displays consistent cycling performance, exhibiting minimal capacity decay with a retention rate of 62.5% after 800 cycles, substantially surpassing that of cells using base electrolytes (29.8%).
2025, 36(1): 110452
doi: 10.1016/j.cclet.2024.110452
Abstract:
Flexible energy storage devices have been paid much attention and adapts to apply in various fields. Benefiting from the active sites of boron (B) and phosphorus (P) doping materials, co-doped carbon materials are widely used in energy storage devices for the enhanced electrochemical performance. Herein, B and P co-doped flexible carbon nanofibers with nitrogen-rich (B-P/NC) are investigated with electrospinning for sodium-ion battery. The flexible of binderless B-P/NC with annealing of 600 ℃ (B-P/NC-600) exhibits the remarkable performance for the robust capacity of 200 mAh/g at 0.1 A/g after 500 cycles and a durable reversible capacity of 160 mAh/g even at 1 A/g after 12, 000 cycles, exhibiting the equally commendable stability of flexible B-P/NC-600. In addition, B-P/NC-600 delivers the reversible capacity of 265 mAh/g with the test temperature of 60 ℃. More importantly, the flexible B-P/NC-600 is fabricated as anode for the whole battery, delivering the capacity of 90 mAh/g at 1 A/g after 200 cycles. Meanwhile, theoretical calculation further verified that boron and phosphorus co-doping can improve the adsorption capacity of nitrogen carbon materials. The favorable performance of flexible B-P/NC-600 can be ascribed to the nitrogen-rich carbon nanofibers with three-dimensional network matrix for the more active site of boron and phosphorus co-doping. Our work paves the way for the improvement of flexible anodes and wide-operating temperature of sodium-ion batteries by doping approach of much heteroatom.
Flexible energy storage devices have been paid much attention and adapts to apply in various fields. Benefiting from the active sites of boron (B) and phosphorus (P) doping materials, co-doped carbon materials are widely used in energy storage devices for the enhanced electrochemical performance. Herein, B and P co-doped flexible carbon nanofibers with nitrogen-rich (B-P/NC) are investigated with electrospinning for sodium-ion battery. The flexible of binderless B-P/NC with annealing of 600 ℃ (B-P/NC-600) exhibits the remarkable performance for the robust capacity of 200 mAh/g at 0.1 A/g after 500 cycles and a durable reversible capacity of 160 mAh/g even at 1 A/g after 12, 000 cycles, exhibiting the equally commendable stability of flexible B-P/NC-600. In addition, B-P/NC-600 delivers the reversible capacity of 265 mAh/g with the test temperature of 60 ℃. More importantly, the flexible B-P/NC-600 is fabricated as anode for the whole battery, delivering the capacity of 90 mAh/g at 1 A/g after 200 cycles. Meanwhile, theoretical calculation further verified that boron and phosphorus co-doping can improve the adsorption capacity of nitrogen carbon materials. The favorable performance of flexible B-P/NC-600 can be ascribed to the nitrogen-rich carbon nanofibers with three-dimensional network matrix for the more active site of boron and phosphorus co-doping. Our work paves the way for the improvement of flexible anodes and wide-operating temperature of sodium-ion batteries by doping approach of much heteroatom.
2025, 36(1): 110491
doi: 10.1016/j.cclet.2024.110491
Abstract:
Herein, vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires (W4MoO3 NWs) rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction (eNRR) electrocatalyst, realizing further enhancement of NRR performance. In 0.1 mol/L Na2SO4, W4MoO3 NWs rich in O vacancies (CTAB-D-W4MoO3) achieve a large NH3 yield of 60.77 µg h-1 mg-1cat. at -0.70 V vs. RHE and a high faradaic efficiency of 56.42% at -0.60 V, much superior to the W4MoO3 NWs deficient in oxygen vacancies (20.26 µg h-1 mg-1cat. and 17.1% at -0.70 V vs. RHE). Meanwhile, W4MoO3 NWs rich in O-vacancies also show high electrochemical stability. Density functional theory (DFT) calculations present that O vacancies in CTAB-D-W4MoO3 reduce the energy barrier formed by the intermediate of *N-NH, facilitate the activation and further hydrogenation of *N-N, promote the NRR process, and improve NRR activity.
Herein, vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires (W4MoO3 NWs) rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction (eNRR) electrocatalyst, realizing further enhancement of NRR performance. In 0.1 mol/L Na2SO4, W4MoO3 NWs rich in O vacancies (CTAB-D-W4MoO3) achieve a large NH3 yield of 60.77 µg h-1 mg-1cat. at -0.70 V vs. RHE and a high faradaic efficiency of 56.42% at -0.60 V, much superior to the W4MoO3 NWs deficient in oxygen vacancies (20.26 µg h-1 mg-1cat. and 17.1% at -0.70 V vs. RHE). Meanwhile, W4MoO3 NWs rich in O-vacancies also show high electrochemical stability. Density functional theory (DFT) calculations present that O vacancies in CTAB-D-W4MoO3 reduce the energy barrier formed by the intermediate of *N-NH, facilitate the activation and further hydrogenation of *N-N, promote the NRR process, and improve NRR activity.
2025, 36(1): 109557
doi: 10.1016/j.cclet.2024.109557
Abstract:
Available online Alkaline water electrolysis (AWE) is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure. Noble metal-based electrocatalysts, owing to their exceptional hydrogen binding energy, exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction (HER). However, the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts. This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst, while considering the principles of sustainable development. The initial discussion covers the fundamental principle of HER, followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals, along with a thorough examination of recent advancements. The subsequent discussion focuses on the strategies employed to improve noble metal-based catalysts, including enhancing the intrinsic activity at active sites and increasing the quantity of active sites. Ultimately, this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
Available online Alkaline water electrolysis (AWE) is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure. Noble metal-based electrocatalysts, owing to their exceptional hydrogen binding energy, exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction (HER). However, the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts. This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst, while considering the principles of sustainable development. The initial discussion covers the fundamental principle of HER, followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals, along with a thorough examination of recent advancements. The subsequent discussion focuses on the strategies employed to improve noble metal-based catalysts, including enhancing the intrinsic activity at active sites and increasing the quantity of active sites. Ultimately, this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
2025, 36(1): 109684
doi: 10.1016/j.cclet.2024.109684
Abstract:
As the global population ages, osteoporotic bone fractures leading to bone defects are increasingly becoming a significant challenge in the field of public health. Treating this disease faces many challenges, especially in the context of an imbalance between osteoblast and osteoclast activities. Therefore, the development of new biomaterials has become the key. This article reviews various design strategies and their advantages and disadvantages for biomaterials aimed at osteoporotic bone defects. Overall, current research progress indicates that innovative design, functionalization, and targeting of materials can significantly enhance bone regeneration under osteoporotic conditions. By comprehensively considering biocompatibility, mechanical properties, and bioactivity, these biomaterials can be further optimized, offering a range of choices and strategies for the repair of osteoporotic bone defects.
As the global population ages, osteoporotic bone fractures leading to bone defects are increasingly becoming a significant challenge in the field of public health. Treating this disease faces many challenges, especially in the context of an imbalance between osteoblast and osteoclast activities. Therefore, the development of new biomaterials has become the key. This article reviews various design strategies and their advantages and disadvantages for biomaterials aimed at osteoporotic bone defects. Overall, current research progress indicates that innovative design, functionalization, and targeting of materials can significantly enhance bone regeneration under osteoporotic conditions. By comprehensively considering biocompatibility, mechanical properties, and bioactivity, these biomaterials can be further optimized, offering a range of choices and strategies for the repair of osteoporotic bone defects.
2025, 36(1): 109724
doi: 10.1016/j.cclet.2024.109724
Abstract:
Despite ongoing advancements in cancer treatment, the emergence of primary and acquired resistance poses a significant challenge for both traditional chemotherapy and immune checkpoint blockade therapies. The demand for targeted therapeutics for multidrug-resistant cancer is more important than ever. Peptides, as emerging alternatives to current anticancer drugs, offer exquisite versatility in facilitating the design of novel oncology drugs, with the core superiorities of good biocompatibility and a low tendency to induce drug resistance. This review comprehensively introduces the pharmacological mechanisms of peptide-based drugs and strategies for overcoming multidrug resistance (MDR) in cancers, including inducing cell membrane lysis, targeting organelles, activating anticancer immune responses, enhancing drug uptake, targeting ATP-binding cassette (ABC) transporters, and targeting B-cell lymphoma-2 (BCL-2) family proteins. Additionally, the current clinical applications of representative peptides in combating MDR cancers and their potential directions for medicinal chemistry research have been thoroughly discussed. This review offers essential insights into the novel treatment approaches for MDR cancers and highlights the trends and perspectives in this field.
Despite ongoing advancements in cancer treatment, the emergence of primary and acquired resistance poses a significant challenge for both traditional chemotherapy and immune checkpoint blockade therapies. The demand for targeted therapeutics for multidrug-resistant cancer is more important than ever. Peptides, as emerging alternatives to current anticancer drugs, offer exquisite versatility in facilitating the design of novel oncology drugs, with the core superiorities of good biocompatibility and a low tendency to induce drug resistance. This review comprehensively introduces the pharmacological mechanisms of peptide-based drugs and strategies for overcoming multidrug resistance (MDR) in cancers, including inducing cell membrane lysis, targeting organelles, activating anticancer immune responses, enhancing drug uptake, targeting ATP-binding cassette (ABC) transporters, and targeting B-cell lymphoma-2 (BCL-2) family proteins. Additionally, the current clinical applications of representative peptides in combating MDR cancers and their potential directions for medicinal chemistry research have been thoroughly discussed. This review offers essential insights into the novel treatment approaches for MDR cancers and highlights the trends and perspectives in this field.
2025, 36(1): 109766
doi: 10.1016/j.cclet.2024.109766
Abstract:
The treatment of skin wounds, especially chronic wounds, remains a critical clinical challenge and places a heavy burden on patients and healthcare systems. In recent years, the engineering strategy of using biomaterial-assisted exosomes has emerged as a powerful tool for skin repair. Compared to treatments such as debridement and regular dressing changes, the design of biomaterial-assisted exosomes not only maintains the bioactivity of exosomes at the wound site but also provides an appropriate microenvironment for the repair of complex tissues, thereby accelerating wound healing. This review systematically introduces the general characteristics of exosomes and their functions in skin wound healing, highlights recent advances in classification of natural exosomes and engineering methods which enriching their functions in intercellular communication. Then, various emerging and innovative approaches based on biomaterials delivery of exosomes are comprehensively discussed. The review seeks to bring an in-depth understanding of bioactive dressings based on exosomes therapeutic strategies, aiming to facilitate new clinical application value.
The treatment of skin wounds, especially chronic wounds, remains a critical clinical challenge and places a heavy burden on patients and healthcare systems. In recent years, the engineering strategy of using biomaterial-assisted exosomes has emerged as a powerful tool for skin repair. Compared to treatments such as debridement and regular dressing changes, the design of biomaterial-assisted exosomes not only maintains the bioactivity of exosomes at the wound site but also provides an appropriate microenvironment for the repair of complex tissues, thereby accelerating wound healing. This review systematically introduces the general characteristics of exosomes and their functions in skin wound healing, highlights recent advances in classification of natural exosomes and engineering methods which enriching their functions in intercellular communication. Then, various emerging and innovative approaches based on biomaterials delivery of exosomes are comprehensively discussed. The review seeks to bring an in-depth understanding of bioactive dressings based on exosomes therapeutic strategies, aiming to facilitate new clinical application value.
2025, 36(1): 109836
doi: 10.1016/j.cclet.2024.109836
Abstract:
As more and more studies have shown that lipid molecules play an important role in the whole biology, in-depth analysis of lipid structure has become particularly important in lipidomics. Mass spectrometry (MS), as the preferred tool for lipid analysis, has greatly promoted the development of this field. However, the existing MS methods still face many difficulties in the in-depth or even comprehensive analysis of lipid structure. In this review, we discuss recent advances in MS methods based on double bond-specific chemistries for the resolving of C=C location and geometry isomers of lipids. This progress has greatly advanced the lipidomics analysis to a deeper structural level and facilitated the development of structural lipid biology.
As more and more studies have shown that lipid molecules play an important role in the whole biology, in-depth analysis of lipid structure has become particularly important in lipidomics. Mass spectrometry (MS), as the preferred tool for lipid analysis, has greatly promoted the development of this field. However, the existing MS methods still face many difficulties in the in-depth or even comprehensive analysis of lipid structure. In this review, we discuss recent advances in MS methods based on double bond-specific chemistries for the resolving of C=C location and geometry isomers of lipids. This progress has greatly advanced the lipidomics analysis to a deeper structural level and facilitated the development of structural lipid biology.
2025, 36(1): 109855
doi: 10.1016/j.cclet.2024.109855
Abstract:
Piperidine is a crucial pharmacophore and a special scaffold in the realm of drug discovery. Its flexibility increases the molecule's capability to bind to the receptor. The piperidine-containing compounds are distinguished by their remarkable activity, and are increasingly becoming a vital category of pesticides. In this review, the research progress of piperidines in the discovery of pesticides was updated according to their active characteristics. The structure-activity relationships (SARs), and mechanisms of action of piperidine-containing compounds were also discussed. This article is meant to enable readers to quickly understand piperidines, while providing ideas for creating piperidines with novel structures and unique mechanisms of action.
Piperidine is a crucial pharmacophore and a special scaffold in the realm of drug discovery. Its flexibility increases the molecule's capability to bind to the receptor. The piperidine-containing compounds are distinguished by their remarkable activity, and are increasingly becoming a vital category of pesticides. In this review, the research progress of piperidines in the discovery of pesticides was updated according to their active characteristics. The structure-activity relationships (SARs), and mechanisms of action of piperidine-containing compounds were also discussed. This article is meant to enable readers to quickly understand piperidines, while providing ideas for creating piperidines with novel structures and unique mechanisms of action.
2025, 36(1): 109861
doi: 10.1016/j.cclet.2024.109861
Abstract:
Poly(butylene adipate-terephthalate) (PBAT), as one of the most common and promising biodegradable plastics, has been widely used in agriculture, packaging, and other industries due to its strong biodegradability properties. It is well known that PBAT suffers a series of natural weathering, mechanical wear, hydrolysis, photochemical transformation, and other abiotic degradation processes before being biodegraded. Therefore, it is particularly important to understand the role of abiotic degradation in the life cycle of PBAT. Since the abiotic degradation of PBAT has not been systematically summarized, this review aims to summarize the mechanisms and main factors of the three major abiotic degradation pathways (hydrolysis, photochemical transformation, and thermochemical degradation) of PBAT. It was found that all of them preferentially destroy the chemical bonds with higher energy (especially C-O and C=O) of PBAT, which eventually leads to the shortening of the polymer chain and then leads to reduction in molecular weight. The main factors affecting these abiotic degradations are closely related to the energy or PBAT structure. These findings provide important theoretical and practical guidance for identifying effective methods for PBAT waste management and proposing advanced schemes to regulate the degradation rate of PBAT.
Poly(butylene adipate-terephthalate) (PBAT), as one of the most common and promising biodegradable plastics, has been widely used in agriculture, packaging, and other industries due to its strong biodegradability properties. It is well known that PBAT suffers a series of natural weathering, mechanical wear, hydrolysis, photochemical transformation, and other abiotic degradation processes before being biodegraded. Therefore, it is particularly important to understand the role of abiotic degradation in the life cycle of PBAT. Since the abiotic degradation of PBAT has not been systematically summarized, this review aims to summarize the mechanisms and main factors of the three major abiotic degradation pathways (hydrolysis, photochemical transformation, and thermochemical degradation) of PBAT. It was found that all of them preferentially destroy the chemical bonds with higher energy (especially C-O and C=O) of PBAT, which eventually leads to the shortening of the polymer chain and then leads to reduction in molecular weight. The main factors affecting these abiotic degradations are closely related to the energy or PBAT structure. These findings provide important theoretical and practical guidance for identifying effective methods for PBAT waste management and proposing advanced schemes to regulate the degradation rate of PBAT.
2025, 36(1): 109955
doi: 10.1016/j.cclet.2024.109955
Abstract:
This review covers the structures of diterpenoids, including chain (72), monocyclic (9), labdane-type (67), clerodane-type (127) abietane-type (716), ent-kaurane-type (89), grayanane-type (331), ingenane-type (55), tigliane-type (154), daphnane-type (237), and aconitine-type diterpene alkaloids (265) with rich biological activities reported in 2013–2023. And the drugs in clinical use or under clinical investigation of diterpenoids and leading compounds were summarized.
This review covers the structures of diterpenoids, including chain (72), monocyclic (9), labdane-type (67), clerodane-type (127) abietane-type (716), ent-kaurane-type (89), grayanane-type (331), ingenane-type (55), tigliane-type (154), daphnane-type (237), and aconitine-type diterpene alkaloids (265) with rich biological activities reported in 2013–2023. And the drugs in clinical use or under clinical investigation of diterpenoids and leading compounds were summarized.
2025, 36(1): 109995
doi: 10.1016/j.cclet.2024.109995
Abstract:
The rapid development of microfluidic technology has led to the evolution of microdroplets from simple emulsion structures to complex multilayered and multicompartmental configurations. These advancements have endowed microdroplets with the capability to contain multiple compartments that remain isolated from one another, enabling them to carry different molecules of interest. Consequently, researchers can now investigate intricate spatially confined chemical reactions and signal transduction pathways within subcellular organelles. Moreover, modern microdroplets often possess excellent optical transparency, allowing fluorescently labelled, multi-layered, and compartmental droplets to provide detailed insights through real-time, in situ, and dynamic fluorescence imaging. Hence, this review systematically summarizes current methodologies for preparing multicomponent microdroplets and their applications, particularly focusing on fluorescent microdroplets. Additionally, it discusses existing critical challenges and outlines future research directions. By offering a comprehensive overview of the preparation methods and applications of fluorescent microdroplets, this review aims to stimulate the interest of researchers and foster their utilization in more complex and biomimetic environments.
The rapid development of microfluidic technology has led to the evolution of microdroplets from simple emulsion structures to complex multilayered and multicompartmental configurations. These advancements have endowed microdroplets with the capability to contain multiple compartments that remain isolated from one another, enabling them to carry different molecules of interest. Consequently, researchers can now investigate intricate spatially confined chemical reactions and signal transduction pathways within subcellular organelles. Moreover, modern microdroplets often possess excellent optical transparency, allowing fluorescently labelled, multi-layered, and compartmental droplets to provide detailed insights through real-time, in situ, and dynamic fluorescence imaging. Hence, this review systematically summarizes current methodologies for preparing multicomponent microdroplets and their applications, particularly focusing on fluorescent microdroplets. Additionally, it discusses existing critical challenges and outlines future research directions. By offering a comprehensive overview of the preparation methods and applications of fluorescent microdroplets, this review aims to stimulate the interest of researchers and foster their utilization in more complex and biomimetic environments.
2025, 36(1): 109998
doi: 10.1016/j.cclet.2024.109998
Abstract:
Photocatalytic CO2 reduction reaction (CO2RR) is one of the promising strategies for sustainably producing solar fuels. The precise identification of catalytic sites and the enhancement of photocatalytic CO2 conversion is imperative yet quite challenging. This critical review summarizes recent advances in porous photo-responsive polymers, including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), and conjugated microporous polymers (CMPs), those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO2 reduction. Additionally, special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance. The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity, as well as for the design of better photocatalysts for CO2 reduction.
Photocatalytic CO2 reduction reaction (CO2RR) is one of the promising strategies for sustainably producing solar fuels. The precise identification of catalytic sites and the enhancement of photocatalytic CO2 conversion is imperative yet quite challenging. This critical review summarizes recent advances in porous photo-responsive polymers, including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs), and conjugated microporous polymers (CMPs), those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO2 reduction. Additionally, special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance. The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity, as well as for the design of better photocatalysts for CO2 reduction.
2025, 36(1): 110100
doi: 10.1016/j.cclet.2024.110100
Abstract:
Surface with well-defined components and structures possesses unique electronic, magnetic, optical and chemical properties. As a result, surface chemistry research plays a crucial role in various fields such as catalysis, energy, materials, quantum, and microelectronics. Surface science mainly investigates the correspondence between surface property and functionality. Scanning probe microscopy (SPM) techniques are important tools to characterize surface properties because of the capability of atomic-scale imaging, spectroscopy and manipulation at the single-atom level. In this review, we summarize recent advances in surface electronic, magnetic and optical properties characterized mainly by SPM-based methods. We focus on elucidating the π-magnetism in graphene-based nanostructures, construction of spin qubits on surfaces, topology properties of surface organic structures, STM-based light emission, tip-enhanced Raman spectroscopy and integration of machine learning in SPM studies.
Surface with well-defined components and structures possesses unique electronic, magnetic, optical and chemical properties. As a result, surface chemistry research plays a crucial role in various fields such as catalysis, energy, materials, quantum, and microelectronics. Surface science mainly investigates the correspondence between surface property and functionality. Scanning probe microscopy (SPM) techniques are important tools to characterize surface properties because of the capability of atomic-scale imaging, spectroscopy and manipulation at the single-atom level. In this review, we summarize recent advances in surface electronic, magnetic and optical properties characterized mainly by SPM-based methods. We focus on elucidating the π-magnetism in graphene-based nanostructures, construction of spin qubits on surfaces, topology properties of surface organic structures, STM-based light emission, tip-enhanced Raman spectroscopy and integration of machine learning in SPM studies.
2025, 36(1): 110117
doi: 10.1016/j.cclet.2024.110117
Abstract:
Organic pollutants are harmful and toxic chemical substances that adversely threaten human health and the living environment all over the world. More and more studies have been investigating the relationship between low level of human exposure of organic compounds and various internal diseases. For the sake of assessing disease risk due to organic compounds contact in a particular location, it is imperative for relevant government departments to make a human health risk assessment in view of the organic pollutants’ bioavailability and their dosage-response correlations. It is inevitable to make use of an efficient method to detect organic pollutants, which is significant for public health and safety. Fluorescent assays based on carbon dots thus would provide a very plausible candidate method. After consulting a large number of literatures, we offer a comprehensive review of the sensing applications of carbon dots for organic pollutants.
Organic pollutants are harmful and toxic chemical substances that adversely threaten human health and the living environment all over the world. More and more studies have been investigating the relationship between low level of human exposure of organic compounds and various internal diseases. For the sake of assessing disease risk due to organic compounds contact in a particular location, it is imperative for relevant government departments to make a human health risk assessment in view of the organic pollutants’ bioavailability and their dosage-response correlations. It is inevitable to make use of an efficient method to detect organic pollutants, which is significant for public health and safety. Fluorescent assays based on carbon dots thus would provide a very plausible candidate method. After consulting a large number of literatures, we offer a comprehensive review of the sensing applications of carbon dots for organic pollutants.
2025, 36(1): 110142
doi: 10.1016/j.cclet.2024.110142
Abstract:
Photocatalysis is widely regarded as a highly promising sustainable technique for addressing the challenges posed by environmental pollution and energy provision. In recent years, metal-loaded MOFs has become a rising star within the domain of photocatalysis due to its high specific surface area and porosity, adjustable structure, diverse and abundant catalytic components, which has exhibited excellent photocatalytic activity and exhibit great potential in a range of disciplines. In this paper, the principles for evaluating the photocatalytic performance of MOFs-based materials were firstly introduced, and some typical examples were also listed accordingly. Along with this, particular emphasis is paid to the main factors affecting the photocatalytic performance of metal-loaded MOFs. Then the synthesis and design strategies of MOFs loaded metal entities of varying sizes (single atoms, nanoclusters, and nanoparticles), and their applications in photocatalytic CO2 reduction, hydrogen production, photooxidation and photocatalytic hydrogenation were summarized and discussed. Finally, the opportunities and challenges faced in this kind of MOFs-based composites were analyzed from different perspectives. This report is expected to help researchers design and develop high-performance MOFs-based photocatalytic materials.
Photocatalysis is widely regarded as a highly promising sustainable technique for addressing the challenges posed by environmental pollution and energy provision. In recent years, metal-loaded MOFs has become a rising star within the domain of photocatalysis due to its high specific surface area and porosity, adjustable structure, diverse and abundant catalytic components, which has exhibited excellent photocatalytic activity and exhibit great potential in a range of disciplines. In this paper, the principles for evaluating the photocatalytic performance of MOFs-based materials were firstly introduced, and some typical examples were also listed accordingly. Along with this, particular emphasis is paid to the main factors affecting the photocatalytic performance of metal-loaded MOFs. Then the synthesis and design strategies of MOFs loaded metal entities of varying sizes (single atoms, nanoclusters, and nanoparticles), and their applications in photocatalytic CO2 reduction, hydrogen production, photooxidation and photocatalytic hydrogenation were summarized and discussed. Finally, the opportunities and challenges faced in this kind of MOFs-based composites were analyzed from different perspectives. This report is expected to help researchers design and develop high-performance MOFs-based photocatalytic materials.
2025, 36(1): 110234
doi: 10.1016/j.cclet.2024.110234
Abstract:
Photocatalytic technology harnesses solar energy to facilitate chemical transformations, presenting significant potential in energy generation and environmental remediation. However, the conventional O2 evolution process is hindered by high reaction barriers and inefficiencies, which limit its widespread application. Therefore, exploring novel photocatalytic coupling strategies to replace water oxidation has become a key route to enhance the efficiency of H2 production. In this review, organic pollutants removal and the valorization of organics as substitutes for water oxidation coupling strategies for photocatalytic H2 production are comprehensively summarized. These strategies not only circumvent the high reaction barriers associated with O2 evolution to enhance the H2 production but also aid in the removing of organic pollutants or synthesis of value-added chemicals. We also present future research directions and underscore the significance of advanced catalyst design, in-depth analysis of reaction mechanisms, and systematic optimization strategies in realizing an efficient and sustainable photocatalytic process. This guidance is anticipated to provide theoretical and practical new insights for the future development of photocatalytic coupling reactions, fostering further explorations in the realm of renewable energy and environmental governance.
Photocatalytic technology harnesses solar energy to facilitate chemical transformations, presenting significant potential in energy generation and environmental remediation. However, the conventional O2 evolution process is hindered by high reaction barriers and inefficiencies, which limit its widespread application. Therefore, exploring novel photocatalytic coupling strategies to replace water oxidation has become a key route to enhance the efficiency of H2 production. In this review, organic pollutants removal and the valorization of organics as substitutes for water oxidation coupling strategies for photocatalytic H2 production are comprehensively summarized. These strategies not only circumvent the high reaction barriers associated with O2 evolution to enhance the H2 production but also aid in the removing of organic pollutants or synthesis of value-added chemicals. We also present future research directions and underscore the significance of advanced catalyst design, in-depth analysis of reaction mechanisms, and systematic optimization strategies in realizing an efficient and sustainable photocatalytic process. This guidance is anticipated to provide theoretical and practical new insights for the future development of photocatalytic coupling reactions, fostering further explorations in the realm of renewable energy and environmental governance.
2025, 36(1): 110368
doi: 10.1016/j.cclet.2024.110368
Abstract:
As battery technology evolves and demand for efficient energy storage solutions, aqueous zinc ion batteries (AZIBs) have garnered significant attention due to their safety and environmental benefits. However, the stability of cathode materials under high-voltage conditions remains a critical challenge in improving its energy density. This review systematically explores the failure mechanisms of high-voltage cathode materials in AZIBs, including hydrogen evolution reaction, phase transformation and dissolution phenomena. To address these challenges, we propose a range of advanced strategies aimed at improving the stability of cathode materials. These strategies include surface coating and doping techniques designed to fortify the surface properties and structure integrity of the cathode materials under high-voltage conditions. Additionally, we emphasize the importance of designing antioxidant electrolytes, with a focus on understanding and optimizing electrolyte decomposition mechanisms. The review also highlights the significance of modifying conductive agents and employing innovative separators to further enhance the stability of AZIBs. By integrating these cutting-edge approaches, this review anticipates substantial advancements in the stability of high-voltage cathode materials, paving the way for the broader application and development of AZIBs in energy storage.
As battery technology evolves and demand for efficient energy storage solutions, aqueous zinc ion batteries (AZIBs) have garnered significant attention due to their safety and environmental benefits. However, the stability of cathode materials under high-voltage conditions remains a critical challenge in improving its energy density. This review systematically explores the failure mechanisms of high-voltage cathode materials in AZIBs, including hydrogen evolution reaction, phase transformation and dissolution phenomena. To address these challenges, we propose a range of advanced strategies aimed at improving the stability of cathode materials. These strategies include surface coating and doping techniques designed to fortify the surface properties and structure integrity of the cathode materials under high-voltage conditions. Additionally, we emphasize the importance of designing antioxidant electrolytes, with a focus on understanding and optimizing electrolyte decomposition mechanisms. The review also highlights the significance of modifying conductive agents and employing innovative separators to further enhance the stability of AZIBs. By integrating these cutting-edge approaches, this review anticipates substantial advancements in the stability of high-voltage cathode materials, paving the way for the broader application and development of AZIBs in energy storage.
2025, 36(1): 110457
doi: 10.1016/j.cclet.2024.110457
Abstract:
Photocatalytic hydrogen peroxide (H2O2) production has been considered as a promising strategy for H2O2 synthesis due to its environmentally friendly. Among various photocatalysts, carbon nitride-based materials are excellent candidates for H2O2 production because of their excellent visible-light response, low cost and high stability. In this review, we summarize in detail the research progress on the photocatalytic production of H2O2 by carbon nitride. First, we summarize the basic principles of photocatalysis and photocatalytic H2O2 production. Second, the classification and modification methods of carbon-nitride-based materials are discussed, including morphology modulation, noble metal loading, defect control, heterojunction regulation, molecular structure engineering and elemental doping. Finally, the different in-situ applications of H2O2 via photosynthesis were discussed, including disinfection and antibiotic resistant genes degradation, organic pollutants degradation, medical applications and fine chemical synthesis. This review brings great promise for in-situ H2O2 photosynthesis, which is expected to serve as a key component in future applications.
Photocatalytic hydrogen peroxide (H2O2) production has been considered as a promising strategy for H2O2 synthesis due to its environmentally friendly. Among various photocatalysts, carbon nitride-based materials are excellent candidates for H2O2 production because of their excellent visible-light response, low cost and high stability. In this review, we summarize in detail the research progress on the photocatalytic production of H2O2 by carbon nitride. First, we summarize the basic principles of photocatalysis and photocatalytic H2O2 production. Second, the classification and modification methods of carbon-nitride-based materials are discussed, including morphology modulation, noble metal loading, defect control, heterojunction regulation, molecular structure engineering and elemental doping. Finally, the different in-situ applications of H2O2 via photosynthesis were discussed, including disinfection and antibiotic resistant genes degradation, organic pollutants degradation, medical applications and fine chemical synthesis. This review brings great promise for in-situ H2O2 photosynthesis, which is expected to serve as a key component in future applications.
2025, 36(1): 110378
doi: 10.1016/j.cclet.2024.110378
Abstract:
2025, 36(1): 110446
doi: 10.1016/j.cclet.2024.110446
Abstract:
