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2024 Volume 35 Issue 2
2024, 35(2): 108308
doi: 10.1016/j.cclet.2023.108308
Abstract:
Lithium-rich layered cathode material (LLM) can meet the requirement of power lithium-ion energy storage devices due to the great energy density. However, the de/intercalation of Li+ will cause the irreversible loss of lattice oxygen and trigger transition metal (TM) ions migrate to Li+ vacancies, resulting in capacity decay. Here we brought Ti4+ in substitution of TM ions in Li1.2Mn0.54Ni0.13Co0.13O2, which could stabilize structure and expand the layer spacing of LLM. Moreover, optimized Ti-substitution can regulate the anions and cations of LLM, enhance the interaction with lattice oxygen, increase Ni3+ and Co3+, and improve Mn4+ coordination, improving reversibility of oxygen redox activation, maintaining the stable framework and facilitating the Li+ diffusion. Furthermore, we found 5% Ti-substitution sample delivered a high discharge capacity of 244.2 mAh/g at 50 mA/g, an improved cycling stability to 87.3% after 100 cycles and enhanced rate performance. Thereby Ti-substitution gives a new pathway to achieve high reversible cycle retention for LLMs.
Lithium-rich layered cathode material (LLM) can meet the requirement of power lithium-ion energy storage devices due to the great energy density. However, the de/intercalation of Li+ will cause the irreversible loss of lattice oxygen and trigger transition metal (TM) ions migrate to Li+ vacancies, resulting in capacity decay. Here we brought Ti4+ in substitution of TM ions in Li1.2Mn0.54Ni0.13Co0.13O2, which could stabilize structure and expand the layer spacing of LLM. Moreover, optimized Ti-substitution can regulate the anions and cations of LLM, enhance the interaction with lattice oxygen, increase Ni3+ and Co3+, and improve Mn4+ coordination, improving reversibility of oxygen redox activation, maintaining the stable framework and facilitating the Li+ diffusion. Furthermore, we found 5% Ti-substitution sample delivered a high discharge capacity of 244.2 mAh/g at 50 mA/g, an improved cycling stability to 87.3% after 100 cycles and enhanced rate performance. Thereby Ti-substitution gives a new pathway to achieve high reversible cycle retention for LLMs.
2024, 35(2): 108309
doi: 10.1016/j.cclet.2023.108309
Abstract:
Understanding the relationship between structure and properties is critical to the development of solid-state luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF6] with two counterions is obtained by simple N-methylation of the ancillary ligand of [Ir1-f][PF6] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders. [Ir1-f][PF6] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission (AIE) activity. On the sharp contrary, [Ir2-f][2PF6] is an aggregation-caused quenching (ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF6] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.
Understanding the relationship between structure and properties is critical to the development of solid-state luminescence materials with desired characteristics and performance optimization. In this work, we elaborately designed and synthesized a pair of mononuclear iridium(Ⅲ) complexes with similar structures but different degrees of cationization. [Ir2-f][2PF6] with two counterions is obtained by simple N-methylation of the ancillary ligand of [Ir1-f][PF6] which is a classic cationic iridium(Ⅲ) complex. Such a tiny modification results in tremendously different optical properties in dilute solutions and powders. [Ir1-f][PF6] exhibits weak light in solution but enhanced emission in solid-state as well as poly(methyl methacrylate) matrix, indicative of its aggregation-induced emission (AIE) activity. On the sharp contrary, [Ir2-f][2PF6] is an aggregation-caused quenching (ACQ) emitter showing strong emission in the isolated state but nearly nonemissive in aggregation states. Benefiting from the appealing characteristics of mechanochromic luminescence and AIE behavior, [Ir1-f][PF6] has been successfully applied in reversible re-writable data recording and cell imaging. These results might provide deep insights into AIE and ACQ phenomenon of iridium(Ⅲ) complexes and facilitate the development of phosphorescent materials with promising properties.
2024, 35(2): 108324
doi: 10.1016/j.cclet.2023.108324
Abstract:
Partial substitution of polyoxometalate (POM) is an efficient route to modulate the catalytic property of maternal POM. In this work, a new Keggin type POM involving {Ni6} cluster, {[Ni(H2O)2(Dach)2][Ni(Dach)2]2}{[Ni6Cl(μ-OH)3(H2O)(Dach)3(WO4)(PW9O34)][Ni6(μ-OH)3(H2O)2(Dach)3(WO4)(PW9O34)]}Cl·27H2O, (1, Dach = 1,2-diaminocyclohexane) was synthesized. Compounds 1 shows excellent catalytic performance in the selective oxidation of aniline to azoxybenzene (AOB) in water. The apparently different results from that with the matrix {PW9O34} ({PW9}) suggest the successful regulation of the catalytic property of {PW9} by the introduction of the {Ni6} cluster into the skeleton. The experimental results indicate that the highlighted performance of 1 is contributed by the synergy of W and Ni sites, which are respectively responsible for the oxidation and condensation steps in the production of AOB. The good selectivity to AOB is essentially attributed to the effective modulation of the reaction rates of oxidation and condensation steps by W and Ni sites, respectively.
Partial substitution of polyoxometalate (POM) is an efficient route to modulate the catalytic property of maternal POM. In this work, a new Keggin type POM involving {Ni6} cluster, {[Ni(H2O)2(Dach)2][Ni(Dach)2]2}{[Ni6Cl(μ-OH)3(H2O)(Dach)3(WO4)(PW9O34)][Ni6(μ-OH)3(H2O)2(Dach)3(WO4)(PW9O34)]}Cl·27H2O, (1, Dach = 1,2-diaminocyclohexane) was synthesized. Compounds 1 shows excellent catalytic performance in the selective oxidation of aniline to azoxybenzene (AOB) in water. The apparently different results from that with the matrix {PW9O34} ({PW9}) suggest the successful regulation of the catalytic property of {PW9} by the introduction of the {Ni6} cluster into the skeleton. The experimental results indicate that the highlighted performance of 1 is contributed by the synergy of W and Ni sites, which are respectively responsible for the oxidation and condensation steps in the production of AOB. The good selectivity to AOB is essentially attributed to the effective modulation of the reaction rates of oxidation and condensation steps by W and Ni sites, respectively.
2024, 35(2): 108341
doi: 10.1016/j.cclet.2023.108341
Abstract:
Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts. Herein, for the first time, nickel foam supported Co4N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy. At the optimal potential, the Co4N/NF catalyst achieves ultra-high Faraday efficiency and NH3 selectivity of 95.4% and 99.4%, respectively. Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia. Theoretical calculations confirm that Co4N with abundant nitrogen vacancies can optimize the adsorption energies of NO3- and intermediates, lower the free energy (ΔG) of the potential-determining step (*NH3 to NH3) and inhibit the formation of N-containing byproducts. In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H2 quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate. This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.
Electrochemical nitrate reduction reaction (NITRR) is regarded as a “two birds-one stone” method for the treatment of nitrate contaminant in polluted water and the synthesis of valuable ammonia, which is retarded by the lack of highly reactive and selective electrocatalysts. Herein, for the first time, nickel foam supported Co4N was designed as a high-performance NITRR catalyst by an in-situ nonmetal leaching-induced strategy. At the optimal potential, the Co4N/NF catalyst achieves ultra-high Faraday efficiency and NH3 selectivity of 95.4% and 99.4%, respectively. Ex situ X-ray absorption spectroscopy (XAS), together with other experiments powerfully reveal that the nitrogen vacancies produced by nitrogen leaching are stable and play a key role in boosting nitrate reduction to ammonia. Theoretical calculations confirm that Co4N with abundant nitrogen vacancies can optimize the adsorption energies of NO3- and intermediates, lower the free energy (ΔG) of the potential-determining step (*NH3 to NH3) and inhibit the formation of N-containing byproducts. In addition, we also conclude that the nitrogen vacancies can stabilize the adsorbed hydrogen, making H2 quite difficult to produce, and lowering ΔG from *NO to *NOH, which facilitates the selective reduction of nitrate. This study reveals significant insights about the in-situ nonmetal leaching to enhance the NITRR activity.
2024, 35(2): 108354
doi: 10.1016/j.cclet.2023.108354
Abstract:
The design and development of energy storage device with high energy/power density has become a research hotspot. Zinc-ion hybrid capacitors (ZHCs) are considered as one of the most promising candidates. However, the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material. In this study, a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide (P-CNT/rGO) aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design. The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera, expanded interlayer spacing, and enhanced pseudocapacitance behavior, thus leading to significantly enhanced specific capacitance and superb ions transport performance. The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life. In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs. Furthermore, the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations. This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.
The design and development of energy storage device with high energy/power density has become a research hotspot. Zinc-ion hybrid capacitors (ZHCs) are considered as one of the most promising candidates. However, the application of ZHCs is hindered by their low energy density at high power density due to the unsatisfactory cathode material. In this study, a novel 3D phosphorus-doped carbon nanotube/reduced graphene oxide (P-CNT/rGO) aerogel cathode is synthesized through a synergistic modification strategy of CNT insertion and P doping modification combined with 3D porous design. The as-obtained P-CNT/rGO aerogel cathode manifests significantly increased surface aera, expanded interlayer spacing, and enhanced pseudocapacitance behavior, thus leading to significantly enhanced specific capacitance and superb ions transport performance. The as-assembled ZHC based on P-CNT/rGO cathode delivers a superior energy density of 42.2 Wh/kg at an extreme-high power density of 80 kW/kg and excellent cycle life. In-depth kinetic analyses are undertaken to prove the enhanced pseudocapacitance behavior and exceptional power output capability of ZHCs. Furthermore, the reaction mechanism of physical and chemical adsorption/desorption of electrolyte ions on the P-CNT/rGO cathode is revealed by systematic ex-situ characterizations. This work can provide a valuable reference for developing advanced graphene-based cathode for high energy/power density ZHCs.
2024, 35(2): 108356
doi: 10.1016/j.cclet.2023.108356
Abstract:
Owing to the large exciton binding energy (>100 meV) of most organic materials, the process of exciton dissociation into free electrons and holes is seriously hindered, which plays a key role in the photocatalytic system. In this study, a series of chalcogen (S, Se)-substituted mesoporous covalent organic frameworks (COFs) have been synthesized for enhanced photocatalytic organic transformations. Photoelectrochemical measurements indicate that the introduction of semi-metallic Se atom and the enlargement of conjugation degree can not only reduce the exciton binding energy accelerating the charge separation, but also reduce the band gap of COFs. As a result, the COF-NUST-36 with the lowest exciton binding energy (39.5 meV) shows the highest photocatalytic performance for selective oxidation of amines (up to 98% Conv. and 97.5% Sel.). This work provides a feasible method for designing COFs with high photocatalytic activity by adjusting exciton binding energy.
Owing to the large exciton binding energy (>100 meV) of most organic materials, the process of exciton dissociation into free electrons and holes is seriously hindered, which plays a key role in the photocatalytic system. In this study, a series of chalcogen (S, Se)-substituted mesoporous covalent organic frameworks (COFs) have been synthesized for enhanced photocatalytic organic transformations. Photoelectrochemical measurements indicate that the introduction of semi-metallic Se atom and the enlargement of conjugation degree can not only reduce the exciton binding energy accelerating the charge separation, but also reduce the band gap of COFs. As a result, the COF-NUST-36 with the lowest exciton binding energy (39.5 meV) shows the highest photocatalytic performance for selective oxidation of amines (up to 98% Conv. and 97.5% Sel.). This work provides a feasible method for designing COFs with high photocatalytic activity by adjusting exciton binding energy.
2024, 35(2): 108358
doi: 10.1016/j.cclet.2023.108358
Abstract:
In order to solve the contradiction between the rapidly growing energy demand and the excessive exploitation of fossil fuels, it is urgent to research and develops more environmentally friendly and efficient energy storage technologies. Therefore, the development of high-performance cathode materials to enhance the energy density of SIB is currently one of the most important topics of scientific research. Advanced high-voltage and low-cost cathode material for SIBs, a composite of carbon-coated Na4MnCr(PO4)3 (NASICON-type), polyvinylpyrrolidone (PVP), and modified carbon nanotubes (CNTs) is prepared by sol-gel and freeze-drying method. Due to the high conductivity of CNTs, the conductivity of the composite is significantly improved, and its initial capacity is increased to 114 mAh/g at 0.5 C and 96 mAh/g at 5 C (Mn2+/Mn4+ conversion for voltage windows 1.4-4.3 V). Moreover, the multi-electrons transfer of Cr3+/Cr4+ and Mn2+/Mn4+ can provide a high capacity of 165 mAh/g at 0.1 C and 102 mAh/g at 5 C in the high voltage window of 1.4-4.6 V. Furthermore, PVP can effectively inhibit the Jahn-Teller effect caused by Mn ion, making the composite have more excellent high-rate performance and stability. In addition, GITT, EIS and CV curves were drawn to better reveal the excellent kinetic properties of Na4MnCr(PO4)3@C@PVP@CNT cathode, and the mechanism of its performance improvement is deeply studied and discussed. Accordingly, the co-doping of CNTs and PVP is a simple way to high conductivity and fast charging of cathode materials for SIBs.
In order to solve the contradiction between the rapidly growing energy demand and the excessive exploitation of fossil fuels, it is urgent to research and develops more environmentally friendly and efficient energy storage technologies. Therefore, the development of high-performance cathode materials to enhance the energy density of SIB is currently one of the most important topics of scientific research. Advanced high-voltage and low-cost cathode material for SIBs, a composite of carbon-coated Na4MnCr(PO4)3 (NASICON-type), polyvinylpyrrolidone (PVP), and modified carbon nanotubes (CNTs) is prepared by sol-gel and freeze-drying method. Due to the high conductivity of CNTs, the conductivity of the composite is significantly improved, and its initial capacity is increased to 114 mAh/g at 0.5 C and 96 mAh/g at 5 C (Mn2+/Mn4+ conversion for voltage windows 1.4-4.3 V). Moreover, the multi-electrons transfer of Cr3+/Cr4+ and Mn2+/Mn4+ can provide a high capacity of 165 mAh/g at 0.1 C and 102 mAh/g at 5 C in the high voltage window of 1.4-4.6 V. Furthermore, PVP can effectively inhibit the Jahn-Teller effect caused by Mn ion, making the composite have more excellent high-rate performance and stability. In addition, GITT, EIS and CV curves were drawn to better reveal the excellent kinetic properties of Na4MnCr(PO4)3@C@PVP@CNT cathode, and the mechanism of its performance improvement is deeply studied and discussed. Accordingly, the co-doping of CNTs and PVP is a simple way to high conductivity and fast charging of cathode materials for SIBs.
Studying the variable energy band structure for energy storage materials in charge/discharge process
2024, 35(2): 108380
doi: 10.1016/j.cclet.2023.108380
Abstract:
So far, a clear understanding about the relationship of variable energy band structure with the corresponding charge-discharge process of energy storage materials is still lacking. Here, using optical spectroscopy (red-green-blue (RGB) value, reflectivity, transmittance, UV–vis, XPS, UPS) to study α-Co(OH)2 electrode working in KOH electrolyte as the research object, we provide direct experimental evidence that: (1) The intercalation of OH– ions will reduce the valence/conduction band (VB and CB) and band gap energy (Eg) values; (2) The deintercalation of OH– ions corresponds with the reversion of VB, CB and Eg to the initial values; (3) The color of Co(OH)2 electrode also exhibit regular variations in RGB value during the charge-discharge process.
So far, a clear understanding about the relationship of variable energy band structure with the corresponding charge-discharge process of energy storage materials is still lacking. Here, using optical spectroscopy (red-green-blue (RGB) value, reflectivity, transmittance, UV–vis, XPS, UPS) to study α-Co(OH)2 electrode working in KOH electrolyte as the research object, we provide direct experimental evidence that: (1) The intercalation of OH– ions will reduce the valence/conduction band (VB and CB) and band gap energy (Eg) values; (2) The deintercalation of OH– ions corresponds with the reversion of VB, CB and Eg to the initial values; (3) The color of Co(OH)2 electrode also exhibit regular variations in RGB value during the charge-discharge process.
2024, 35(2): 108406
doi: 10.1016/j.cclet.2023.108406
Abstract:
Rechargeable alkaline aqueous zinc batteries (RAZBs) have attracted increasing attention. However, most RAZBs are hindered by the limited availability of cathode materials. The practical electrochemical performance of most cathode materials is lower than the theoretical value due to their poor electrical conductivity and low utilization capacity. In this work, we develop a facile hydrothermal procedure to prepare highly uniform bimetallic sulfides as novel cathode materials for RAZBs. Copper-cobalt binary metallic oxides materials possess higher conductivity and larger capacity compared with their mono-metal oxides compounds due to bimetallic synergistic effects and multiple oxidation states. Furthermore, bimetallic sulfide compounds have smaller bond energy and longer bond length than their oxides, leading to less structural damage, faster kinetics of electrochemical reactions, and better stability. The as-prepared Co-Cu bimetallic sulfides show enhanced electrochemical performance due to various valences of Co and Cu as well as the existence of S. As a result, aqueous Zn/CuCo2S4 battery shows a high specific capacity of 117.4 mAh/g at 4 A/g and a good cycle life of over 8000 cycles. Based on PANa hydrogel electrolytes, a flexible Zn/CuCo2S4 battery demonstrates excellent cycling stability. This battery can also meet the requirements of electronic devices with different shapes and performs well in extreme environments, such as freezing, drilling, and hammering. This work opens new avenues to obtain high-rate and long-life cathode materials for RAZBs by utilizing the synergistic effects of bimetallic sulfides and provides a new platform for flexible energy storage devices.
Rechargeable alkaline aqueous zinc batteries (RAZBs) have attracted increasing attention. However, most RAZBs are hindered by the limited availability of cathode materials. The practical electrochemical performance of most cathode materials is lower than the theoretical value due to their poor electrical conductivity and low utilization capacity. In this work, we develop a facile hydrothermal procedure to prepare highly uniform bimetallic sulfides as novel cathode materials for RAZBs. Copper-cobalt binary metallic oxides materials possess higher conductivity and larger capacity compared with their mono-metal oxides compounds due to bimetallic synergistic effects and multiple oxidation states. Furthermore, bimetallic sulfide compounds have smaller bond energy and longer bond length than their oxides, leading to less structural damage, faster kinetics of electrochemical reactions, and better stability. The as-prepared Co-Cu bimetallic sulfides show enhanced electrochemical performance due to various valences of Co and Cu as well as the existence of S. As a result, aqueous Zn/CuCo2S4 battery shows a high specific capacity of 117.4 mAh/g at 4 A/g and a good cycle life of over 8000 cycles. Based on PANa hydrogel electrolytes, a flexible Zn/CuCo2S4 battery demonstrates excellent cycling stability. This battery can also meet the requirements of electronic devices with different shapes and performs well in extreme environments, such as freezing, drilling, and hammering. This work opens new avenues to obtain high-rate and long-life cathode materials for RAZBs by utilizing the synergistic effects of bimetallic sulfides and provides a new platform for flexible energy storage devices.
2024, 35(2): 108427
doi: 10.1016/j.cclet.2023.108427
Abstract:
Stimuli-responsive smart materials exhibit reverse chemical/physical changes in response to external stimuli and research on stimuli-responsive smart materials with self-powered properties is still uncultivated ground. Here, we report perovskite crystalline self-powered multiple stimuli-responsive materials triggered by chemical and thermal stimuli. [HMEP]PbI3·(H2O) (1; HMEP is a hydroxytris(1-methylethyl)phosphorus cation) crystallizes in a chiral space group P21 at 293 K and has the piezoelectric reaction (d33 = 10 pC/N and output voltage = 1 V) of self-powered modes, this value is larger than the value of 3 pC/N for the classical piezoelectric material ZnO. Piezoelectric materials can generate energy due to mechanical deformation, and using thermal heating to lose water, [HMEP]PbI3 (2) can be obtained. 2 crystallizes in the non-centrosymmetric space group, undergoes two reversible phase transitions at 243/255 K and 315/348 K, and shows second harmonic generation switching. Interestingly, 2 can return to the hydrated form 1 after absorbing water. This work will lay the foundation for self-powered stimuli-responsive compounds and contribute to the construction of novel organic-inorganic hybrid materials with second harmonic generation switching.
Stimuli-responsive smart materials exhibit reverse chemical/physical changes in response to external stimuli and research on stimuli-responsive smart materials with self-powered properties is still uncultivated ground. Here, we report perovskite crystalline self-powered multiple stimuli-responsive materials triggered by chemical and thermal stimuli. [HMEP]PbI3·(H2O) (1; HMEP is a hydroxytris(1-methylethyl)phosphorus cation) crystallizes in a chiral space group P21 at 293 K and has the piezoelectric reaction (d33 = 10 pC/N and output voltage = 1 V) of self-powered modes, this value is larger than the value of 3 pC/N for the classical piezoelectric material ZnO. Piezoelectric materials can generate energy due to mechanical deformation, and using thermal heating to lose water, [HMEP]PbI3 (2) can be obtained. 2 crystallizes in the non-centrosymmetric space group, undergoes two reversible phase transitions at 243/255 K and 315/348 K, and shows second harmonic generation switching. Interestingly, 2 can return to the hydrated form 1 after absorbing water. This work will lay the foundation for self-powered stimuli-responsive compounds and contribute to the construction of novel organic-inorganic hybrid materials with second harmonic generation switching.
2024, 35(2): 108445
doi: 10.1016/j.cclet.2023.108445
Abstract:
Achieving high activity and durability for the oxygen reduction reaction (ORR) with an ultra-low amount of platinum is significant to promote the widespread application of proton exchange membrane fuel cells (PEMFCs). Here we report a new ultrathin (~1 nm) ternary PtNiGa alloy nanowires (PtNiGa NWs) electrocatalyst, in which the presence of gallium (Ga) enhances the oxidation resistance of platinum (Pt) and nickel (Ni) and suppresses the dissolution of Ni. The mass and specific activities of PtNiGa NWs are about 11.2 and 7.6 times higher than those of commercial Pt/C catalysts for ORR. Moreover, the mass activity of PtNiGa/C NWs nanocatalyst decreased only by 12.8% and largely retained its electrochemical surface area (ECSA) after 10,000 potential cycles, compared with 38% loss of ECSA for commercial Pt/C catalyst. Therefore, this work provides a general guideline for preparing ternary alloy electrocatalysts and enhancing the activity and stability of the cathode ORR reaction of PEMFCs.
Achieving high activity and durability for the oxygen reduction reaction (ORR) with an ultra-low amount of platinum is significant to promote the widespread application of proton exchange membrane fuel cells (PEMFCs). Here we report a new ultrathin (~1 nm) ternary PtNiGa alloy nanowires (PtNiGa NWs) electrocatalyst, in which the presence of gallium (Ga) enhances the oxidation resistance of platinum (Pt) and nickel (Ni) and suppresses the dissolution of Ni. The mass and specific activities of PtNiGa NWs are about 11.2 and 7.6 times higher than those of commercial Pt/C catalysts for ORR. Moreover, the mass activity of PtNiGa/C NWs nanocatalyst decreased only by 12.8% and largely retained its electrochemical surface area (ECSA) after 10,000 potential cycles, compared with 38% loss of ECSA for commercial Pt/C catalyst. Therefore, this work provides a general guideline for preparing ternary alloy electrocatalysts and enhancing the activity and stability of the cathode ORR reaction of PEMFCs.
2024, 35(2): 108450
doi: 10.1016/j.cclet.2023.108450
Abstract:
We report a facile template-free fabrication of heterostructured Co3O4/CuO hollow nanospheres using pre-synthesized Co/Cu-glycerate as conformal precursor. The introduction of copper nitrate in the solvothermal reaction system of glycerol/isopropanol/cobalt nitrate readily induces the conversion from solid Co-glycerate to hollow Co/Cu-glycerate nanospheres, and the effect of the Co/Cu atomic ratio on the structure evolution of the metal glycerates as well as their corresponding oxides were investigated. When examined as anode materials for lithium-ion batteries, the well-defined Co3O4/CuO hollow nanospheres with Co/Cu molar ratio of 2.0 demonstrate excellent lithium storage performance, delivering a high reversible capacity of 930 mAh/g after 300 cycles at a current density of 0.5 A/g and a stable capacity of 650 mAh/g after 500 cycles even at a higher current density of 2.0 A/g, which are much better than their counterparts of bare CuO and Co3O4. The enhanced lithium storage performance can be attributed to the synergistic effect of the CuO and Co3O4 heterostructure with hollow spherical morphology, which greatly enhances the charge/electrolyte transfer and effectively buffers the volume changes upon lithiation/delithiation cycling.
We report a facile template-free fabrication of heterostructured Co3O4/CuO hollow nanospheres using pre-synthesized Co/Cu-glycerate as conformal precursor. The introduction of copper nitrate in the solvothermal reaction system of glycerol/isopropanol/cobalt nitrate readily induces the conversion from solid Co-glycerate to hollow Co/Cu-glycerate nanospheres, and the effect of the Co/Cu atomic ratio on the structure evolution of the metal glycerates as well as their corresponding oxides were investigated. When examined as anode materials for lithium-ion batteries, the well-defined Co3O4/CuO hollow nanospheres with Co/Cu molar ratio of 2.0 demonstrate excellent lithium storage performance, delivering a high reversible capacity of 930 mAh/g after 300 cycles at a current density of 0.5 A/g and a stable capacity of 650 mAh/g after 500 cycles even at a higher current density of 2.0 A/g, which are much better than their counterparts of bare CuO and Co3O4. The enhanced lithium storage performance can be attributed to the synergistic effect of the CuO and Co3O4 heterostructure with hollow spherical morphology, which greatly enhances the charge/electrolyte transfer and effectively buffers the volume changes upon lithiation/delithiation cycling.
2024, 35(2): 108466
doi: 10.1016/j.cclet.2023.108466
Abstract:
Patients with epidermal growth factor receptor (EGFR) wild-type non-small cell lung cancer (NSCLC) often show primary resistance to gefitinib therapy. It is thus necessary to study the metabolism of gefitinib in NSCLC cells to comprehensively reveal the reasons for the primary resistance of tumors. Herein, we develop a platform for studying drug metabolism heterogeneity based on single-cell mass spectrometry (sDMH-scMS) by integrating living-cell electrolaunching ionization MS (ILCEI-MS) and high-performance liquid chromatography-MS (HPLC-MS) analysis, and the primary resistance of NSCLC cells to gefitinib was studied using this platform. The ILCEI-MS analysis showed that approximately 11.9% of NSCLC single cells contained the gefitinib metabolite M11; HPLC-MS detection diluted the intensity of M11 in subpopulations and concealed the heterogeneity of drug metabolism in tumor single cells. The intensity of gefitinib in EGFR wild-type A549 cells was markedly lower than in mutant PC9 cells, and the intensity of gefitinib metabolites was significantly higher than in PC9 cells, suggesting that the primary resistance of NSCLC cells is related to gefitinib metabolism. Moreover, the combination of gefitinib and the drug-metabolizing enzyme inhibitor α-naphthoflavone was shown to overcome the primary resistance of the NSCLC cells. Overall, the results of this study are expected to be applicable for clinical drug resistance diagnosis and treatment at the single-cell level.
Patients with epidermal growth factor receptor (EGFR) wild-type non-small cell lung cancer (NSCLC) often show primary resistance to gefitinib therapy. It is thus necessary to study the metabolism of gefitinib in NSCLC cells to comprehensively reveal the reasons for the primary resistance of tumors. Herein, we develop a platform for studying drug metabolism heterogeneity based on single-cell mass spectrometry (sDMH-scMS) by integrating living-cell electrolaunching ionization MS (ILCEI-MS) and high-performance liquid chromatography-MS (HPLC-MS) analysis, and the primary resistance of NSCLC cells to gefitinib was studied using this platform. The ILCEI-MS analysis showed that approximately 11.9% of NSCLC single cells contained the gefitinib metabolite M11; HPLC-MS detection diluted the intensity of M11 in subpopulations and concealed the heterogeneity of drug metabolism in tumor single cells. The intensity of gefitinib in EGFR wild-type A549 cells was markedly lower than in mutant PC9 cells, and the intensity of gefitinib metabolites was significantly higher than in PC9 cells, suggesting that the primary resistance of NSCLC cells is related to gefitinib metabolism. Moreover, the combination of gefitinib and the drug-metabolizing enzyme inhibitor α-naphthoflavone was shown to overcome the primary resistance of the NSCLC cells. Overall, the results of this study are expected to be applicable for clinical drug resistance diagnosis and treatment at the single-cell level.
2024, 35(2): 108505
doi: 10.1016/j.cclet.2023.108505
Abstract:
Native amino-directed palladium-catalyzed C(sp3)–H activation/functionalization has been developed for modification of α-amino acids and peptides. Herein a palladium(Ⅱ)-catalyzed C(sp2)–H arylation of α-amino-β-aryl esters has been disclosed, using the native amino as the directing group. A variety of chiral α-amino-β-aryl esters can be functionalized to give the corresponding ortho-substituted mono- and di-arylated products.
Native amino-directed palladium-catalyzed C(sp3)–H activation/functionalization has been developed for modification of α-amino acids and peptides. Herein a palladium(Ⅱ)-catalyzed C(sp2)–H arylation of α-amino-β-aryl esters has been disclosed, using the native amino as the directing group. A variety of chiral α-amino-β-aryl esters can be functionalized to give the corresponding ortho-substituted mono- and di-arylated products.
2024, 35(2): 108506
doi: 10.1016/j.cclet.2023.108506
Abstract:
Bone metastasis, a life-threatening complication of advanced breast cancer, is often accompanied by debilitating pain (cancer-induced bone pain, CIBP) that severely impairs life quality and survival. The concurrent treatment of bone metastases and CIBP remains a clinical challenge because the therapeutic options are limited. In this study, we construct a near-infrared light-activated nano-therapeutic system to meet this conundrum. In detail, sorafenib (SRF) and photosensitizer (chlorin e6, Ce6) are encapsulated into mesoporous hydroxyapatite nanoparticles (HANPs), which are further functionalized with hyaluronic acid (HA) to obtain HA-SRF/Ce6@HANPs system. The designed nanoplatform destroys tumor cells in vitro and in vivo via the synergism of SRF (interrupting the exchange of cystine/glutamate by inhibiting SLC7A11) and photodynamic therapy (PDT, inducing reactive oxygen species generation). The decrease in tumor burden and reduction of extracellular glutamate significantly attenuate CIBP in mice model with developing bone cancer. Moreover, the combination of HA-SRF/Ce6@HANPs and PDT inhibit osteoclasts activation, promote osteoblast differentiation and accelerate bone repair. Overall, the nanoagent with good biocompatibility may provide an effective therapy method for the concurrent treatment of breast cancer bone metastasis and CIBP.
Bone metastasis, a life-threatening complication of advanced breast cancer, is often accompanied by debilitating pain (cancer-induced bone pain, CIBP) that severely impairs life quality and survival. The concurrent treatment of bone metastases and CIBP remains a clinical challenge because the therapeutic options are limited. In this study, we construct a near-infrared light-activated nano-therapeutic system to meet this conundrum. In detail, sorafenib (SRF) and photosensitizer (chlorin e6, Ce6) are encapsulated into mesoporous hydroxyapatite nanoparticles (HANPs), which are further functionalized with hyaluronic acid (HA) to obtain HA-SRF/Ce6@HANPs system. The designed nanoplatform destroys tumor cells in vitro and in vivo via the synergism of SRF (interrupting the exchange of cystine/glutamate by inhibiting SLC7A11) and photodynamic therapy (PDT, inducing reactive oxygen species generation). The decrease in tumor burden and reduction of extracellular glutamate significantly attenuate CIBP in mice model with developing bone cancer. Moreover, the combination of HA-SRF/Ce6@HANPs and PDT inhibit osteoclasts activation, promote osteoblast differentiation and accelerate bone repair. Overall, the nanoagent with good biocompatibility may provide an effective therapy method for the concurrent treatment of breast cancer bone metastasis and CIBP.
2024, 35(2): 108519
doi: 10.1016/j.cclet.2023.108519
Abstract:
Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer, regulate adsorption energy of reaction intermediates, and provide additional active sites, which are regarded as valid means for improving catalytic activity. However, the underlying mechanism of synergistic regulation of interfacial charge transfer and optimization of electrocatalytic activity by combining vacancy and Mott-Schottky junction remains unclear. Herein, the growth of a bifunctional NiCo/NiCoP Mott-Schottky electrode with abundant phosphorus vacancies on foam nickel (NF) has been synthesized through continuous phosphating and reduction processes. The obtained NiCo/NiCoP heterojunctions show remarkable OER and HER activities, and the overpotentials for OER and HER are as low as 117 and 60 mV at 10 mA/cm2 in 1 mol/L KOH, respectively. Moreover, as both the cathode and anode of overall water splitting, the voltage of the bifunctional NiCo/NiCoP electrocatalyst is 1.44 V at 10 mA/cm2, which are far exceeding the benchmark commercial electrodes. DFT theoretical calculation results confirm that the phosphorus vacancies and build-in electric field can effectively accelerate ion and electron transfer between NiCo alloy and NiCoP semiconductor, tailor the electronic structure of the metal centers and lower the Gibbs free energy of the intermediates. Furthermore, the unique self-supported integrated structure is beneficial to facilitate the exposure of the active site, avoid catalyst shedding, thus improving the activity and structural stability of NiCo/NiCoP. This study provides an avenue for the controllable synthesis and performance optimization of Mott-Schottky electrocatalysts.
Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer, regulate adsorption energy of reaction intermediates, and provide additional active sites, which are regarded as valid means for improving catalytic activity. However, the underlying mechanism of synergistic regulation of interfacial charge transfer and optimization of electrocatalytic activity by combining vacancy and Mott-Schottky junction remains unclear. Herein, the growth of a bifunctional NiCo/NiCoP Mott-Schottky electrode with abundant phosphorus vacancies on foam nickel (NF) has been synthesized through continuous phosphating and reduction processes. The obtained NiCo/NiCoP heterojunctions show remarkable OER and HER activities, and the overpotentials for OER and HER are as low as 117 and 60 mV at 10 mA/cm2 in 1 mol/L KOH, respectively. Moreover, as both the cathode and anode of overall water splitting, the voltage of the bifunctional NiCo/NiCoP electrocatalyst is 1.44 V at 10 mA/cm2, which are far exceeding the benchmark commercial electrodes. DFT theoretical calculation results confirm that the phosphorus vacancies and build-in electric field can effectively accelerate ion and electron transfer between NiCo alloy and NiCoP semiconductor, tailor the electronic structure of the metal centers and lower the Gibbs free energy of the intermediates. Furthermore, the unique self-supported integrated structure is beneficial to facilitate the exposure of the active site, avoid catalyst shedding, thus improving the activity and structural stability of NiCo/NiCoP. This study provides an avenue for the controllable synthesis and performance optimization of Mott-Schottky electrocatalysts.
2024, 35(2): 108528
doi: 10.1016/j.cclet.2023.108528
Abstract:
Although it has been developed for many years, nucleic acid aptamer screening technology still fails to be widely used, a considerable part of it is due to the variability of tumor cell morphology, which leads to the use of immortalized cell lines in the laboratory to screen nucleic acid aptamers for recognition ability of tumor cells in the diseased body. To address this, primary cells that can be stably passaged were isolated and extracted from spontaneous tumors of genetically engineered pancreatic ductal adenocarcinoma model mice in this study. Next, an automated screening instrument for nucleic acid aptamers developed autonomously by our group was used to perform efficient aptamer screening using a limited number of cells, and the obtained nucleic acid aptamers were affinity verified at the cellular level. Finally, to answer the question of the cell growth environment difference on the recognition ability of nucleic acid aptamers, we verified its targeting ability to tumors in vivo on a nude mice xenograft tumor model, and further used a common antitumor drug doxorubicin combined with nucleic acid aptamers to verify the drug loading ability of this aptamer combined with the targeting therapeutic ability.
Although it has been developed for many years, nucleic acid aptamer screening technology still fails to be widely used, a considerable part of it is due to the variability of tumor cell morphology, which leads to the use of immortalized cell lines in the laboratory to screen nucleic acid aptamers for recognition ability of tumor cells in the diseased body. To address this, primary cells that can be stably passaged were isolated and extracted from spontaneous tumors of genetically engineered pancreatic ductal adenocarcinoma model mice in this study. Next, an automated screening instrument for nucleic acid aptamers developed autonomously by our group was used to perform efficient aptamer screening using a limited number of cells, and the obtained nucleic acid aptamers were affinity verified at the cellular level. Finally, to answer the question of the cell growth environment difference on the recognition ability of nucleic acid aptamers, we verified its targeting ability to tumors in vivo on a nude mice xenograft tumor model, and further used a common antitumor drug doxorubicin combined with nucleic acid aptamers to verify the drug loading ability of this aptamer combined with the targeting therapeutic ability.
2024, 35(2): 108534
doi: 10.1016/j.cclet.2023.108534
Abstract:
Developing precise extracellular vesicles (EVs) labelling techniques with minimal disturbance is of great importance to the follow-up EVs detection and analysis. However, currently available methods such as using probes to conjugate phospholipids or membrane proteins have certain limitations due to EV steric hindrance, dye aggregation, etc. Here, we present a microfluidic platform to enhance EVs' labelling efficiency and improve their detection. This platform provides excellent sample throughput and high-efficiency EV labelling at lower label concentrations with an optimized flowing rate. Flow cytometry analysis (FCM) and cellular uptake results show that EV labelling by utilizing this platform possesses the merits of a higher labelling efficiency with 64.1% relative improvement than conventional co-incubation method and a lower background noise. Moreover, this technique maintains EVs' size, morphology and biological activities. After the recipient cells uptake the EVs treated by the microfluidic platform, the spatial and temporal distribution of EVs in the cells are clearly observed. These results demonstrate that our method holds great potential in efficient labelling of EVs, which is essential to subsequent EV quantification and analysis.
Developing precise extracellular vesicles (EVs) labelling techniques with minimal disturbance is of great importance to the follow-up EVs detection and analysis. However, currently available methods such as using probes to conjugate phospholipids or membrane proteins have certain limitations due to EV steric hindrance, dye aggregation, etc. Here, we present a microfluidic platform to enhance EVs' labelling efficiency and improve their detection. This platform provides excellent sample throughput and high-efficiency EV labelling at lower label concentrations with an optimized flowing rate. Flow cytometry analysis (FCM) and cellular uptake results show that EV labelling by utilizing this platform possesses the merits of a higher labelling efficiency with 64.1% relative improvement than conventional co-incubation method and a lower background noise. Moreover, this technique maintains EVs' size, morphology and biological activities. After the recipient cells uptake the EVs treated by the microfluidic platform, the spatial and temporal distribution of EVs in the cells are clearly observed. These results demonstrate that our method holds great potential in efficient labelling of EVs, which is essential to subsequent EV quantification and analysis.
2024, 35(2): 108536
doi: 10.1016/j.cclet.2023.108536
Abstract:
Immune checkpoint inhibitors (ICIs) therapy targeting programmed cell death ligand 1 (PD-L1) and programmed death protein 1 (PD-1) had exhibited significant clinical benefits for cancer treatment such as triple negative breast cancer (TNBC). However, the relatively low anti-tumor immune response rate and ICIs drug resistance highlight the necessity of developing ICIs combination therapy strategies to improve the anti-tumor effect of immunotherapy. Herein, the immunomodulator epigallocatechin gallate palmitate (PEGCG) and the immunoadjuvant metformin (MET) self-assembled into tumor-targeted micelles via hydrogen bond and electrostatic interaction, which encapsulated the therapeutic agents doxorubicin (DOX)-loaded PEGCG-MET micelles (PMD) and combined with ICIs (anti-PD-1 antibody) as therapeutic strategy to reduce the endogenous expression of PD-L1 and improve the tumor immunosuppressive microenvironment. The results presented that PMD integrated chemotherapy and immunotherapy to enhance antitumor efficacy in vitro and in vivo, compared with DOX or anti-PD-1 antibody for the therapy of TNBC. PMD micelles might be a potential candidate, which could remedy the shortcomings of antibody-based ICIs and provide synergistic effect to enhance the antitumor effects of ICIs in tumor therapy.
Immune checkpoint inhibitors (ICIs) therapy targeting programmed cell death ligand 1 (PD-L1) and programmed death protein 1 (PD-1) had exhibited significant clinical benefits for cancer treatment such as triple negative breast cancer (TNBC). However, the relatively low anti-tumor immune response rate and ICIs drug resistance highlight the necessity of developing ICIs combination therapy strategies to improve the anti-tumor effect of immunotherapy. Herein, the immunomodulator epigallocatechin gallate palmitate (PEGCG) and the immunoadjuvant metformin (MET) self-assembled into tumor-targeted micelles via hydrogen bond and electrostatic interaction, which encapsulated the therapeutic agents doxorubicin (DOX)-loaded PEGCG-MET micelles (PMD) and combined with ICIs (anti-PD-1 antibody) as therapeutic strategy to reduce the endogenous expression of PD-L1 and improve the tumor immunosuppressive microenvironment. The results presented that PMD integrated chemotherapy and immunotherapy to enhance antitumor efficacy in vitro and in vivo, compared with DOX or anti-PD-1 antibody for the therapy of TNBC. PMD micelles might be a potential candidate, which could remedy the shortcomings of antibody-based ICIs and provide synergistic effect to enhance the antitumor effects of ICIs in tumor therapy.
2024, 35(2): 108539
doi: 10.1016/j.cclet.2023.108539
Abstract:
Photodynamic therapy (PDT) is an effective treatment method for tumors. But the specifically accumulated of photosensitizer was very difficult in the tumor site, which greatly limited the efficacy of PDT. Here, mitochondria-targeted Janus mesoporous nanoplatform (JPMO-Pt-CTPP-ZnPc) for PDT was prepared, the nanoplatform has uniform size (275 nm) and good dispersion and biocompatibility. The confocal laser scanning microscopy (CLSM) revealed the signal of ZnPc of JPMO-Pt-CTPP-ZnPc were higher than JPMO-Pt-ZnPc in tumor cells, and flow cytometry results showed the cell uptake efficiency of JPMO-Pt-CTPP-ZnPc was 2.5-fold higher than that of JPMO-Pt-ZnPc. This revealed the modification of CTPP significantly improves the targeting ability of the nanoplatform. In vitro anti-tumor experiment showed the JPMO-Pt-CTPP-ZnPc significantly inhibited the growth of tumor cells upon the irradiation of low-power laser, and the survival rate of cells incubated with 60 µg/mL JPMO-Pt-CTPP-ZnPc was only 3%. Simultaneously, compared with JPMO-Pt-ZnPc (not modified with mitochondria targeting molecules CTPP), the PDT efficacy of JPMO-Pt-CTPP-ZnPc was significantly better, as it has targeted mitochondria in cells.
Photodynamic therapy (PDT) is an effective treatment method for tumors. But the specifically accumulated of photosensitizer was very difficult in the tumor site, which greatly limited the efficacy of PDT. Here, mitochondria-targeted Janus mesoporous nanoplatform (JPMO-Pt-CTPP-ZnPc) for PDT was prepared, the nanoplatform has uniform size (275 nm) and good dispersion and biocompatibility. The confocal laser scanning microscopy (CLSM) revealed the signal of ZnPc of JPMO-Pt-CTPP-ZnPc were higher than JPMO-Pt-ZnPc in tumor cells, and flow cytometry results showed the cell uptake efficiency of JPMO-Pt-CTPP-ZnPc was 2.5-fold higher than that of JPMO-Pt-ZnPc. This revealed the modification of CTPP significantly improves the targeting ability of the nanoplatform. In vitro anti-tumor experiment showed the JPMO-Pt-CTPP-ZnPc significantly inhibited the growth of tumor cells upon the irradiation of low-power laser, and the survival rate of cells incubated with 60 µg/mL JPMO-Pt-CTPP-ZnPc was only 3%. Simultaneously, compared with JPMO-Pt-ZnPc (not modified with mitochondria targeting molecules CTPP), the PDT efficacy of JPMO-Pt-CTPP-ZnPc was significantly better, as it has targeted mitochondria in cells.
2024, 35(2): 108546
doi: 10.1016/j.cclet.2023.108546
Abstract:
An atom economic β-C(sp3)−H chlorination of amide derivatives has been developed. This mild protocol employs CuCl2 instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-stage functionalization of medicine derivatives. Mechanism studies suggest a plausible visible light triggered ligand-to-metal charge transfer (LMCT)/1,4-hydrogen atom transfer (HAT) cascade.
An atom economic β-C(sp3)−H chlorination of amide derivatives has been developed. This mild protocol employs CuCl2 instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-stage functionalization of medicine derivatives. Mechanism studies suggest a plausible visible light triggered ligand-to-metal charge transfer (LMCT)/1,4-hydrogen atom transfer (HAT) cascade.
2024, 35(2): 108551
doi: 10.1016/j.cclet.2023.108551
Abstract:
Two-dimensional (2D) carbon nitride sheets (CNs) with atomically thin structures are regarded as one of the most promising materials for solar energy conversion. However, due to their substantially enlarged bandgap caused by the strong quantum size effect and their incomplete polymerisation with a large number of non-condensed surface amino groups, the practical applicability of CNs in photocatalysis is limited. In this study, CNs with broad visible-light absorption were synthesised using a 5-min fast thermal annealing. The removal of uncondensed amine groups reduces the bandgap of CNs from 3.06 eV to 2.60 eV, increasing their absorption of visible light. Interestingly, the CNs were distorted after annealing, which can differentiate the spatial positions of electrons and holes, enhancing the visible-light absorption efficiency. As a result, when exposed to visible light, the photocatalytic hydrogen production activity of atomically thin 2D CNs rose by 8.38 times. This research presents a dependable and speedy method for creating highly effective visible-light photocatalysts with narrowed bandgaps and improved visible-light absorption.
Two-dimensional (2D) carbon nitride sheets (CNs) with atomically thin structures are regarded as one of the most promising materials for solar energy conversion. However, due to their substantially enlarged bandgap caused by the strong quantum size effect and their incomplete polymerisation with a large number of non-condensed surface amino groups, the practical applicability of CNs in photocatalysis is limited. In this study, CNs with broad visible-light absorption were synthesised using a 5-min fast thermal annealing. The removal of uncondensed amine groups reduces the bandgap of CNs from 3.06 eV to 2.60 eV, increasing their absorption of visible light. Interestingly, the CNs were distorted after annealing, which can differentiate the spatial positions of electrons and holes, enhancing the visible-light absorption efficiency. As a result, when exposed to visible light, the photocatalytic hydrogen production activity of atomically thin 2D CNs rose by 8.38 times. This research presents a dependable and speedy method for creating highly effective visible-light photocatalysts with narrowed bandgaps and improved visible-light absorption.
2024, 35(2): 108560
doi: 10.1016/j.cclet.2023.108560
Abstract:
Protein S-sulfenylation (protein sulfenic acid), as one of the most significant oxidative post-translational modifications (OxiPTMs), plays a vital role in regulating protein function. A variety of activity-based probes have been developed to profile sulfenic acid in living cells. However, due to the transient presence and low content of sulfenic acid in living cell, high doses of probes are needed to achieve efficient labeling. More importantly, current probes have no temporal control over sulfenic acid labeling. To overcome these limitations, two caged cysteine sulfenic acid probes DYn-2-ONB and DYn-2-Cou with either an o-nitrobenzyl or coumarin protecting group were developed in this study. Both probes can be efficiently uncaged via irradiation to produce the active C-nucleophile probe DYn-2. Labeling assay in living cells demonstrated DYn-2-ONB exhibited better labeling capacity compared with DYn-2, providing it as a powerful tool for improved monitoring of protein S-sulfenylation in living cells.
Protein S-sulfenylation (protein sulfenic acid), as one of the most significant oxidative post-translational modifications (OxiPTMs), plays a vital role in regulating protein function. A variety of activity-based probes have been developed to profile sulfenic acid in living cells. However, due to the transient presence and low content of sulfenic acid in living cell, high doses of probes are needed to achieve efficient labeling. More importantly, current probes have no temporal control over sulfenic acid labeling. To overcome these limitations, two caged cysteine sulfenic acid probes DYn-2-ONB and DYn-2-Cou with either an o-nitrobenzyl or coumarin protecting group were developed in this study. Both probes can be efficiently uncaged via irradiation to produce the active C-nucleophile probe DYn-2. Labeling assay in living cells demonstrated DYn-2-ONB exhibited better labeling capacity compared with DYn-2, providing it as a powerful tool for improved monitoring of protein S-sulfenylation in living cells.
2024, 35(2): 108568
doi: 10.1016/j.cclet.2023.108568
Abstract:
Establishing an effective charge transfer mechanism in carbon nitride (g-C3N4) to enhance its photocatalytic activity remains a limiting nuisance. Herein, the combination design of a single Cu atom with hollow g-C3N4 nanospheres (Cu-N3 structure) has been proven to offer significant opportunities for this crucial challenge. Moreover, this structure endows two pathways for charge transfer in the reaction, namely, the N atoms in the three-dimensional planar structure are only bonded with a single Cu atom, and charge transfer occurs between the plane and the layered structure due to the bending of the interlayered g-C3N4 hollow nanospheres. Notably, Cu-N3 and hollow nanosphere structures have been certified to greatly enhance the efficiency of photogenerated carrier separation and transfer between the layers and planes by ultrafast spectral analysis. As a result, this catalyst possesses unparalleled photocatalytic efficiency. Specifically, the hydrogen production rate up to 2040 µmol h−1 g−1, which is 51 times that of pure C3N4 under visible light conditions. The photocatalytic degradation performance of tetracycline and oxidation performance of benzene is also expressed, with a degradation rate of 100%, a conversion of 97.3% and a selectivity of 99.9%. This work focuses on the structure-activity relationship to provide the possibilities for the development of potential photocatalytic materials.
Establishing an effective charge transfer mechanism in carbon nitride (g-C3N4) to enhance its photocatalytic activity remains a limiting nuisance. Herein, the combination design of a single Cu atom with hollow g-C3N4 nanospheres (Cu-N3 structure) has been proven to offer significant opportunities for this crucial challenge. Moreover, this structure endows two pathways for charge transfer in the reaction, namely, the N atoms in the three-dimensional planar structure are only bonded with a single Cu atom, and charge transfer occurs between the plane and the layered structure due to the bending of the interlayered g-C3N4 hollow nanospheres. Notably, Cu-N3 and hollow nanosphere structures have been certified to greatly enhance the efficiency of photogenerated carrier separation and transfer between the layers and planes by ultrafast spectral analysis. As a result, this catalyst possesses unparalleled photocatalytic efficiency. Specifically, the hydrogen production rate up to 2040 µmol h−1 g−1, which is 51 times that of pure C3N4 under visible light conditions. The photocatalytic degradation performance of tetracycline and oxidation performance of benzene is also expressed, with a degradation rate of 100%, a conversion of 97.3% and a selectivity of 99.9%. This work focuses on the structure-activity relationship to provide the possibilities for the development of potential photocatalytic materials.
2024, 35(2): 108575
doi: 10.1016/j.cclet.2023.108575
Abstract:
Accurate and sensitive strategies for Concanavalin A (Con A) sensing are conducive to the better cognition of various important biological and physiological processes. Here, by designing dextran-functionalized fluorescent microspheres (DxFMs) and boric acid-modified carbon dots (BCDs) as recognition unit and built-in signal reference respectively, a ratiometric fluorescent detection platform was proposed for Con A detection with high reliability. In this protocol, the BCDs/DxFMs precipitation was formed due to the covalent interactions between cis-diol of DxFMs and boronic acid groups of BCDs, thus only fluorescence of BCDs could be detected in the supernatant. When Con A was presented, it could bind to DxFMs through its carbohydrate recognition ability and suppress the subsequent assembly between DxFMs and BCDs, leading to the simultaneous capture of DxFMs and BCDs fluorescence in the supernatant. Since the BCDs content was superfluous, their fluorescence intensities were basically constant in all cases. Based on the unchanged BCDs fluorescence signal and target-dependent DxFMs fluorescence signal in supernatant, the ratiometric detection of Con A was realized. Under optimized conditions, this ratiometric fluorescent platform displayed a linear detection range from 0.125 µg/mL to 12.5 µg/mL with a detection limit of 0.089 µg/mL. Moreover, satisfied analytical outcomes for Con A detection in serum samples were obtained, manifesting huge application potential of this ratiometric fluorescent platform in clinical diagnosis.
Accurate and sensitive strategies for Concanavalin A (Con A) sensing are conducive to the better cognition of various important biological and physiological processes. Here, by designing dextran-functionalized fluorescent microspheres (DxFMs) and boric acid-modified carbon dots (BCDs) as recognition unit and built-in signal reference respectively, a ratiometric fluorescent detection platform was proposed for Con A detection with high reliability. In this protocol, the BCDs/DxFMs precipitation was formed due to the covalent interactions between cis-diol of DxFMs and boronic acid groups of BCDs, thus only fluorescence of BCDs could be detected in the supernatant. When Con A was presented, it could bind to DxFMs through its carbohydrate recognition ability and suppress the subsequent assembly between DxFMs and BCDs, leading to the simultaneous capture of DxFMs and BCDs fluorescence in the supernatant. Since the BCDs content was superfluous, their fluorescence intensities were basically constant in all cases. Based on the unchanged BCDs fluorescence signal and target-dependent DxFMs fluorescence signal in supernatant, the ratiometric detection of Con A was realized. Under optimized conditions, this ratiometric fluorescent platform displayed a linear detection range from 0.125 µg/mL to 12.5 µg/mL with a detection limit of 0.089 µg/mL. Moreover, satisfied analytical outcomes for Con A detection in serum samples were obtained, manifesting huge application potential of this ratiometric fluorescent platform in clinical diagnosis.
2024, 35(2): 108576
doi: 10.1016/j.cclet.2023.108576
Abstract:
We report the photo-mediated 1,2-aryl migration of 2–chloro-1-arylpropanones to 2-arylpropionic acids using HCOONa as an acid scavenger. This pragmatically focused study obviates the multiple-step sequence in the industrially employed, ZnO-promoted rearrangement strategy, and offers rapid access to various 2-arylpropionic acids under environmentally friendly conditions. Furthermore, the successful transfer of this batch photochemistry to a continuous flow platform led to improved scalability and enabled the gram-scale synthesis of loxoprofen.
We report the photo-mediated 1,2-aryl migration of 2–chloro-1-arylpropanones to 2-arylpropionic acids using HCOONa as an acid scavenger. This pragmatically focused study obviates the multiple-step sequence in the industrially employed, ZnO-promoted rearrangement strategy, and offers rapid access to various 2-arylpropionic acids under environmentally friendly conditions. Furthermore, the successful transfer of this batch photochemistry to a continuous flow platform led to improved scalability and enabled the gram-scale synthesis of loxoprofen.
2024, 35(2): 108578
doi: 10.1016/j.cclet.2023.108578
Abstract:
Rapid analysis of metal ions and organic compounds in strong acidic solutions is of sustainable interest in multiple disciplines. However, complicated and time-consuming pretreatments are always required for MS analysis of the compounds in strong acidic solutions. Otherwise, it will result in a weak signal and cause serious damage to the mass spectrometer. Herein, a simple method inherited from nano-ESI MS was developed for rapid analysis of strong acidic solutions. Nanoliter (nL) strong acidic solution was first loaded in the nano-ESI emitter, followed by evaporation to remove the H+ and leave the analytes on the wall of the nano-ESI emitter. The evaporation process can be completed within 1 min because of the extremely tiny volume (≤1 nL) of the loaded solution. Then, the dried analytes on the wall of the nano-ESI emitter were redissolved by loading a new solvent, followed by nano-ESI MS analysis. By using this method, metal ions and organic compounds in the strong acidic solution can be detected with low sample consumption (1 nL), high speed (< 2 min/sample), high sensitivity (limit of detection = 0.2 µg/L), and high accuracy (> 90%). Proof-of-concept applications of the present method have been successfully achieved for the analysis of gastric juice (pH of the sample = 1), monitoring reaction catalyzed by strong acid (pH of the system = 0), and micro-area analysis of ores (pH of the extraction solvent = 0), showing great application potential in multiple fields.
Rapid analysis of metal ions and organic compounds in strong acidic solutions is of sustainable interest in multiple disciplines. However, complicated and time-consuming pretreatments are always required for MS analysis of the compounds in strong acidic solutions. Otherwise, it will result in a weak signal and cause serious damage to the mass spectrometer. Herein, a simple method inherited from nano-ESI MS was developed for rapid analysis of strong acidic solutions. Nanoliter (nL) strong acidic solution was first loaded in the nano-ESI emitter, followed by evaporation to remove the H+ and leave the analytes on the wall of the nano-ESI emitter. The evaporation process can be completed within 1 min because of the extremely tiny volume (≤1 nL) of the loaded solution. Then, the dried analytes on the wall of the nano-ESI emitter were redissolved by loading a new solvent, followed by nano-ESI MS analysis. By using this method, metal ions and organic compounds in the strong acidic solution can be detected with low sample consumption (1 nL), high speed (< 2 min/sample), high sensitivity (limit of detection = 0.2 µg/L), and high accuracy (> 90%). Proof-of-concept applications of the present method have been successfully achieved for the analysis of gastric juice (pH of the sample = 1), monitoring reaction catalyzed by strong acid (pH of the system = 0), and micro-area analysis of ores (pH of the extraction solvent = 0), showing great application potential in multiple fields.
2024, 35(2): 108581
doi: 10.1016/j.cclet.2023.108581
Abstract:
Biomass pyrolysis oil can be improved effectively by electrocatalytic hydrogenation (ECH). However, the unclear interactions among different components lead to low bio-oil upgrading efficiency in the conversion process. Herein, benzaldehyde and phenol, as common compounds in bio-oil, were chosen as model compounds. The interactions between the two components were explored in the ECH process by combining experiments and theoretical calculations. Results showed that phenol could accelerate the conversion of benzaldehyde in the ECH. The selectivity of benzyl alcohol was increased from 60.9% of unadded phenol to 99.1% with 30 mmol/L phenol concentration at 5 h. Benzaldehyde inhibited the ECH of phenol. In the presence of benzaldehyde, the conversion rate of phenol was below 10.0% with no cyclohexanone and cyclohexanol formation at 5 h. The density functional theory (DFT) calculations revealed that the phenol could promote the adsorption of benzaldehyde and facilitate the targeted conversion of benzaldehyde on the active site by lowering the reaction energy barrier. The research on the interaction between phenol and benzaldehyde in the ECH provides a theoretical basis for the application of ECH in practical bio-oil upgrading.
Biomass pyrolysis oil can be improved effectively by electrocatalytic hydrogenation (ECH). However, the unclear interactions among different components lead to low bio-oil upgrading efficiency in the conversion process. Herein, benzaldehyde and phenol, as common compounds in bio-oil, were chosen as model compounds. The interactions between the two components were explored in the ECH process by combining experiments and theoretical calculations. Results showed that phenol could accelerate the conversion of benzaldehyde in the ECH. The selectivity of benzyl alcohol was increased from 60.9% of unadded phenol to 99.1% with 30 mmol/L phenol concentration at 5 h. Benzaldehyde inhibited the ECH of phenol. In the presence of benzaldehyde, the conversion rate of phenol was below 10.0% with no cyclohexanone and cyclohexanol formation at 5 h. The density functional theory (DFT) calculations revealed that the phenol could promote the adsorption of benzaldehyde and facilitate the targeted conversion of benzaldehyde on the active site by lowering the reaction energy barrier. The research on the interaction between phenol and benzaldehyde in the ECH provides a theoretical basis for the application of ECH in practical bio-oil upgrading.
2024, 35(2): 108591
doi: 10.1016/j.cclet.2023.108591
Abstract:
Interface engineering is of great importance to improve the photocatalytic performance. Herein, in-situ formation plasmon Bi/BiOCl nanosheets assembled heterojunction microspheres are fabricated via facile reductive solvothermal approach. The aldehyde group in the DMF structure is used to exert the weak reducing property of the solvent and thus strip out the metal Bi in BiOCl. The metal Bi is anchored on surface of BiOCl firmly due to in-situ formation engineered interface, which could realize efficient charge transfer channel. The resultant Bi/BiOCl heterojunctions assemblies with narrow bandgap of 3.05 eV and mesoporous structure extend the photoresponse to visible light region and could provide sufficient surface active sites. The visible-light-driven photocatalytic degradation of high-toxic norfloxacin for Bi/BiOCl heterojunctions is up to 95.5% within 20 min, representing several times that of pristine BiOCl nanosheets and the physical mixture. It is attributed to the in-situ formation of Bi/BiOCl heterojunctions and surface plasmon resonance (SPR) effect of plasmon Bi promoting charge transfer, and the obvious photothermal effect promoting the photocatalytic reaction, which are verified by experimental and density functional theory (DFT) calculations. This strategy provides ideal perspectives for fabricating metal/semiconductor heterojunctions photocatalysts with high-performance.
Interface engineering is of great importance to improve the photocatalytic performance. Herein, in-situ formation plasmon Bi/BiOCl nanosheets assembled heterojunction microspheres are fabricated via facile reductive solvothermal approach. The aldehyde group in the DMF structure is used to exert the weak reducing property of the solvent and thus strip out the metal Bi in BiOCl. The metal Bi is anchored on surface of BiOCl firmly due to in-situ formation engineered interface, which could realize efficient charge transfer channel. The resultant Bi/BiOCl heterojunctions assemblies with narrow bandgap of 3.05 eV and mesoporous structure extend the photoresponse to visible light region and could provide sufficient surface active sites. The visible-light-driven photocatalytic degradation of high-toxic norfloxacin for Bi/BiOCl heterojunctions is up to 95.5% within 20 min, representing several times that of pristine BiOCl nanosheets and the physical mixture. It is attributed to the in-situ formation of Bi/BiOCl heterojunctions and surface plasmon resonance (SPR) effect of plasmon Bi promoting charge transfer, and the obvious photothermal effect promoting the photocatalytic reaction, which are verified by experimental and density functional theory (DFT) calculations. This strategy provides ideal perspectives for fabricating metal/semiconductor heterojunctions photocatalysts with high-performance.
2024, 35(2): 108596
doi: 10.1016/j.cclet.2023.108596
Abstract:
Predictive modeling of photocatalytic NO removal is highly desirable for efficient air pollution abatement. However, great challenges remain in precisely predicting photocatalytic performance and understanding interactions of diverse features in the catalytic systems. Herein, a dataset of g-C3N4-based catalysts with 255 data points was collected from peer-reviewed publications and machine learning (ML) model was proposed to predict the NO removal rate. The result shows that the Gradient Boosting Decision Tree (GBDT) demonstrated the greatest prediction accuracy with R2 of 0.999 and 0.907 on the training and test data, respectively. The SHAP value and feature importance analysis revealed that the empirical categories for NO removal rate, in the order of importance, were catalyst characteristics > reaction process > preparation conditions. Moreover, the partial dependence plots broke the ML black box to further quantify the marginal contributions of the input features (e.g., doping ratio, flow rate, and pore volume) to the model output outcomes. This ML approach presents a pure data-driven, interpretable framework, which provides new insights into the influence of catalyst characteristics, reaction process, and preparation conditions on NO removal.
Predictive modeling of photocatalytic NO removal is highly desirable for efficient air pollution abatement. However, great challenges remain in precisely predicting photocatalytic performance and understanding interactions of diverse features in the catalytic systems. Herein, a dataset of g-C3N4-based catalysts with 255 data points was collected from peer-reviewed publications and machine learning (ML) model was proposed to predict the NO removal rate. The result shows that the Gradient Boosting Decision Tree (GBDT) demonstrated the greatest prediction accuracy with R2 of 0.999 and 0.907 on the training and test data, respectively. The SHAP value and feature importance analysis revealed that the empirical categories for NO removal rate, in the order of importance, were catalyst characteristics > reaction process > preparation conditions. Moreover, the partial dependence plots broke the ML black box to further quantify the marginal contributions of the input features (e.g., doping ratio, flow rate, and pore volume) to the model output outcomes. This ML approach presents a pure data-driven, interpretable framework, which provides new insights into the influence of catalyst characteristics, reaction process, and preparation conditions on NO removal.
2024, 35(2): 108607
doi: 10.1016/j.cclet.2023.108607
Abstract:
Photoreduction of CO2 to solar fuels has caused great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, we designed a S-scheme heterojunction (Cu-TiO2/WO3) with Cu single atom to significantly boost the photoreduction of CO2. Notably, the developed Cu-TiO2/WO3 achieved the solar-driven conversion of CO2 to CH4 with an evolution rate of 98.69 µmol g−1 h−1, and the electron selectivity of CH4 reached 88.5%. The yield was much higher than those of pristine WO3, TiO2/WO3 and Cu-TiO2 samples. Experimental and theoretical analysis suggested that the S-scheme heterojunction accelerated charge migration and inhibited the recombination of electron-hole pairs. Importantly, the charge separation effect of the heterojunction meliorated the position of the d-band. The uplifted d-band centers of Cu and Ti on Cu-TiO2/WO3 not only improved the electron interaction between Cu single atoms and substrate-TiO2, accelerated the adsorption and activation of CO2 on the active sites of Cu single atom, but also optimized the Gibbs free energies of CH4 formation pathway, leading to excellent selectivity toward CH4. This work provides new insights into the design of photocatalyst systems with high photocatalytic performance.
Photoreduction of CO2 to solar fuels has caused great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, we designed a S-scheme heterojunction (Cu-TiO2/WO3) with Cu single atom to significantly boost the photoreduction of CO2. Notably, the developed Cu-TiO2/WO3 achieved the solar-driven conversion of CO2 to CH4 with an evolution rate of 98.69 µmol g−1 h−1, and the electron selectivity of CH4 reached 88.5%. The yield was much higher than those of pristine WO3, TiO2/WO3 and Cu-TiO2 samples. Experimental and theoretical analysis suggested that the S-scheme heterojunction accelerated charge migration and inhibited the recombination of electron-hole pairs. Importantly, the charge separation effect of the heterojunction meliorated the position of the d-band. The uplifted d-band centers of Cu and Ti on Cu-TiO2/WO3 not only improved the electron interaction between Cu single atoms and substrate-TiO2, accelerated the adsorption and activation of CO2 on the active sites of Cu single atom, but also optimized the Gibbs free energies of CH4 formation pathway, leading to excellent selectivity toward CH4. This work provides new insights into the design of photocatalyst systems with high photocatalytic performance.
2024, 35(2): 108618
doi: 10.1016/j.cclet.2023.108618
Abstract:
Stepwise energy transfer is ubiquitous in natural photosynthesis, which greatly promotes the widespread use of solar energy. Herein, we constructed a supramolecular light harvesting system based on sequential energy transfer through the hierarchical self-assembly of M, which contains a cyanostilbene core flanked by two ureidopyrimidinone motifs, endowing itself with both aggregation-induced emission behavior and quadruple hydrogen bonding ability. The monomer M can self-assemble into hydrogen bonded polymers and then form supramolecular polymeric nanoparticles in water through a mini-emulsion process. The nanoparticles were further utilized to encapsulate the relay acceptor ESY and the final acceptor NDI to form a two-step FRET system. Tunable fluorescence including a white-light emission was successfully achieved. Our work not only shows a desirable way for the fabrication of efficient two-step light harvesting systems, but also shows great potential in tunable photoluminescent nanomaterials.
Stepwise energy transfer is ubiquitous in natural photosynthesis, which greatly promotes the widespread use of solar energy. Herein, we constructed a supramolecular light harvesting system based on sequential energy transfer through the hierarchical self-assembly of M, which contains a cyanostilbene core flanked by two ureidopyrimidinone motifs, endowing itself with both aggregation-induced emission behavior and quadruple hydrogen bonding ability. The monomer M can self-assemble into hydrogen bonded polymers and then form supramolecular polymeric nanoparticles in water through a mini-emulsion process. The nanoparticles were further utilized to encapsulate the relay acceptor ESY and the final acceptor NDI to form a two-step FRET system. Tunable fluorescence including a white-light emission was successfully achieved. Our work not only shows a desirable way for the fabrication of efficient two-step light harvesting systems, but also shows great potential in tunable photoluminescent nanomaterials.
2024, 35(2): 108635
doi: 10.1016/j.cclet.2023.108635
Abstract:
The presence of alkali metals in exhaust gas from stationary resources causes a grand challenge for the practical application of selective catalytic reduction (SCR) of NOx with NH3. Here, alkali-resistant NOx reduction has been successfully implemented via tailoring the electron transfer over Fe and V species on FeVO4/TiO2 catalysts. The strong interaction between Fe and V induced electron transfer from V to Fe and strengthened the adsorption and activation of NH3 and NO over active VOx sites. In the presence of K2O, the strong electron withdrawing effect of Fe offset the electron donating effect of K on the VOx species, thus protecting the active species VOx to maintain the NOx reduction ability. The enhanced adsorption and activation of NH3 allowed SCR reaction to proceed via E-R mechanism even after K2O poisoning. This work elucidated the electronic effects on the alkali metals resistance of traditional ferric vanadate SCR catalysts and provided a promising strategy to design SCR catalysts with superior alkali resistance.
The presence of alkali metals in exhaust gas from stationary resources causes a grand challenge for the practical application of selective catalytic reduction (SCR) of NOx with NH3. Here, alkali-resistant NOx reduction has been successfully implemented via tailoring the electron transfer over Fe and V species on FeVO4/TiO2 catalysts. The strong interaction between Fe and V induced electron transfer from V to Fe and strengthened the adsorption and activation of NH3 and NO over active VOx sites. In the presence of K2O, the strong electron withdrawing effect of Fe offset the electron donating effect of K on the VOx species, thus protecting the active species VOx to maintain the NOx reduction ability. The enhanced adsorption and activation of NH3 allowed SCR reaction to proceed via E-R mechanism even after K2O poisoning. This work elucidated the electronic effects on the alkali metals resistance of traditional ferric vanadate SCR catalysts and provided a promising strategy to design SCR catalysts with superior alkali resistance.
2024, 35(2): 108644
doi: 10.1016/j.cclet.2023.108644
Abstract:
The construction of hydrogels with good mechanical properties and phosphorescent properties is full of challenges. Herein, we report a supramolecular phosphorescent hydrogel with long lifetime, high tensile strength and self-healing property, which can be easily constructed through in-situ thermal-initiated polymerization of isocyanatoethyl acrylate-modified β-cyclodextrin (β-CD-DA) and acrylate-modified adamantane (Ad-DA), acrylic acid (AA), followed by the non-covalent association with carbon dots (CNDs). The lifetime of phosphorescent hydrogel can reach 1261 ms at room temperature, and the quantum yield is 11%. Importantly, through the efficient triplet to singlet Förster resonance energy transfer (TS-FRET), the phosphorescent hydrogel shows the good phosphorescence energy transfer property for organic dyes Rhodamine B and Eosin Y with the delayed fluorescence lifetime up to 730 ms and 585 ms as well as the energy transfer efficiency (ΦET) up to 99.9% and 99.3%, respectively. Moreover, owing to the host-guest interactions between β-CD-DA and Ad-DA, the three-dimensional cross-linked network phosphorescent hydrogel can be easily stretched to 18 times of its original length, and can achieve self-healing of the cut surfaces within 30 min. These results will expand the scope of phosphorescent materials and provide new ideas and opportunities for materials science.
The construction of hydrogels with good mechanical properties and phosphorescent properties is full of challenges. Herein, we report a supramolecular phosphorescent hydrogel with long lifetime, high tensile strength and self-healing property, which can be easily constructed through in-situ thermal-initiated polymerization of isocyanatoethyl acrylate-modified β-cyclodextrin (β-CD-DA) and acrylate-modified adamantane (Ad-DA), acrylic acid (AA), followed by the non-covalent association with carbon dots (CNDs). The lifetime of phosphorescent hydrogel can reach 1261 ms at room temperature, and the quantum yield is 11%. Importantly, through the efficient triplet to singlet Förster resonance energy transfer (TS-FRET), the phosphorescent hydrogel shows the good phosphorescence energy transfer property for organic dyes Rhodamine B and Eosin Y with the delayed fluorescence lifetime up to 730 ms and 585 ms as well as the energy transfer efficiency (ΦET) up to 99.9% and 99.3%, respectively. Moreover, owing to the host-guest interactions between β-CD-DA and Ad-DA, the three-dimensional cross-linked network phosphorescent hydrogel can be easily stretched to 18 times of its original length, and can achieve self-healing of the cut surfaces within 30 min. These results will expand the scope of phosphorescent materials and provide new ideas and opportunities for materials science.
2024, 35(2): 108646
doi: 10.1016/j.cclet.2023.108646
Abstract:
Microfluidic combined with magnetic field have been demonstrated to be the promising solutions for fast and low-damage particles separation. However, the difficulties in the precise layout of magnets and accurate prediction of particle trajectories lead to under and over separation of target particles. A novel particle separation lab-on-chip (LOC) prototype integrated with microstructures and micropolar arrays is designed and characterized. Meanwhile, a numerical model for the separation of magnetic particles by the synergistic effect of geometry-induced hydrodynamics and magnetic field is constructed. The effect of geometry and magnetic field layout on particle deflection is systematically analyzed to implement accurate prediction of particle trajectories. It is found that the separation efficiency of magnetic particles increased from 50.2% to 91.7% and decreased from 88.6% to 85.7% in the range of depth factors from 15 µm to 27 µm and width factors from 30 µm to 60 µm, respectively. In particular, the combined effect of the offset distance of permanent magnets and the distance from the main flow channel exhibits a significant difference from the conventional perception. Finally, the developed LOC prototype was generalized for extension to arbitrary systems. This work provides a new insight and robust method for the microfluidic separation of magnetic particles.
Microfluidic combined with magnetic field have been demonstrated to be the promising solutions for fast and low-damage particles separation. However, the difficulties in the precise layout of magnets and accurate prediction of particle trajectories lead to under and over separation of target particles. A novel particle separation lab-on-chip (LOC) prototype integrated with microstructures and micropolar arrays is designed and characterized. Meanwhile, a numerical model for the separation of magnetic particles by the synergistic effect of geometry-induced hydrodynamics and magnetic field is constructed. The effect of geometry and magnetic field layout on particle deflection is systematically analyzed to implement accurate prediction of particle trajectories. It is found that the separation efficiency of magnetic particles increased from 50.2% to 91.7% and decreased from 88.6% to 85.7% in the range of depth factors from 15 µm to 27 µm and width factors from 30 µm to 60 µm, respectively. In particular, the combined effect of the offset distance of permanent magnets and the distance from the main flow channel exhibits a significant difference from the conventional perception. Finally, the developed LOC prototype was generalized for extension to arbitrary systems. This work provides a new insight and robust method for the microfluidic separation of magnetic particles.
2024, 35(2): 108648
doi: 10.1016/j.cclet.2023.108648
Abstract:
Antimicrobial photodynamic therapy (aPDT) has been considered a noninvasive and effective modality against the bacterial infection of peri–implantitis, especially the aPDT triggered by near-infrared (NIR) light due to the large penetration depth in tissue. However, the complexity of hypoxia microenvironments and the distance of aPDT sterilization still pose challenges before realizing the aPDT clinical application. Due to the long lifespan and transmission distance of therapeutic gas molecules, we design a multi-functional gas generator that combines aPDT as well as O2 and CO gas release function, which can solve the problem of hypoxia (O2) in PDT and the problem of inflammation regulation (CO) in the distal part of peri–implant inflammation under near-infrared (NIR) irradiation. In the composite nanoplatform that spin-coated on the surface of titanium implants, up-conversion nanoparticles (UCNPs) were involved in converting the NIR to visible, which further excites the partially oxidized stannic sulfide (SnS2), realizing the therapeutic gas release. Indocyanine green (ICG) was further integrated to enhance the aPDT performance (Ti-U@SnS2/I). Therefore, reactive oxygen species (ROS), CO, and O2 can be controllably administered via a composite nano-platform mediated by a single NIR light (808 nm). This implant surface modification strategy could achieve great self-enhancement antibacterial effectiveness and regulate the lingering questions, such as relieving the anoxic microenvironment and reaching deep infection sites, providing a viable antibiotic-free technique to combat peri–implantitis.
Antimicrobial photodynamic therapy (aPDT) has been considered a noninvasive and effective modality against the bacterial infection of peri–implantitis, especially the aPDT triggered by near-infrared (NIR) light due to the large penetration depth in tissue. However, the complexity of hypoxia microenvironments and the distance of aPDT sterilization still pose challenges before realizing the aPDT clinical application. Due to the long lifespan and transmission distance of therapeutic gas molecules, we design a multi-functional gas generator that combines aPDT as well as O2 and CO gas release function, which can solve the problem of hypoxia (O2) in PDT and the problem of inflammation regulation (CO) in the distal part of peri–implant inflammation under near-infrared (NIR) irradiation. In the composite nanoplatform that spin-coated on the surface of titanium implants, up-conversion nanoparticles (UCNPs) were involved in converting the NIR to visible, which further excites the partially oxidized stannic sulfide (SnS2), realizing the therapeutic gas release. Indocyanine green (ICG) was further integrated to enhance the aPDT performance (Ti-U@SnS2/I). Therefore, reactive oxygen species (ROS), CO, and O2 can be controllably administered via a composite nano-platform mediated by a single NIR light (808 nm). This implant surface modification strategy could achieve great self-enhancement antibacterial effectiveness and regulate the lingering questions, such as relieving the anoxic microenvironment and reaching deep infection sites, providing a viable antibiotic-free technique to combat peri–implantitis.
2024, 35(2): 108649
doi: 10.1016/j.cclet.2023.108649
Abstract:
Boosting the interfacial stability between electrolyte and Li-rich cathode material at high operating voltage is vital important to enhance the cycling stability of Li-rich cathode materials for high-performance Li-ion batteries. In this work, vinyltrimethylsilane as a new type of organic silicon electrolyte additive is studied to address the interfacial instability of Li-rich cathode material at high operating voltage. The cells using vinyltrimethylsilane additive shows the high capacity retention of 73.9% after 300 cycles at 1 C, whereas the cells without this kind of additive only have the capacity retention of 58.9%. The improvement of stability is mainly attributed to the additive helping to form a more stable surface film for Li-rich cathode material, thus avoiding direct contact between the electrolyte and the cathode material, slowing down the dissolution of metal ions and the decomposition of the electrolyte under high operating voltage. Our findings in this work shed some light on the design of stable cycling performance of Li-rich cathode toward advanced Li-ion batteries.
Boosting the interfacial stability between electrolyte and Li-rich cathode material at high operating voltage is vital important to enhance the cycling stability of Li-rich cathode materials for high-performance Li-ion batteries. In this work, vinyltrimethylsilane as a new type of organic silicon electrolyte additive is studied to address the interfacial instability of Li-rich cathode material at high operating voltage. The cells using vinyltrimethylsilane additive shows the high capacity retention of 73.9% after 300 cycles at 1 C, whereas the cells without this kind of additive only have the capacity retention of 58.9%. The improvement of stability is mainly attributed to the additive helping to form a more stable surface film for Li-rich cathode material, thus avoiding direct contact between the electrolyte and the cathode material, slowing down the dissolution of metal ions and the decomposition of the electrolyte under high operating voltage. Our findings in this work shed some light on the design of stable cycling performance of Li-rich cathode toward advanced Li-ion batteries.
2024, 35(2): 108651
doi: 10.1016/j.cclet.2023.108651
Abstract:
The efficiency of photocatalytic CO2 reduction reaction (PCRR) is restricted by the low solubility and mobility of CO2 in water, poor CO2 adsorption capacity of catalyst, and competition with hydrogen evolution reaction (HER). Recently, hydrophobic modification of the catalyst surface has been proposed as a potential solution to induce the formation of triple-phase contact points (TPCPs) of CO2 (gas phase), H2O (liquid phase), and catalysts (solid phase) near the surface of the catalyst, enabling direct delivery of highly concentrated CO2 molecules to the active reaction sites, resulting in higher CO2 and lower H+ surface concentrations. The TPCPs thus act as the ideal reaction points with enhanced PCRR and suppressed HER. However, the initial synthesis of triple-phase photocatalysts tends to possess a lower bulk density of TPCPs due to the simple structure leading to limited active points and CO2 adsorption sites. Here, based on constructing a hydrophobic hierarchical porous TiO2 (o-HPT) with interconnected macropores and mesopores structure, we have significantly increased the density of TPCPs in a unit volume of the photocatalyst. Compared with hydrophobic macroporous TiO2 (o-MacPT) or mesoporous TiO2 (o-MesPT), the o-HPT with increased TPCP density leads to enhanced photoactivity, enabling a high methanol production rate with 1111.5 µmol g−1 h−1 from PCRR. These results emphasize the significance of high-density TPCPs design and propose a potential path for developing efficient PCRR systems.
The efficiency of photocatalytic CO2 reduction reaction (PCRR) is restricted by the low solubility and mobility of CO2 in water, poor CO2 adsorption capacity of catalyst, and competition with hydrogen evolution reaction (HER). Recently, hydrophobic modification of the catalyst surface has been proposed as a potential solution to induce the formation of triple-phase contact points (TPCPs) of CO2 (gas phase), H2O (liquid phase), and catalysts (solid phase) near the surface of the catalyst, enabling direct delivery of highly concentrated CO2 molecules to the active reaction sites, resulting in higher CO2 and lower H+ surface concentrations. The TPCPs thus act as the ideal reaction points with enhanced PCRR and suppressed HER. However, the initial synthesis of triple-phase photocatalysts tends to possess a lower bulk density of TPCPs due to the simple structure leading to limited active points and CO2 adsorption sites. Here, based on constructing a hydrophobic hierarchical porous TiO2 (o-HPT) with interconnected macropores and mesopores structure, we have significantly increased the density of TPCPs in a unit volume of the photocatalyst. Compared with hydrophobic macroporous TiO2 (o-MacPT) or mesoporous TiO2 (o-MesPT), the o-HPT with increased TPCP density leads to enhanced photoactivity, enabling a high methanol production rate with 1111.5 µmol g−1 h−1 from PCRR. These results emphasize the significance of high-density TPCPs design and propose a potential path for developing efficient PCRR systems.
2024, 35(2): 108658
doi: 10.1016/j.cclet.2023.108658
Abstract:
Nasopharyngeal carcinoma (NPC), a malignant tumor originating from the nasopharynx, is one of the common malignant tumors of the head and neck. There are significant geographical differences in the incidence of nasopharyngeal carcinoma, with a high incidence in China and Southeast Asian countries. Herein, we designed and synthesized a novel near-infrared fluorescent (NIRF) probe to detect glutathione (GSH) in cellular and tumor environments using semi-naphthofluorescein (SNAFL) as the fluorescent molecular backbone and 2-fluoro-4-nitrobenzenesulfonate as the recognition moiety. Upon reaction with GSH, SNAFL-GSH emitted a fluorescence signal, and its emission wavelength at 650 nm was remarkably enhanced. The results of selectivity experiments indicated that SNAFL-GSH was able to discriminate GSH from Cys, Hcy, and H2S. Moreover, SNAFL-GSH could image both endogenous and exogenous GSH and distinguish normal and cancer cells by fluorescence signal difference. At the cellular level, cisplatin (DDP)-induced ferroptosis and inhibition of proliferation of various NPC cell lines (CNE2, CNE1, 5–8F cells) by erastin combined with DDP were visualized with the help of SNAFL-GSH. In a mouse tumor xenograft model, we successfully employed SNAFL-GSH for the evaluation of the efficacy of erastin combined with DDP in the treatment of NPC. More importantly, the probe could image cancerous tissue sections from NPC patients with an imaging depth of approximately 80 µm. It was foreseen that SNAFL-GSH offered great potential for application in the diagnosis and evaluation of the therapeutic efficacy of NPC, and these results would also provide new ideas for the clinical treatment of NPC.
Nasopharyngeal carcinoma (NPC), a malignant tumor originating from the nasopharynx, is one of the common malignant tumors of the head and neck. There are significant geographical differences in the incidence of nasopharyngeal carcinoma, with a high incidence in China and Southeast Asian countries. Herein, we designed and synthesized a novel near-infrared fluorescent (NIRF) probe to detect glutathione (GSH) in cellular and tumor environments using semi-naphthofluorescein (SNAFL) as the fluorescent molecular backbone and 2-fluoro-4-nitrobenzenesulfonate as the recognition moiety. Upon reaction with GSH, SNAFL-GSH emitted a fluorescence signal, and its emission wavelength at 650 nm was remarkably enhanced. The results of selectivity experiments indicated that SNAFL-GSH was able to discriminate GSH from Cys, Hcy, and H2S. Moreover, SNAFL-GSH could image both endogenous and exogenous GSH and distinguish normal and cancer cells by fluorescence signal difference. At the cellular level, cisplatin (DDP)-induced ferroptosis and inhibition of proliferation of various NPC cell lines (CNE2, CNE1, 5–8F cells) by erastin combined with DDP were visualized with the help of SNAFL-GSH. In a mouse tumor xenograft model, we successfully employed SNAFL-GSH for the evaluation of the efficacy of erastin combined with DDP in the treatment of NPC. More importantly, the probe could image cancerous tissue sections from NPC patients with an imaging depth of approximately 80 µm. It was foreseen that SNAFL-GSH offered great potential for application in the diagnosis and evaluation of the therapeutic efficacy of NPC, and these results would also provide new ideas for the clinical treatment of NPC.
2024, 35(2): 108660
doi: 10.1016/j.cclet.2023.108660
Abstract:
Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities, such as free carboxylic acid, aldehyde, halogen (including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp3)–H bonds, and short-lived reactive intermediates (aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode (BUME) with nano-electrospray ionization mass spectrometry.
Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities, such as free carboxylic acid, aldehyde, halogen (including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp3)–H bonds, and short-lived reactive intermediates (aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode (BUME) with nano-electrospray ionization mass spectrometry.
2024, 35(2): 108670
doi: 10.1016/j.cclet.2023.108670
Abstract:
Targeting delivery of tumor-associated carbohydrate antigen (TACA)-based vaccine to antigen-presenting cells (APCs) mediated by endogenous antibodies can improve the immunogenicity of TACA. However, an essential requirement of this approach is to generate high titers of endogenous antibodies in vivo through pre-immunization, which complicates the immunization procedure and may cause side effects. Herein, we report a new generation of APC-targeting TACA-based supramolecular complex vaccine, assembled by sialyl Thomsen-nouveau-bovine serum albumin-adamantine (sTn-BSA-Ada) and heptavalent rhamnose (Rha)-modified β-cyclodextrin (β-CD) via host–guest interaction. The complex vaccine retained anti-Rha antibodies recruiting capability and facilitated the APCs uptake of the vaccine via the interaction of the Fc-domain with the Fc receptors on APCs. We demonstrate that direct immunization of complex vaccine elicited anti-Rha and anti-sTn specific immune response synchronously, generating a novel self-enhancement effect that can improve the antigen delivery to APCs in high efficacy. The structure–activity relationship (SAR) study proved that complex vaccine 4 with polyethylene glycol 6 (PEG6) linker in host molecule provoked a robust and specific sTn immune response comparable to the pre-immunization approach. The antisera induced by complex vaccine, either through direct immunization or pre-immunization, exhibited equal potency of cytotoxicity against the sTn expression cancer cells. This study provides a general platform for TACA-based vaccines with self-enhancement effects without the need for pre-immunization.
Targeting delivery of tumor-associated carbohydrate antigen (TACA)-based vaccine to antigen-presenting cells (APCs) mediated by endogenous antibodies can improve the immunogenicity of TACA. However, an essential requirement of this approach is to generate high titers of endogenous antibodies in vivo through pre-immunization, which complicates the immunization procedure and may cause side effects. Herein, we report a new generation of APC-targeting TACA-based supramolecular complex vaccine, assembled by sialyl Thomsen-nouveau-bovine serum albumin-adamantine (sTn-BSA-Ada) and heptavalent rhamnose (Rha)-modified β-cyclodextrin (β-CD) via host–guest interaction. The complex vaccine retained anti-Rha antibodies recruiting capability and facilitated the APCs uptake of the vaccine via the interaction of the Fc-domain with the Fc receptors on APCs. We demonstrate that direct immunization of complex vaccine elicited anti-Rha and anti-sTn specific immune response synchronously, generating a novel self-enhancement effect that can improve the antigen delivery to APCs in high efficacy. The structure–activity relationship (SAR) study proved that complex vaccine 4 with polyethylene glycol 6 (PEG6) linker in host molecule provoked a robust and specific sTn immune response comparable to the pre-immunization approach. The antisera induced by complex vaccine, either through direct immunization or pre-immunization, exhibited equal potency of cytotoxicity against the sTn expression cancer cells. This study provides a general platform for TACA-based vaccines with self-enhancement effects without the need for pre-immunization.
2024, 35(2): 108683
doi: 10.1016/j.cclet.2023.108683
Abstract:
Small interfering RNA (siRNA)-based gene silencing has been considered as a potential therapy modality against inflammatory diseases. Nevertheless, the effective delivery of siRNA to desired destination still remains challenging due to poor stability, high molecular weight and negative charge. Currently, ionizable lipid nanoparticle (LNP) has been extensively used as vector for effective delivery of siRNA. Herein, we report a mannose-modified LNP (M-MC3 LNP@TNFα) loading tumor necrosis factor α (TNFα) siRNA for targeting liver macrophages, achieving effectively inhibit acute liver injury. The M-MC3 LNP@TNFα not only increases the internalization of LNP by macrophages, but also enhances the gene silencing efficiency of TNFα in vitro. Additionally, the M-MC3 LNP@TNFα exhibits higher accumulation in liver of healthy mice than that of MC3 LNP@TNFα (un-modified LNP) owing to the targeting effect of mannose. As expected, the M-MC3 LNP@TNFα significantly suppresses the expression of TNFα and ameliorates liver damage in acute liver injury model. Such a LNP targeting siRNA delivery holds great potential for the treatment of diseases associated with liver in the future.
Small interfering RNA (siRNA)-based gene silencing has been considered as a potential therapy modality against inflammatory diseases. Nevertheless, the effective delivery of siRNA to desired destination still remains challenging due to poor stability, high molecular weight and negative charge. Currently, ionizable lipid nanoparticle (LNP) has been extensively used as vector for effective delivery of siRNA. Herein, we report a mannose-modified LNP (M-MC3 LNP@TNFα) loading tumor necrosis factor α (TNFα) siRNA for targeting liver macrophages, achieving effectively inhibit acute liver injury. The M-MC3 LNP@TNFα not only increases the internalization of LNP by macrophages, but also enhances the gene silencing efficiency of TNFα in vitro. Additionally, the M-MC3 LNP@TNFα exhibits higher accumulation in liver of healthy mice than that of MC3 LNP@TNFα (un-modified LNP) owing to the targeting effect of mannose. As expected, the M-MC3 LNP@TNFα significantly suppresses the expression of TNFα and ameliorates liver damage in acute liver injury model. Such a LNP targeting siRNA delivery holds great potential for the treatment of diseases associated with liver in the future.
2024, 35(2): 108687
doi: 10.1016/j.cclet.2023.108687
Abstract:
Passive daytime radiative cooling (PDRC) technology is emerging as one of the most promising solutions to the global problem of spacing cooling, but its practical application is limited due to reduced cooling effectiveness caused by daily wear and tear, as well as dirt contamination. To tackle this problem, we report a novel strategy by introducing a renewable armor structure for prolonging the anti-fouling and cooling effectiveness properties of the PDRC coatings. The armor structure is designed by decorating fluorinated hollow glass microspheres (HGM) inside rigid resin composite matrices. The HGM serve triple purposes, including providing isolated cavities for enhanced solar reflectance, reinforcing the matrices to form robust armored structures, and increasing thermal emittance. When the coatings are worn, the HGM on the surface expose their concave cavities with numerous hydrophobic fragments, generating a highly rough surface that guarantee the superhydrophobic function. The coatings show a high sunlight reflectance (0.93) and thermal emittance (0.94) in the long-wave infrared window, leading to a cooling of 5 ℃ below ambient temperature under high solar flux (~900 W/m2). When anti-fouling functions are reduced, they can be regenerated more than 100 cycles without compromising the PDRC function by simple wearing treatment. Furthermore, these coatings can be easily prepared using a one-pot spray method with low-cost materials, exhibit strong adhesion to a variety of substrates, and demonstrate exceptional environmental stability. Therefore, we anticipate their immediate application opportunities for spacing cooling.
Passive daytime radiative cooling (PDRC) technology is emerging as one of the most promising solutions to the global problem of spacing cooling, but its practical application is limited due to reduced cooling effectiveness caused by daily wear and tear, as well as dirt contamination. To tackle this problem, we report a novel strategy by introducing a renewable armor structure for prolonging the anti-fouling and cooling effectiveness properties of the PDRC coatings. The armor structure is designed by decorating fluorinated hollow glass microspheres (HGM) inside rigid resin composite matrices. The HGM serve triple purposes, including providing isolated cavities for enhanced solar reflectance, reinforcing the matrices to form robust armored structures, and increasing thermal emittance. When the coatings are worn, the HGM on the surface expose their concave cavities with numerous hydrophobic fragments, generating a highly rough surface that guarantee the superhydrophobic function. The coatings show a high sunlight reflectance (0.93) and thermal emittance (0.94) in the long-wave infrared window, leading to a cooling of 5 ℃ below ambient temperature under high solar flux (~900 W/m2). When anti-fouling functions are reduced, they can be regenerated more than 100 cycles without compromising the PDRC function by simple wearing treatment. Furthermore, these coatings can be easily prepared using a one-pot spray method with low-cost materials, exhibit strong adhesion to a variety of substrates, and demonstrate exceptional environmental stability. Therefore, we anticipate their immediate application opportunities for spacing cooling.
2024, 35(2): 108690
doi: 10.1016/j.cclet.2023.108690
Abstract:
Nicotinamide adenine dinucleotide (NADH) regeneration is necessary for the sustainable application of enzymatic industry. The Rh-based complex [Cp*Rh(bpy)(H)]+ has been widely used as an important mediator in NADH regeneration systems, but it is limited by complexity and high cost. Here, a Z-scheme was constructed by loading Rh onto carbon nitride nanosheets/carbon nitride quantum dots (CN-CNQD). The resultant catalyst achieved a high yield of NADH in a mediator-free (M-free) system of 0.283 mmol L−1 g−1 min−1, which is 5.29 times that of pure CN. ADH enzyme introduction experiments confirmed that the enzyme active product 1,4-NADH could reach 34.21% selectivity in the M-free system. Mechanism research revealed that the heterojunction between CNs and CNQDs improved the NADH regeneration activity in the traditional M-involved system, while Rh loading was proved to optimize the yield and selectivity of 1,4-NADH in M-free system. The immobilized Rh shows more competitiveness than [Cp*Rh(bpy)(H)]+. This study contributes to the construction of an M-free system for further application in greener, lower-cost enzymatic processes.
Nicotinamide adenine dinucleotide (NADH) regeneration is necessary for the sustainable application of enzymatic industry. The Rh-based complex [Cp*Rh(bpy)(H)]+ has been widely used as an important mediator in NADH regeneration systems, but it is limited by complexity and high cost. Here, a Z-scheme was constructed by loading Rh onto carbon nitride nanosheets/carbon nitride quantum dots (CN-CNQD). The resultant catalyst achieved a high yield of NADH in a mediator-free (M-free) system of 0.283 mmol L−1 g−1 min−1, which is 5.29 times that of pure CN. ADH enzyme introduction experiments confirmed that the enzyme active product 1,4-NADH could reach 34.21% selectivity in the M-free system. Mechanism research revealed that the heterojunction between CNs and CNQDs improved the NADH regeneration activity in the traditional M-involved system, while Rh loading was proved to optimize the yield and selectivity of 1,4-NADH in M-free system. The immobilized Rh shows more competitiveness than [Cp*Rh(bpy)(H)]+. This study contributes to the construction of an M-free system for further application in greener, lower-cost enzymatic processes.
2024, 35(2): 108737
doi: 10.1016/j.cclet.2023.108737
Abstract:
We report SiO2-supported monometallic Pt, Pd, Au, Ni, Cu and Co catalysts for proton-driven NAD+ regeneration, co-producing H2. All metals are fully selective to NAD+ where the order of turnover frequencies (Pt > Pd > Cu > Au, Ni and Co) coincides with those otherwise observed in electrochemical hydrogen evolution reactions. This has revealed that NADH is capable of converting the metal sites into a "cathode" without an external potential and the NADH to NAD+ reaction involves transferring electron and hydrogen atom separately. Electron-deficient Ptδ+ (on CeO2) enhances TOF and the heterogeneous Pt/CeO2 catalyst is recyclable without losing any activity/selectivity.
We report SiO2-supported monometallic Pt, Pd, Au, Ni, Cu and Co catalysts for proton-driven NAD+ regeneration, co-producing H2. All metals are fully selective to NAD+ where the order of turnover frequencies (Pt > Pd > Cu > Au, Ni and Co) coincides with those otherwise observed in electrochemical hydrogen evolution reactions. This has revealed that NADH is capable of converting the metal sites into a "cathode" without an external potential and the NADH to NAD+ reaction involves transferring electron and hydrogen atom separately. Electron-deficient Ptδ+ (on CeO2) enhances TOF and the heterogeneous Pt/CeO2 catalyst is recyclable without losing any activity/selectivity.
2024, 35(2): 108746
doi: 10.1016/j.cclet.2023.108746
Abstract:
Remodeling tumor microenvironment (TME) is a very promising and effective strategy to enhance the effects of chemotherapy, photodynamic therapy, and immunotherapy. Normalization of tumor vasculature as well as depletion of glutathione (GSH) can improve the TME. Here, we developed a novel therapeutic nanoparticle functional enzyme ultra QDAU5 nanoparticles (FEUQ Nps) based on a fluorescence-on and releasable strategy by combining a vascular normalization inducer, a GSH depleting agent, and an activated fluorophore. In which the cleavage of disulfide bonds releases active molecules that induce vascular normalization and improve the hypoxic microenvironment. In addition, it may deplete GSH in cancer cells, thus inducing the production of reactive oxygen species (ROS) and lipid peroxide (LPO) and promoting iron toxicity. It may also lead to endoplasmic stress and release of calmodulin, which activates the immune system. Meanwhile, quenched fluorophores are turned on in the presence of galactosidase (GLU) for tumor-specific labeling. In summary, we developed novel therapeutic agent nanoparticles with the function of vascular normalization inducers to achieve specific labeling of hepatocellular carcinoma while exerting efficient antitumor effects in vivo.
Remodeling tumor microenvironment (TME) is a very promising and effective strategy to enhance the effects of chemotherapy, photodynamic therapy, and immunotherapy. Normalization of tumor vasculature as well as depletion of glutathione (GSH) can improve the TME. Here, we developed a novel therapeutic nanoparticle functional enzyme ultra QDAU5 nanoparticles (FEUQ Nps) based on a fluorescence-on and releasable strategy by combining a vascular normalization inducer, a GSH depleting agent, and an activated fluorophore. In which the cleavage of disulfide bonds releases active molecules that induce vascular normalization and improve the hypoxic microenvironment. In addition, it may deplete GSH in cancer cells, thus inducing the production of reactive oxygen species (ROS) and lipid peroxide (LPO) and promoting iron toxicity. It may also lead to endoplasmic stress and release of calmodulin, which activates the immune system. Meanwhile, quenched fluorophores are turned on in the presence of galactosidase (GLU) for tumor-specific labeling. In summary, we developed novel therapeutic agent nanoparticles with the function of vascular normalization inducers to achieve specific labeling of hepatocellular carcinoma while exerting efficient antitumor effects in vivo.
2024, 35(2): 108756
doi: 10.1016/j.cclet.2023.108756
Abstract:
Paclitaxel (PTX) is widely applied for the treatment of unresectable and metastasis breast carcinoma as well as other cancers, whereas its efficacy is always impeded by poor solubility. Liposomes are one kind of the most successful drug carriers which are capable of solubilizing PTX and improving patients' tolerance owing to excellent biocompatibility and biodegradability. However, poor compatibility between PTX and liposomes compromises the stability, drug loading and anti-tumor capacity of liposomal formulations. To address this issue, three lipids with various chain lengths, namely, myristic acid (MA, 14C), palmitic acid (PA, 16C) and stearic acid (SA, 18C), were conjugated to PTX via ester bonds and the synthesized prodrugs with high lipophilicity were further formulated into liposomes, respectively. All liposomes show high stability and drug loadings, as well as sustained drug release. The chain lengths of lipids are negatively correlated with drug release and enzymatic conversion rates, which further impact the pharmacokinetics, tumor accumulation, and anti-tumor efficacy of liposomal PTX. Neither rapid nor slow drug release facilitates high tumor accumulation as well as anti-tumor efficacy of PTX. Among all liposomes, PTX-PA-loaded liposomes show the longest circulation and highest tumor accumulation of PTX and exert the most potent anti-tumor capacities in vivo, owing to its moderate drug release and enzymatic conversion rate. Witnessing its superior safety, PTX-PA liposomes hold potential for further clinical translation.
Paclitaxel (PTX) is widely applied for the treatment of unresectable and metastasis breast carcinoma as well as other cancers, whereas its efficacy is always impeded by poor solubility. Liposomes are one kind of the most successful drug carriers which are capable of solubilizing PTX and improving patients' tolerance owing to excellent biocompatibility and biodegradability. However, poor compatibility between PTX and liposomes compromises the stability, drug loading and anti-tumor capacity of liposomal formulations. To address this issue, three lipids with various chain lengths, namely, myristic acid (MA, 14C), palmitic acid (PA, 16C) and stearic acid (SA, 18C), were conjugated to PTX via ester bonds and the synthesized prodrugs with high lipophilicity were further formulated into liposomes, respectively. All liposomes show high stability and drug loadings, as well as sustained drug release. The chain lengths of lipids are negatively correlated with drug release and enzymatic conversion rates, which further impact the pharmacokinetics, tumor accumulation, and anti-tumor efficacy of liposomal PTX. Neither rapid nor slow drug release facilitates high tumor accumulation as well as anti-tumor efficacy of PTX. Among all liposomes, PTX-PA-loaded liposomes show the longest circulation and highest tumor accumulation of PTX and exert the most potent anti-tumor capacities in vivo, owing to its moderate drug release and enzymatic conversion rate. Witnessing its superior safety, PTX-PA liposomes hold potential for further clinical translation.
2024, 35(2): 108758
doi: 10.1016/j.cclet.2023.108758
Abstract:
Calcium dibutyryladenosine cyclophosphate is a widely used cardiovascular drug. The traditional batch synthesis process suffers from long reaction times, tedious operations, and unstable yields. Herein, a sequential continuous flow synthesis combined with a multistage in-line purification process of calcium dibutyryladenosine cyclophosphate was developed. The acylation reaction was completed in a continuous coil reactor at 160 ℃ in 20 min. And the high toxic solvent pyridine was replaced by acetonitrile. Furthermore, the multistage in-line purification process was integrated into the homemade 3D circular cyclone-type micromixer chip. Combining with the membrane phase separators, the residence time of the purification step was 30 s. The isolated yield of this sequential continuous process was 92% with 99% purity.
Calcium dibutyryladenosine cyclophosphate is a widely used cardiovascular drug. The traditional batch synthesis process suffers from long reaction times, tedious operations, and unstable yields. Herein, a sequential continuous flow synthesis combined with a multistage in-line purification process of calcium dibutyryladenosine cyclophosphate was developed. The acylation reaction was completed in a continuous coil reactor at 160 ℃ in 20 min. And the high toxic solvent pyridine was replaced by acetonitrile. Furthermore, the multistage in-line purification process was integrated into the homemade 3D circular cyclone-type micromixer chip. Combining with the membrane phase separators, the residence time of the purification step was 30 s. The isolated yield of this sequential continuous process was 92% with 99% purity.
2024, 35(2): 108780
doi: 10.1016/j.cclet.2023.108780
Abstract:
Functional materials with multiple properties are urgent to be explored to reach high requirements for applications nowadays. In this work, a new multifunctional one-dimensional (1D) chain compound [N(C3H7)4][Cu(ohpma)]·H2O 1 (ohpma = deprotonated N-(2-hydoxyphenyl)oxamic acid) exhibiting both 1D antiferromagnetic and nonlinear optical properties, which are both originated from the same polar [Cu(C8H4NO4)] magnetic units, has been successfully synthesized by evaporation at room temperature. Bis-polydentate nature of the (ohpma)3− ligand with constrained tridentate and bidentate coordination sites conducts Cu2+ ions coordinating in different geometries and forms 1D chains along the c axis, which are further separated by the [N(C3H7)4]+ cations. And the 1D magnetic chains further exhibit noncentrosymmetric polar arrangement. Nonlinear optical study shows polar compound 1 exhibits a discernible second-harmonic generation (SHG) efficiency and the calculation of the partial density of states indicates that the SHG efficiency of 1 is mainly originated from the polar [Cu(C8H4NO4)] magnetic units. Moreover, magnetic susceptibility shows a broad maximum around 70 K with strong intrachain interaction of J/kB = −113.0 K but no long-range order is observed down to 2 K, suggesting that 1 shows a good 1D magnetism. Both good 1D magnetism and SHG activity suggest that 1 could be as a potential multifunctional material, particularly.
Functional materials with multiple properties are urgent to be explored to reach high requirements for applications nowadays. In this work, a new multifunctional one-dimensional (1D) chain compound [N(C3H7)4][Cu(ohpma)]·H2O 1 (ohpma = deprotonated N-(2-hydoxyphenyl)oxamic acid) exhibiting both 1D antiferromagnetic and nonlinear optical properties, which are both originated from the same polar [Cu(C8H4NO4)] magnetic units, has been successfully synthesized by evaporation at room temperature. Bis-polydentate nature of the (ohpma)3− ligand with constrained tridentate and bidentate coordination sites conducts Cu2+ ions coordinating in different geometries and forms 1D chains along the c axis, which are further separated by the [N(C3H7)4]+ cations. And the 1D magnetic chains further exhibit noncentrosymmetric polar arrangement. Nonlinear optical study shows polar compound 1 exhibits a discernible second-harmonic generation (SHG) efficiency and the calculation of the partial density of states indicates that the SHG efficiency of 1 is mainly originated from the polar [Cu(C8H4NO4)] magnetic units. Moreover, magnetic susceptibility shows a broad maximum around 70 K with strong intrachain interaction of J/kB = −113.0 K but no long-range order is observed down to 2 K, suggesting that 1 shows a good 1D magnetism. Both good 1D magnetism and SHG activity suggest that 1 could be as a potential multifunctional material, particularly.
2024, 35(2): 108796
doi: 10.1016/j.cclet.2023.108796
Abstract:
The compatibility of the gate dielectrics with semiconductors is vital for constructing efficient conducting channel for high charge transport. However, it is still a highly challenging mission to clearly clarify the relationship between the dielectric layers and the chemical structure of semiconductors, especially vacuum-deposited small molecules. Here, interfacial molecular screening of polyimide (Kapton) dielectric in organic field-effect transistors (OFETs) is comprehensively studied. It is found that the semiconducting small molecules with alkyl side chains prefer to form a high-quality charge transport layer on polyimide (PI) dielectrics compared with the molecules without alkyl side chains. On this basis, the fabricated transistors could reach the mobility of 1.2 cm2 V−1 s−1 the molecule with alkyl side chains on bare PI dielectric. What is more, the compatible semiconductor and dielectric would further produce a low activation energy (EA) of 3.01 meV towards efficient charge transport even at low temperature (e.g., 100 K, 0.9 cm2 V−1 s−1). Our research provides a guiding scheme for the construction of high-performance thin-film field-effect transistors based on PI dielectric layer at room and low temperatures.
The compatibility of the gate dielectrics with semiconductors is vital for constructing efficient conducting channel for high charge transport. However, it is still a highly challenging mission to clearly clarify the relationship between the dielectric layers and the chemical structure of semiconductors, especially vacuum-deposited small molecules. Here, interfacial molecular screening of polyimide (Kapton) dielectric in organic field-effect transistors (OFETs) is comprehensively studied. It is found that the semiconducting small molecules with alkyl side chains prefer to form a high-quality charge transport layer on polyimide (PI) dielectrics compared with the molecules without alkyl side chains. On this basis, the fabricated transistors could reach the mobility of 1.2 cm2 V−1 s−1 the molecule with alkyl side chains on bare PI dielectric. What is more, the compatible semiconductor and dielectric would further produce a low activation energy (EA) of 3.01 meV towards efficient charge transport even at low temperature (e.g., 100 K, 0.9 cm2 V−1 s−1). Our research provides a guiding scheme for the construction of high-performance thin-film field-effect transistors based on PI dielectric layer at room and low temperatures.
2024, 35(2): 108803
doi: 10.1016/j.cclet.2023.108803
Abstract:
Activated hepatic stellate cells (aHSCs), the main source of extracellular matrix deposition, are key targets in liver fibrosis. However, no effective drug specific to aHSCs has been clinically applied due to poor drug delivery efficiency. Herein, we designed a CXC chemokine receptor 4 (CXCR4)-targeted reactive oxygen species (ROS)-responsive platform AMD-Dex-ROS-responsive-sorafenib (ARS) based on natural polysaccharide and thioctic acid frame, which can deliver anti-fibrosis drug represented by sorafenib specifically to aHSCs on account of CXCR4 over-expression on aHSCs, and smartly disassemble via ROS-responsive thioketal rupture relying on high intracellular ROS in HSCs, realized on-demand drug release and effective liver fibrosis reversion. Notably, in this platform, the CXCR4 antagonist AMD3100 not only enhanced aHSCs targeting efficiency of sorafenib but also effectively magnified the aHSCs elimination of sorafenib by blocking stroma cell derived factor-1 (SDF-1)/CXCR4-induced aHSCs protection, resulting in synergistic anti-fibrosis effect. The platform provided a new approach for drug delivery system design and liver fibrosis treatment.
Activated hepatic stellate cells (aHSCs), the main source of extracellular matrix deposition, are key targets in liver fibrosis. However, no effective drug specific to aHSCs has been clinically applied due to poor drug delivery efficiency. Herein, we designed a CXC chemokine receptor 4 (CXCR4)-targeted reactive oxygen species (ROS)-responsive platform AMD-Dex-ROS-responsive-sorafenib (ARS) based on natural polysaccharide and thioctic acid frame, which can deliver anti-fibrosis drug represented by sorafenib specifically to aHSCs on account of CXCR4 over-expression on aHSCs, and smartly disassemble via ROS-responsive thioketal rupture relying on high intracellular ROS in HSCs, realized on-demand drug release and effective liver fibrosis reversion. Notably, in this platform, the CXCR4 antagonist AMD3100 not only enhanced aHSCs targeting efficiency of sorafenib but also effectively magnified the aHSCs elimination of sorafenib by blocking stroma cell derived factor-1 (SDF-1)/CXCR4-induced aHSCs protection, resulting in synergistic anti-fibrosis effect. The platform provided a new approach for drug delivery system design and liver fibrosis treatment.
2024, 35(2): 108824
doi: 10.1016/j.cclet.2023.108824
Abstract:
Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures. However, the relationship between the molecular structure of fluorescent probes and their membrane permeability and intracellular distribution is poorly understood. In this paper, we reported a series of 1,8-naphthalimide dyes and carried out cell imaging experiments, and found that the presence of amino hydrogen in these dyes played a crucial role in their cell membrane permeability and intracellular distribution. The secondary amino group containing compounds 1–4 show excellent membrane permeability and strong fluorescence in living cells. While the tertiary amine containing dyes 5 and 6 can hardly permeate the cell membrane though they show extremely similar structure with compounds 2–4. Compound 1 can selectively image lipid droplets by selecting the wavelength of excitation light. With the specificity for lysosomes, 2 and 4 have been used in long-term time-lapses imaging of lysosomal dynamics and tracking the process of lysosome–lysosome interaction, fusion and movement. The effect of hydrogen-containing amino substituent on the cell membrane permeability of fluorescent molecules is promising for the development of better biocompatible probes.
Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures. However, the relationship between the molecular structure of fluorescent probes and their membrane permeability and intracellular distribution is poorly understood. In this paper, we reported a series of 1,8-naphthalimide dyes and carried out cell imaging experiments, and found that the presence of amino hydrogen in these dyes played a crucial role in their cell membrane permeability and intracellular distribution. The secondary amino group containing compounds 1–4 show excellent membrane permeability and strong fluorescence in living cells. While the tertiary amine containing dyes 5 and 6 can hardly permeate the cell membrane though they show extremely similar structure with compounds 2–4. Compound 1 can selectively image lipid droplets by selecting the wavelength of excitation light. With the specificity for lysosomes, 2 and 4 have been used in long-term time-lapses imaging of lysosomal dynamics and tracking the process of lysosome–lysosome interaction, fusion and movement. The effect of hydrogen-containing amino substituent on the cell membrane permeability of fluorescent molecules is promising for the development of better biocompatible probes.
2024, 35(2): 108831
doi: 10.1016/j.cclet.2023.108831
Abstract:
Chiroptical switches based on circularly polarized luminescence (CPL) have shown the promising applications in advanced information technologies. Herein, a pair of lanthanide coordination polymer enantiomers [Eu2(LR)3(BTFPO)2]n and [Eu2(LS)3(BTFPO)2]n with light-regulated CPL property are designed, which are assembled by a chiral binuclear triple-stranded Eu3+ helicates [Eu2(LR/S)3] coordinated with two photochromic triphenylphosphine oxides (BTFPO). Upon the alternative UV and 526 nm light irradiation, the complexes show the reversible photochromism, PL and CPL responses. Notably, the luminescence dissymmetry factor, glum of 5D0→7F1 (591 nm) transition shows an obvious increase from 0.19 to 0.29 before and after 275 nm light irradiation. Additionally, the emission from Eu3+ center is not completely quenched in closed-ring state due to the low photocyclization (Фo-c) quantum yield of the polymer. The partial maintenance of emissive intensity is of essential importance for the monitor of CPL signal. More importantly, the CPL photo-switching property of the complexes in solid hybrid film is maintained, and still displays the enhanced CPL emission in photostationary state. Further, the potential applications of the doping film in logic gate and anti-counterfeiting were investigated.
Chiroptical switches based on circularly polarized luminescence (CPL) have shown the promising applications in advanced information technologies. Herein, a pair of lanthanide coordination polymer enantiomers [Eu2(LR)3(BTFPO)2]n and [Eu2(LS)3(BTFPO)2]n with light-regulated CPL property are designed, which are assembled by a chiral binuclear triple-stranded Eu3+ helicates [Eu2(LR/S)3] coordinated with two photochromic triphenylphosphine oxides (BTFPO). Upon the alternative UV and 526 nm light irradiation, the complexes show the reversible photochromism, PL and CPL responses. Notably, the luminescence dissymmetry factor, glum of 5D0→7F1 (591 nm) transition shows an obvious increase from 0.19 to 0.29 before and after 275 nm light irradiation. Additionally, the emission from Eu3+ center is not completely quenched in closed-ring state due to the low photocyclization (Фo-c) quantum yield of the polymer. The partial maintenance of emissive intensity is of essential importance for the monitor of CPL signal. More importantly, the CPL photo-switching property of the complexes in solid hybrid film is maintained, and still displays the enhanced CPL emission in photostationary state. Further, the potential applications of the doping film in logic gate and anti-counterfeiting were investigated.
2024, 35(2): 108880
doi: 10.1016/j.cclet.2023.108880
Abstract:
Prostate cancer (PC) biomarker-citrate detection is clinically important to diagnose PC in early stages. Methylquinolinium iodide (Q) conjugated indole-phenylboronic acid (IB) was designed as a red-emissive QIB probe for the detection of citrate through Lewis acid–base reaction and intramolecular charge transfer (ICT) sensing mechanisms. Boronic acid acts as Lewis acid as well as citrate (Lewis base) recognition unit. The probe reacted with citrate, showing enhanced red emissions. Since the probe has excellent water solubility and great biocompatibility, practical application in biological systems is possible. Citrate was monitored precisely in the mitochondria organelle (in vitro) of living cells with a positive charge on QIB. Also, endogenous (in situ) citrate was detected quantitatively to discriminate non-cancerous and PC mice, observed strong and lower (negligible) emission intensity on non-cancerous and cancerous prostate tissues, respectively. Because, the concentration of citrate is higher in healthy prostate compared with PC prostate. Furthermore, the analysis of sliced prostate tissues can give PC-related information for clinical diagnosis to prevent and treat PC in the initial stages. Therefore, we believe that the present probe is a promising biochemical reagent in diagnosing PC.
Prostate cancer (PC) biomarker-citrate detection is clinically important to diagnose PC in early stages. Methylquinolinium iodide (Q) conjugated indole-phenylboronic acid (IB) was designed as a red-emissive QIB probe for the detection of citrate through Lewis acid–base reaction and intramolecular charge transfer (ICT) sensing mechanisms. Boronic acid acts as Lewis acid as well as citrate (Lewis base) recognition unit. The probe reacted with citrate, showing enhanced red emissions. Since the probe has excellent water solubility and great biocompatibility, practical application in biological systems is possible. Citrate was monitored precisely in the mitochondria organelle (in vitro) of living cells with a positive charge on QIB. Also, endogenous (in situ) citrate was detected quantitatively to discriminate non-cancerous and PC mice, observed strong and lower (negligible) emission intensity on non-cancerous and cancerous prostate tissues, respectively. Because, the concentration of citrate is higher in healthy prostate compared with PC prostate. Furthermore, the analysis of sliced prostate tissues can give PC-related information for clinical diagnosis to prevent and treat PC in the initial stages. Therefore, we believe that the present probe is a promising biochemical reagent in diagnosing PC.
2024, 35(2): 108923
doi: 10.1016/j.cclet.2023.108923
Abstract:
Si-based materials have shown great potential as lithium-ion batteries (LIBs) anodes due to their natural reserves and high theoretical capacity. However, the large volume changes during cycles and poor conductivity of Si lead to rapid capacity decay and poor cycling stability, ultimately limiting their commercial applications. Herein, we have skillfully utilized the microporous MCM-22 zeolite as the unique silicon source to produce porous Si (pSi) sheets by a simple magnesiothermic reduction, followed by a carbon coating and further Ti3C2Tx MXene assembly, obtaining the ternary pSi@NC@TNSs composite. In the design, porous Si sheets provide more active sites and shorten Li-ion transport paths for electrochemical reactions. The N-doped carbon (NC) layer serves as a bonding layer to couple pSi and Ti3C2Tx. The conductive network formed by 2D Ti3C2Tx and medium NC layer effectively enhances the overall charge transport of the electrode material, and helps to stabilize the electrode structure. Therefore, the as-made pSi@NC@TNSs anode delivers an improved lithium storage performance, exhibiting a high reversible capacity of 925 mAh/g at 0.5 A/g after 100 cycles. This present strategy provides an effective way towards high-performance Si-based anodes for LIBs.
Si-based materials have shown great potential as lithium-ion batteries (LIBs) anodes due to their natural reserves and high theoretical capacity. However, the large volume changes during cycles and poor conductivity of Si lead to rapid capacity decay and poor cycling stability, ultimately limiting their commercial applications. Herein, we have skillfully utilized the microporous MCM-22 zeolite as the unique silicon source to produce porous Si (pSi) sheets by a simple magnesiothermic reduction, followed by a carbon coating and further Ti3C2Tx MXene assembly, obtaining the ternary pSi@NC@TNSs composite. In the design, porous Si sheets provide more active sites and shorten Li-ion transport paths for electrochemical reactions. The N-doped carbon (NC) layer serves as a bonding layer to couple pSi and Ti3C2Tx. The conductive network formed by 2D Ti3C2Tx and medium NC layer effectively enhances the overall charge transport of the electrode material, and helps to stabilize the electrode structure. Therefore, the as-made pSi@NC@TNSs anode delivers an improved lithium storage performance, exhibiting a high reversible capacity of 925 mAh/g at 0.5 A/g after 100 cycles. This present strategy provides an effective way towards high-performance Si-based anodes for LIBs.
2024, 35(2): 108932
doi: 10.1016/j.cclet.2023.108932
Abstract:
The unique properties of metal oxide surfaces, crystal surfaces and defects play vital roles in biomass upgrading reactions. In this work, hierarchical porous bowl-shaped ZrO2 (HB-ZrO2) with mixed crystal phase was designed and employed as the support for loading AuPd bimetal with different proportions to synthesize AuPd/HB-ZrO2 catalysts. The effects of surface chemistry, oxygen defects, bimetal interaction and metal-support interaction of AuPd/HB-ZrO2 on catalytic performance for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) were systematically investigated. The Au2Pd1/HB-ZrO2 catalyst afforded a satisfactory FDCA yield of 99.9% from HMF oxidation using O2 as the oxidant in water, accompanied with an excellent FDCA productivity at 97.6 mmol g−1 h−1. This work offers fresh insights into rationally designing efficient catalysts with oxygen-rich defects for the catalytic upgrading of biomass platform chemicals.
The unique properties of metal oxide surfaces, crystal surfaces and defects play vital roles in biomass upgrading reactions. In this work, hierarchical porous bowl-shaped ZrO2 (HB-ZrO2) with mixed crystal phase was designed and employed as the support for loading AuPd bimetal with different proportions to synthesize AuPd/HB-ZrO2 catalysts. The effects of surface chemistry, oxygen defects, bimetal interaction and metal-support interaction of AuPd/HB-ZrO2 on catalytic performance for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) were systematically investigated. The Au2Pd1/HB-ZrO2 catalyst afforded a satisfactory FDCA yield of 99.9% from HMF oxidation using O2 as the oxidant in water, accompanied with an excellent FDCA productivity at 97.6 mmol g−1 h−1. This work offers fresh insights into rationally designing efficient catalysts with oxygen-rich defects for the catalytic upgrading of biomass platform chemicals.
2024, 35(2): 108935
doi: 10.1016/j.cclet.2023.108935
Abstract:
Nitrate (NO3−) electroreduction reaction (NO3−RR) provides an attractive and sustainable route for NO3− pollution mitigation or energy-saved ammonia (NH3) synthesis. In this work, high-quality B and Fe co-doped Co2P hollow nanocubes (B/Fe-Co2P HNCs) are successfully synthesized though simultaneous boronation-phosphorization treatment, which reveal outstanding selectivity, activity, stability for the NO3− to NH3 conversion in neutral electrolyte because of big surface area, fast mass transport, superhydrophilic surface, and optimized electronic structure. B/Fe-Co2P HNCs can achieve the high NH3 yield rate (22.67 mg h−1 mgcat−1) as well as Faradaic efficiency (97.54%) for NO3−RR, greatly outperforming most of non-precious metal based NO3−RR electrocatalysts.
Nitrate (NO3−) electroreduction reaction (NO3−RR) provides an attractive and sustainable route for NO3− pollution mitigation or energy-saved ammonia (NH3) synthesis. In this work, high-quality B and Fe co-doped Co2P hollow nanocubes (B/Fe-Co2P HNCs) are successfully synthesized though simultaneous boronation-phosphorization treatment, which reveal outstanding selectivity, activity, stability for the NO3− to NH3 conversion in neutral electrolyte because of big surface area, fast mass transport, superhydrophilic surface, and optimized electronic structure. B/Fe-Co2P HNCs can achieve the high NH3 yield rate (22.67 mg h−1 mgcat−1) as well as Faradaic efficiency (97.54%) for NO3−RR, greatly outperforming most of non-precious metal based NO3−RR electrocatalysts.
2024, 35(2): 108938
doi: 10.1016/j.cclet.2023.108938
Abstract:
Deoximation is an important transformation in synthetic industry. It can be employed in protection, characterization and purification of the carbonyls, and in the synthesis of ketones from non-carbonyl molecules. In the field, oxidative deoximation reaction can utilize the driving force caused by the oxidation process so that the reaction can occur under relatively mild conditions. Recently, we designed and prepared polyaniline-supported molybdenum (Mo@PANI) just by immersing PANI into the EtOH/H2O solution of MoCl5. The material was successfully applied as the efficient catalyst for oxidative deoximation reactions, which were performed in ethanol using H2O2 as the clean oxidant. The substrate scope of the reaction was wide. It could be applied on heterocycle-containing substrates, making this protocol preferable for pharmaceutical intermediate synthesis. Since Mo is a necessary trace element for both animals and plants, this method is environment-friendly and is suitable for large-scale preparation. This work as the first example of Mo-catalyzed oxidative deoximation reaction may inspire novel ideas for both catalyst design and synthetic process development.
Deoximation is an important transformation in synthetic industry. It can be employed in protection, characterization and purification of the carbonyls, and in the synthesis of ketones from non-carbonyl molecules. In the field, oxidative deoximation reaction can utilize the driving force caused by the oxidation process so that the reaction can occur under relatively mild conditions. Recently, we designed and prepared polyaniline-supported molybdenum (Mo@PANI) just by immersing PANI into the EtOH/H2O solution of MoCl5. The material was successfully applied as the efficient catalyst for oxidative deoximation reactions, which were performed in ethanol using H2O2 as the clean oxidant. The substrate scope of the reaction was wide. It could be applied on heterocycle-containing substrates, making this protocol preferable for pharmaceutical intermediate synthesis. Since Mo is a necessary trace element for both animals and plants, this method is environment-friendly and is suitable for large-scale preparation. This work as the first example of Mo-catalyzed oxidative deoximation reaction may inspire novel ideas for both catalyst design and synthetic process development.
2024, 35(2): 108948
doi: 10.1016/j.cclet.2023.108948
Abstract:
Multifunctional molecules with both optical signal and pharmacological activity play an important role in drug development, disease diagnosis, and basic theoretical research. Aminopeptidase N (APN), as a representative tumor biomarker with anti-tumor potential, still lacks a high-precision theranostic probe specifically targeting it. In this study, a novel quaternity design strategy for APN theranostic probe was developed. This proposed strategy utilizes advanced machine learning and molecular dynamics simulations, and cleverly employs the strategy of conformation-induced fluorescence recovery to achieve multi-objective optimization and integration of functional fragments. Through this strategy, a unique "Off–On" theranostic probe, ABTP-DPTB, was ingeniously constructed to light up APN through fluorescence restoration, relying on conformation-induced effects and solvent restriction. Differ from the common diagnostic probes, the intelligent design with non-substrated linkage makes ABTP-DPTB for long-term in-situ imaging. The fabricated probe was used for detecting and inhibiting APN in various environments, with a better in vitro inhibitory than golden-standard drug bestatin.
Multifunctional molecules with both optical signal and pharmacological activity play an important role in drug development, disease diagnosis, and basic theoretical research. Aminopeptidase N (APN), as a representative tumor biomarker with anti-tumor potential, still lacks a high-precision theranostic probe specifically targeting it. In this study, a novel quaternity design strategy for APN theranostic probe was developed. This proposed strategy utilizes advanced machine learning and molecular dynamics simulations, and cleverly employs the strategy of conformation-induced fluorescence recovery to achieve multi-objective optimization and integration of functional fragments. Through this strategy, a unique "Off–On" theranostic probe, ABTP-DPTB, was ingeniously constructed to light up APN through fluorescence restoration, relying on conformation-induced effects and solvent restriction. Differ from the common diagnostic probes, the intelligent design with non-substrated linkage makes ABTP-DPTB for long-term in-situ imaging. The fabricated probe was used for detecting and inhibiting APN in various environments, with a better in vitro inhibitory than golden-standard drug bestatin.
2024, 35(2): 108956
doi: 10.1016/j.cclet.2023.108956
Abstract:
Cyclic polymers are a class of polymers that feature endless topology, and the synthesis of cyclic polymers has attracted the attention of many researchers. Herein, cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations. Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)) (P(OEGA-co-DDA)) precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization using a bifunctional chain transfer agent with two anthryl end groups. The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water. By irradiating the aqueous solution of the nanoparticles with 365 nm UV light, cyclic polymers were synthesized successfully via coupling of anthryl groups. The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA) copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via 1H nuclear magnetic resonance (1H NMR), dynamic light scattering (DLS), UV‒visible (vis) analysis, three-detection size exclusion chromatography (TD-SEC) and transmission electron microscopy (TEM). It was found that by adjusting the content of the hydrophilic segments in linear precursors, single chain polymeric nanoparticles (SCPNs) can be generated at high polymer concentrations. Therefore, cyclic polymers with high purity can be constructed efficiently. This method overcomes the limitation of traditional ring-closure method, which is typically conducted in highly dilute conditions, providing an efficient method for the scalable preparation of cyclic polymers.
Cyclic polymers are a class of polymers that feature endless topology, and the synthesis of cyclic polymers has attracted the attention of many researchers. Herein, cyclic polymers were efficiently constructed by self-folding cyclization technique at high concentrations. Linear poly((oligo(ethylene glycol)acrylate)-co-(dodecyl acrylate)) (P(OEGA-co-DDA)) precursors with different ratios of hydrophilic and hydrophobic moieties were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization using a bifunctional chain transfer agent with two anthryl end groups. The amphiphilic linear precursors underwent the self-folding process to generate polymeric nanoparticles in water. By irradiating the aqueous solution of the nanoparticles with 365 nm UV light, cyclic polymers were synthesized successfully via coupling of anthryl groups. The effects of the ratios of hydrophilic and hydrophobic moieties in linear P(OEGA-co-DDA) copolymers and polymer concentration on the purity of the obtained cyclic polymers were explored in detail via 1H nuclear magnetic resonance (1H NMR), dynamic light scattering (DLS), UV‒visible (vis) analysis, three-detection size exclusion chromatography (TD-SEC) and transmission electron microscopy (TEM). It was found that by adjusting the content of the hydrophilic segments in linear precursors, single chain polymeric nanoparticles (SCPNs) can be generated at high polymer concentrations. Therefore, cyclic polymers with high purity can be constructed efficiently. This method overcomes the limitation of traditional ring-closure method, which is typically conducted in highly dilute conditions, providing an efficient method for the scalable preparation of cyclic polymers.
2024, 35(2): 108979
doi: 10.1016/j.cclet.2023.108979
Abstract:
A charge transfer complex (CTC)-enabled photoreduction of ether phosphonium salts for the generation of oxyalkyl radicals was described. The photoreduction provides a convenient method to achieve selective oxyalkylation of enamides with broad substrate scope. The method features operational simplicity, mild and inherent green conditions.
A charge transfer complex (CTC)-enabled photoreduction of ether phosphonium salts for the generation of oxyalkyl radicals was described. The photoreduction provides a convenient method to achieve selective oxyalkylation of enamides with broad substrate scope. The method features operational simplicity, mild and inherent green conditions.
2024, 35(2): 109002
doi: 10.1016/j.cclet.2023.109002
Abstract:
Modulating surface charge redistribution based on interface and defect engineering has been considered as a resultful means to boost electrocatalytic activity. However, the mechanism of synergistic regulation of heterojunction and vacancy defects remains unclear. Herein, a Vs-CoP-CoS2/C n-n heterojunction with sulfur vacancies is successfully constructed, which manifests superior electrocatalytic activity for oxygen evolution, as demonstrated by a low overpotential of 170 mV to reach 10 mA/cm2. The experimental results and density functional theory calculations testify that the outstanding OER performance of Vs-CoP-CoS2/C heterojunction is owed to the synergistic effect of sulfur vacancies and built-in electric field at n-n heterogeneous interface, which accelerates the electron transfer, induces the charge redistribution, and regulates the adsorption energy of active intermediates during the reaction. This study affords a promising means to regulate the electrocatalytic performance by the construction of heterogeneous interfaces and defects, and in-depth explores the synergistic mechanisms of n-n heterojunction and vacancies.
Modulating surface charge redistribution based on interface and defect engineering has been considered as a resultful means to boost electrocatalytic activity. However, the mechanism of synergistic regulation of heterojunction and vacancy defects remains unclear. Herein, a Vs-CoP-CoS2/C n-n heterojunction with sulfur vacancies is successfully constructed, which manifests superior electrocatalytic activity for oxygen evolution, as demonstrated by a low overpotential of 170 mV to reach 10 mA/cm2. The experimental results and density functional theory calculations testify that the outstanding OER performance of Vs-CoP-CoS2/C heterojunction is owed to the synergistic effect of sulfur vacancies and built-in electric field at n-n heterogeneous interface, which accelerates the electron transfer, induces the charge redistribution, and regulates the adsorption energy of active intermediates during the reaction. This study affords a promising means to regulate the electrocatalytic performance by the construction of heterogeneous interfaces and defects, and in-depth explores the synergistic mechanisms of n-n heterojunction and vacancies.
2024, 35(2): 109018
doi: 10.1016/j.cclet.2023.109018
Abstract:
Improving the performance of all-small-molecule organic solar cells (ASM-OSCs) largely depends on the design and application of novel donors with appropriate crystallinity. Extending molecular conjugation is an effective method for regulating molecular stacking and crystallinity. In this work, we successfully designed and synthesized two novel acceptor-donor-donor-donor-acceptor (A-D-D-D-A) type oligomeric donors with three dithieno[2,3-d:2’,3’-d’]benzo[1,2-b:4,5-b’]dithiophene (DTBDT) as the central unit, named as 3DTBDT-Cl and 3DTBDT, depending on with and without chlorine substitution on the thiophene side chains. We found that the introduction of chlorine atoms makes the blend films display stronger crystallinity but with large-scale phase separation morphology and more defects, which eventually leads to a power conversion efficiency (PCE) of only 10.83%, whereas the blend films based 3DTBDT with appropriate crystallinity achieved 13.74% PCE. Compared with 3DTBDT-Cl/L8-BO, the 3DTBDT/L8-BO films exhibited a nanoscale bi-continuous interpenetrating network morphology with a smaller domain size and more suitable crystallinity, which guarantees the corresponding devices obtained more efficient exciton dissociation, efficient charge transport, reduced bimolecular recombination, and performed more balanced carrier mobility. These results demonstrated that regulating the crystallinity of oligomeric donors to obtain the desired phase separation morphology in the blend films could facilitate further improving the performance of ASM-OSCs.
Improving the performance of all-small-molecule organic solar cells (ASM-OSCs) largely depends on the design and application of novel donors with appropriate crystallinity. Extending molecular conjugation is an effective method for regulating molecular stacking and crystallinity. In this work, we successfully designed and synthesized two novel acceptor-donor-donor-donor-acceptor (A-D-D-D-A) type oligomeric donors with three dithieno[2,3-d:2’,3’-d’]benzo[1,2-b:4,5-b’]dithiophene (DTBDT) as the central unit, named as 3DTBDT-Cl and 3DTBDT, depending on with and without chlorine substitution on the thiophene side chains. We found that the introduction of chlorine atoms makes the blend films display stronger crystallinity but with large-scale phase separation morphology and more defects, which eventually leads to a power conversion efficiency (PCE) of only 10.83%, whereas the blend films based 3DTBDT with appropriate crystallinity achieved 13.74% PCE. Compared with 3DTBDT-Cl/L8-BO, the 3DTBDT/L8-BO films exhibited a nanoscale bi-continuous interpenetrating network morphology with a smaller domain size and more suitable crystallinity, which guarantees the corresponding devices obtained more efficient exciton dissociation, efficient charge transport, reduced bimolecular recombination, and performed more balanced carrier mobility. These results demonstrated that regulating the crystallinity of oligomeric donors to obtain the desired phase separation morphology in the blend films could facilitate further improving the performance of ASM-OSCs.
2024, 35(2): 109058
doi: 10.1016/j.cclet.2023.109058
Abstract:
The preparation of medium-sized benzo[b]azocines has always been challenging because of inherently unfavorable enthalpy and entropy factors. This report presents a novel approach for accessing 8-membered seleno-benzo[b]azocines via electrochemically-driven seleno-cyclization. This method enables room-temperature preparation of various structurally diverse medium-sized seleno-benzo[b]azocines. The facile deselenation of the seleno-cyclization products to generate functionalized dienes is an additional benefit of this indispensable reaction. Mechanistic insights are presented based on radical inhibition experiments and cyclic voltammetry measurements, which elucidate the radical pathway. Finally, density functional theory calculations further rationalize the rate-determining step and the unique chemoselectivity observed in this transformation.
The preparation of medium-sized benzo[b]azocines has always been challenging because of inherently unfavorable enthalpy and entropy factors. This report presents a novel approach for accessing 8-membered seleno-benzo[b]azocines via electrochemically-driven seleno-cyclization. This method enables room-temperature preparation of various structurally diverse medium-sized seleno-benzo[b]azocines. The facile deselenation of the seleno-cyclization products to generate functionalized dienes is an additional benefit of this indispensable reaction. Mechanistic insights are presented based on radical inhibition experiments and cyclic voltammetry measurements, which elucidate the radical pathway. Finally, density functional theory calculations further rationalize the rate-determining step and the unique chemoselectivity observed in this transformation.
2024, 35(2): 109066
doi: 10.1016/j.cclet.2023.109066
Abstract:
A bottleneck in biomimetic synthesis consists in the full copy of, for example, the hierarchical structure of proteins directed by weak interactions. By contrast with covalent bonds bearing definite orientation and high stability, weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design. In this endeavor, a ligand-dominated strategy that embodies tunable electrostatic repulsion and π…π stacking was first employed to shape polyoxovanadate-based metal-organic polyhedra (VMOPs). Structural evolution involving transformation, interlock, and discovery of an unprecedented prototype of the Star of David was hence achievable. Not only as a handy tool for the primary structural control over VMOPs, these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors, representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.
A bottleneck in biomimetic synthesis consists in the full copy of, for example, the hierarchical structure of proteins directed by weak interactions. By contrast with covalent bonds bearing definite orientation and high stability, weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design. In this endeavor, a ligand-dominated strategy that embodies tunable electrostatic repulsion and π…π stacking was first employed to shape polyoxovanadate-based metal-organic polyhedra (VMOPs). Structural evolution involving transformation, interlock, and discovery of an unprecedented prototype of the Star of David was hence achievable. Not only as a handy tool for the primary structural control over VMOPs, these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors, representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.
2024, 35(2): 109107
doi: 10.1016/j.cclet.2023.109107
Abstract:
An additive-free and environmentally friendly strategy has been realized for the construction of S-substituted isothioureas through visible-light-induced multicomponent reaction starting from α-diazoesters, aryl isothiocyanates, amines and cyclic ethers. This methodology features simple operation, mild reaction conditions, favorable functional group tolerance, easily available starting materials and high efficiency.
An additive-free and environmentally friendly strategy has been realized for the construction of S-substituted isothioureas through visible-light-induced multicomponent reaction starting from α-diazoesters, aryl isothiocyanates, amines and cyclic ethers. This methodology features simple operation, mild reaction conditions, favorable functional group tolerance, easily available starting materials and high efficiency.
2024, 35(2): 109144
doi: 10.1016/j.cclet.2023.109144
Abstract:
Lithium (Li) dendrite issue, which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase (SEI), impedes the further development of high-energy Li metal batteries. However, the integrated construction of a high-stable SEI layer that can regulate uniform nucleation and facilitate fast Li-ion diffusion kinetics for Li metal anode still falls short. Herein, we designed an artificial SEI with hybrid ionic/electronic interphase to regulate Li deposition by in-situ constructing metal Co clusters embedded in LiF matrix. The generated Co and LiF both enable fast Li-ion diffusion kinetics, meanwhile, the lithiophilic properties of Co clusters can serve as Li-ion nucleation sites, thereby contributing to uniform Li nucleation and non-dendritic growth. As a result, a dendrite-free Li deposition with a low overpotential (16.1 mV) is achieved, which enables an extended lifespan over 750 h under strict conditions. The full cells with high-mass-loading LiFePO4 (11.5 mg/cm2) as cathodes exhibit a remarkable rate capacity of 84.1 mAh/g at 5 C and an improved cycling performance with a capacity retention of 96.4% after undergoing 180 cycles.
Lithium (Li) dendrite issue, which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase (SEI), impedes the further development of high-energy Li metal batteries. However, the integrated construction of a high-stable SEI layer that can regulate uniform nucleation and facilitate fast Li-ion diffusion kinetics for Li metal anode still falls short. Herein, we designed an artificial SEI with hybrid ionic/electronic interphase to regulate Li deposition by in-situ constructing metal Co clusters embedded in LiF matrix. The generated Co and LiF both enable fast Li-ion diffusion kinetics, meanwhile, the lithiophilic properties of Co clusters can serve as Li-ion nucleation sites, thereby contributing to uniform Li nucleation and non-dendritic growth. As a result, a dendrite-free Li deposition with a low overpotential (16.1 mV) is achieved, which enables an extended lifespan over 750 h under strict conditions. The full cells with high-mass-loading LiFePO4 (11.5 mg/cm2) as cathodes exhibit a remarkable rate capacity of 84.1 mAh/g at 5 C and an improved cycling performance with a capacity retention of 96.4% after undergoing 180 cycles.
2024, 35(2): 109155
doi: 10.1016/j.cclet.2023.109155
Abstract:
Organofluorine compounds are widely used in the realm of drug discovery and material science. Herein, we developed palladium catalyzed intermolecular aminofluorination and oxy-aminofluorination of gem-difluoroalkenes with N-fluorobenzenesulfonimide (NFSI), in which NFSI was used as the nitrogen source and oxidant. The reaction provides an efficient and straightforward synthesis route of a series of α-trifluoromethyl benzylic amines. Notably, three/four components oxy-aminofluorination processes were realized to give α-trifluoromethyl benzylic ether with a terminal amino group, which proceed through C(sp3)–O bond cleavage of easily available ether and simultaneous introduced a fluorine, an amino and an oxy substituent in one pot with excellent regioselectivity. The divergent reactivity not only included the incorporation of one ether molecular, but also much more challenged two ether insertion with excellent selectivity through succession C(sp3)–O bonds cleavage. This protocol allows for concise synthesis of high value amines with fluoroalkyl-substituents and selectively transformation of easily available ethers by high-valent palladium catalysis.
Organofluorine compounds are widely used in the realm of drug discovery and material science. Herein, we developed palladium catalyzed intermolecular aminofluorination and oxy-aminofluorination of gem-difluoroalkenes with N-fluorobenzenesulfonimide (NFSI), in which NFSI was used as the nitrogen source and oxidant. The reaction provides an efficient and straightforward synthesis route of a series of α-trifluoromethyl benzylic amines. Notably, three/four components oxy-aminofluorination processes were realized to give α-trifluoromethyl benzylic ether with a terminal amino group, which proceed through C(sp3)–O bond cleavage of easily available ether and simultaneous introduced a fluorine, an amino and an oxy substituent in one pot with excellent regioselectivity. The divergent reactivity not only included the incorporation of one ether molecular, but also much more challenged two ether insertion with excellent selectivity through succession C(sp3)–O bonds cleavage. This protocol allows for concise synthesis of high value amines with fluoroalkyl-substituents and selectively transformation of easily available ethers by high-valent palladium catalysis.
2024, 35(2): 109184
doi: 10.1016/j.cclet.2023.109184
Abstract:
Bridged polycyclic lactams are important structural units in organic functional materials, natural products, and pharmaceuticals. A flexible and efficient anion cascade reaction was developed for the preparation of bridged polycyclic lactams from readily available malonamides and 1, 4-dien-3-ones. Various highly substituted bridged polycyclic lactams were synthesized in good to excellent yields by tandem nucleophilic sequences in the presence of BuOK in commercially available EtOH solvent at 60 ℃. Notably, the simple reactions can be run on a gram scale. Mechanistically, bis-Michael addition reaction and hemiaminalization reactions are involved in the tandem transformation.
Bridged polycyclic lactams are important structural units in organic functional materials, natural products, and pharmaceuticals. A flexible and efficient anion cascade reaction was developed for the preparation of bridged polycyclic lactams from readily available malonamides and 1, 4-dien-3-ones. Various highly substituted bridged polycyclic lactams were synthesized in good to excellent yields by tandem nucleophilic sequences in the presence of BuOK in commercially available EtOH solvent at 60 ℃. Notably, the simple reactions can be run on a gram scale. Mechanistically, bis-Michael addition reaction and hemiaminalization reactions are involved in the tandem transformation.
2024, 35(2): 109255
doi: 10.1016/j.cclet.2023.109255
Abstract:
The cubic S/N co-doped TiO2 (TNSx, x is the calcination temperature) photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH2-MIL-125 for the photocatalytic removal of gaseous formaldehyde (a volatile organic compound). Among the obtained catalysts, the presence of oxygen vacancies restricted photogenerated electron and holes recombination. 98.00% removal of gaseous formaldehyde in 150 min could be achieved over TNS600 by xenon lamp. The removal efficiency for formaldehyde was well retained for five cycle experiment. The results from PL, TRPL and EIS revealed that TNS600 had the best separation efficiency of photogenerated electrons and holes, and the enhanced charge separation led to a significant increase in photocatalytic activity. The photocatalytic oxidation mechanism indicated that the •OH and •O2− radicals were mainly involved in the efficient elimination of gaseous formaldehyde and were able to mineralize formaldehyde to H2O and CO2.
The cubic S/N co-doped TiO2 (TNSx, x is the calcination temperature) photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH2-MIL-125 for the photocatalytic removal of gaseous formaldehyde (a volatile organic compound). Among the obtained catalysts, the presence of oxygen vacancies restricted photogenerated electron and holes recombination. 98.00% removal of gaseous formaldehyde in 150 min could be achieved over TNS600 by xenon lamp. The removal efficiency for formaldehyde was well retained for five cycle experiment. The results from PL, TRPL and EIS revealed that TNS600 had the best separation efficiency of photogenerated electrons and holes, and the enhanced charge separation led to a significant increase in photocatalytic activity. The photocatalytic oxidation mechanism indicated that the •OH and •O2− radicals were mainly involved in the efficient elimination of gaseous formaldehyde and were able to mineralize formaldehyde to H2O and CO2.
2024, 35(2): 108337
doi: 10.1016/j.cclet.2023.108337
Abstract:
Aqueous zinc metal batteries are considered as promising candidates for next-generation electrochemical energy storage devices, especially for large-scale energy storage, due to the advantages of high-safety, high energy density and low cost. As the bridge connecting cathode and anode, electrolyte provides a realistic operating environment. In alkaline and neutral aqueous zinc metal batteries, issues associated with electrolyte and anode are still intractable. In this review, we reveal the development and evolution of electrolytes for aqueous zinc metal batteries from alkaline to neutral via the description of fundamentals and challenges in terms of comparison and connection. We also elaborate the strategies in electrolytes regulation and highlight the basic roles and progresses in additives engineering.
Aqueous zinc metal batteries are considered as promising candidates for next-generation electrochemical energy storage devices, especially for large-scale energy storage, due to the advantages of high-safety, high energy density and low cost. As the bridge connecting cathode and anode, electrolyte provides a realistic operating environment. In alkaline and neutral aqueous zinc metal batteries, issues associated with electrolyte and anode are still intractable. In this review, we reveal the development and evolution of electrolytes for aqueous zinc metal batteries from alkaline to neutral via the description of fundamentals and challenges in terms of comparison and connection. We also elaborate the strategies in electrolytes regulation and highlight the basic roles and progresses in additives engineering.
2024, 35(2): 108468
doi: 10.1016/j.cclet.2023.108468
Abstract:
Rare earth luminescence has attracted widespread attention for several decades, among which near-infrared (NIR) light-related up-conversion luminescence and NIR-Ⅱ luminescence are widely used in the biomedical field. The NIR-related luminescence is widely studied due to the excellent performance, such as good biocompatibility, deep tissue penetration depth, low self-fluorescence and minimal light damage to organisms. In this review, we mainly introduce the mechanism for rare earth up-conversion luminescence, NIR-Ⅱ luminescence and conclude their advantages compared with traditional luminescence. These excellent priorities provide the basis for NIR-related luminescence bioimaging in vivo. Additionally, we hilglight the scheme for the sensitive detection of substances in organisms and various methods for biological therapy. In spite of the existing research, it is outlined that NIR-related luminescence has great potential to be applied in different aspects, expanding perspectives and future challenges of research in related fields. Based on the current scientific achievements, this review can provide reference for research in the areas mentioned above, expand the research direction and arouse a broad interest in different disciplines to pay attention to rare earth luminescence.
Rare earth luminescence has attracted widespread attention for several decades, among which near-infrared (NIR) light-related up-conversion luminescence and NIR-Ⅱ luminescence are widely used in the biomedical field. The NIR-related luminescence is widely studied due to the excellent performance, such as good biocompatibility, deep tissue penetration depth, low self-fluorescence and minimal light damage to organisms. In this review, we mainly introduce the mechanism for rare earth up-conversion luminescence, NIR-Ⅱ luminescence and conclude their advantages compared with traditional luminescence. These excellent priorities provide the basis for NIR-related luminescence bioimaging in vivo. Additionally, we hilglight the scheme for the sensitive detection of substances in organisms and various methods for biological therapy. In spite of the existing research, it is outlined that NIR-related luminescence has great potential to be applied in different aspects, expanding perspectives and future challenges of research in related fields. Based on the current scientific achievements, this review can provide reference for research in the areas mentioned above, expand the research direction and arouse a broad interest in different disciplines to pay attention to rare earth luminescence.
2024, 35(2): 108533
doi: 10.1016/j.cclet.2023.108533
Abstract:
Two-dimensional (2D) MXenes have emerged as an archetypical layered material combining the properties of an organic-inorganic hybrid offering materials sustainability for a range of applications. Their surface functional groups and the associated chemical properties' tailorability through functionalizing MXenes with other materials as well as hydrophilicity and high conductivity enable them to be the best successor for various applications in textile industries, especially in the advancement of smart textiles and remediation of textile wastewater. MXene-based textile composite performs superb smartness in high-performance wearables as well as in the reduction of textile dyes from wastewater. This article critically reviews the significance of MXenes in two sectors of the textile industry. Firstly, we review the improvement of textile raw materials such as fiber, yarn, and fabric by using MXene as electrodes in supercapacitors, pressure sensors. Secondly, we review advancements in the removal of dyes from textile wastewater utilizing MXene as an absorbent by the adsorption process. MXene-based textiles demonstrated superior strength through the strong bonding between MXene and textile structures as well as the treatment of adsorbate by adsorbent (MXene in the adsorption process). We identify critical gaps for further research to enable their real-life applications.
Two-dimensional (2D) MXenes have emerged as an archetypical layered material combining the properties of an organic-inorganic hybrid offering materials sustainability for a range of applications. Their surface functional groups and the associated chemical properties' tailorability through functionalizing MXenes with other materials as well as hydrophilicity and high conductivity enable them to be the best successor for various applications in textile industries, especially in the advancement of smart textiles and remediation of textile wastewater. MXene-based textile composite performs superb smartness in high-performance wearables as well as in the reduction of textile dyes from wastewater. This article critically reviews the significance of MXenes in two sectors of the textile industry. Firstly, we review the improvement of textile raw materials such as fiber, yarn, and fabric by using MXene as electrodes in supercapacitors, pressure sensors. Secondly, we review advancements in the removal of dyes from textile wastewater utilizing MXene as an absorbent by the adsorption process. MXene-based textiles demonstrated superior strength through the strong bonding between MXene and textile structures as well as the treatment of adsorbate by adsorbent (MXene in the adsorption process). We identify critical gaps for further research to enable their real-life applications.
2024, 35(2): 108557
doi: 10.1016/j.cclet.2023.108557
Abstract:
After a century of standstill, bacteria-based tumor therapy has resurged recently benefiting from the revolution of tumor immunotherapy, which provides unique solutions to tackle the obstacles of traditional tumor treatments. Obligate and facultative anaerobes with active tropism can selectively colonize at tumor sites and suppress tumor growth via different mechanisms, serving as attractive tools for tumor treatment either as a monotherapy or combining with other therapies for synergistic anti-tumor effects. In this critical review, we introduce the recent advances of bacteria-based tumor therapy from the following aspects. First, the general properties of bacteria are reviewed emphasizing on their structural components related to tumor immunotherapy, and the main bacteria that have been used in tumor therapy are listed. Then, the benefits of bacteria for tumor therapy are illustrated, such as tumor targetability, deep penetration, and facile genetic engineering for attenuation, enhanced efficacy, as well as bioimaging. Next, anti-tumor mechanisms of bacteria are summarized, which refer to intrinsic tumoricidal activities, immune activation, bacteria metabolism, and their capability to regulate gut microbiota homeostasis. Moreover, bacteria could act as carriers to deliver various types of therapeutics to achieve combination therapy with improved efficacy. In addition, several challenges for anti-tumor applications of bacteria are discussed regarding the delivery, efficacy and safety issues, and potential solutions are also provided. Finally, the possible improvements and perspectives are discussed in the end, which provide a guideline for the design of advanced bacteria-based tumor therapeutics in the future.
After a century of standstill, bacteria-based tumor therapy has resurged recently benefiting from the revolution of tumor immunotherapy, which provides unique solutions to tackle the obstacles of traditional tumor treatments. Obligate and facultative anaerobes with active tropism can selectively colonize at tumor sites and suppress tumor growth via different mechanisms, serving as attractive tools for tumor treatment either as a monotherapy or combining with other therapies for synergistic anti-tumor effects. In this critical review, we introduce the recent advances of bacteria-based tumor therapy from the following aspects. First, the general properties of bacteria are reviewed emphasizing on their structural components related to tumor immunotherapy, and the main bacteria that have been used in tumor therapy are listed. Then, the benefits of bacteria for tumor therapy are illustrated, such as tumor targetability, deep penetration, and facile genetic engineering for attenuation, enhanced efficacy, as well as bioimaging. Next, anti-tumor mechanisms of bacteria are summarized, which refer to intrinsic tumoricidal activities, immune activation, bacteria metabolism, and their capability to regulate gut microbiota homeostasis. Moreover, bacteria could act as carriers to deliver various types of therapeutics to achieve combination therapy with improved efficacy. In addition, several challenges for anti-tumor applications of bacteria are discussed regarding the delivery, efficacy and safety issues, and potential solutions are also provided. Finally, the possible improvements and perspectives are discussed in the end, which provide a guideline for the design of advanced bacteria-based tumor therapeutics in the future.
2024, 35(2): 108567
doi: 10.1016/j.cclet.2023.108567
Abstract:
Artificial photocatalytic energy conversion is considered as the most potential strategy for solving the increasingly serious energy crisis and environmental pollution problems by directly capturing solar energy. Therefore, high efficiency photocatalyst has drawn significant research attention in recent years. Due to the excellent electronic, optical, structural, and physicochemical performances, silver-based g-C3N4 have become promising photocatalysts. This review emphasizes the recent progresses and challenges on g-C3N4 decorated with silver for photocatalytic energy conversion. The extensive use of g-C3N4 decorated with silver in diverse photocatalytic reactions, including hydrogen evolution, pollutant degradation and carbon dioxide reduction, is also fully introduced. In addition, we propose the perspectives of g-C3N4 decorated with silver on photocatalytic applications. We hope that this review will shed some light on the photocatalytic energy conversion of g-C3N4 decorated with silver.
Artificial photocatalytic energy conversion is considered as the most potential strategy for solving the increasingly serious energy crisis and environmental pollution problems by directly capturing solar energy. Therefore, high efficiency photocatalyst has drawn significant research attention in recent years. Due to the excellent electronic, optical, structural, and physicochemical performances, silver-based g-C3N4 have become promising photocatalysts. This review emphasizes the recent progresses and challenges on g-C3N4 decorated with silver for photocatalytic energy conversion. The extensive use of g-C3N4 decorated with silver in diverse photocatalytic reactions, including hydrogen evolution, pollutant degradation and carbon dioxide reduction, is also fully introduced. In addition, we propose the perspectives of g-C3N4 decorated with silver on photocatalytic applications. We hope that this review will shed some light on the photocatalytic energy conversion of g-C3N4 decorated with silver.
2024, 35(2): 108571
doi: 10.1016/j.cclet.2023.108571
Abstract:
One of the urgent and challenging topics in diversified sustainable energy conversion is the development of high-performance, low-cost, and well durable catalysts. Cu single-atom catalysts (SACs) have become promising catalysts for diversified sustainable energy conversion due to their capability to maximize the utilization efficiency, acquire modulated electronic structure and optimized binding strength with intermediates. In this review, we have provided an interview of the recent progress achieved in the field of electrocatalysis, photocatalysis, and heterogeneous reaction based on Cu SACs. Started by this review, we have summarized some advanced synthetic strategies for the construction of Cu SACs. Subsequently, the performance-improving strategies are discussed in terms of the coordination environments of the reaction center, reaction mechanism and selectivity, based on free energy diagram and electron structure analysis. Finally, the remaining issues, challenges, and opportunities of Cu SACs are also provided, affording a perspective for future studies. This review not only offers us a deep understanding on the catalytic mechanism of Cu SACs for energy conversion, but also encourages more endeavors in prompting their practical application.
One of the urgent and challenging topics in diversified sustainable energy conversion is the development of high-performance, low-cost, and well durable catalysts. Cu single-atom catalysts (SACs) have become promising catalysts for diversified sustainable energy conversion due to their capability to maximize the utilization efficiency, acquire modulated electronic structure and optimized binding strength with intermediates. In this review, we have provided an interview of the recent progress achieved in the field of electrocatalysis, photocatalysis, and heterogeneous reaction based on Cu SACs. Started by this review, we have summarized some advanced synthetic strategies for the construction of Cu SACs. Subsequently, the performance-improving strategies are discussed in terms of the coordination environments of the reaction center, reaction mechanism and selectivity, based on free energy diagram and electron structure analysis. Finally, the remaining issues, challenges, and opportunities of Cu SACs are also provided, affording a perspective for future studies. This review not only offers us a deep understanding on the catalytic mechanism of Cu SACs for energy conversion, but also encourages more endeavors in prompting their practical application.
2024, 35(2): 108601
doi: 10.1016/j.cclet.2023.108601
Abstract:
DNA nanomaterials hold great promise in biomedical fields due to its excellent sequence programmability, molecular recognition ability and biocompatibility. Hybridization chain reaction (HCR) is a simple and efficient isothermal enzyme-free amplification strategy of DNA, generating nicked double helices with repeated units. Through the design of HCR hairpins, multiple nanomaterials with desired functions are assembled by DNA, exhibiting great potential in biomedical applications. Herein, the recent progress of HCR-based DNA nanomaterials for biosensing, bioimaging and therapeutics are summarized. Representative works are exemplified to demonstrate how HCR-based DNA nanomaterials are designed and constructed. The challenges and prospects of the development of HCR-based DNA nanomaterials are discussed. We envision that rationally designing HCR-based DNA nanomaterials will facilitate the development of biomedical applications.
DNA nanomaterials hold great promise in biomedical fields due to its excellent sequence programmability, molecular recognition ability and biocompatibility. Hybridization chain reaction (HCR) is a simple and efficient isothermal enzyme-free amplification strategy of DNA, generating nicked double helices with repeated units. Through the design of HCR hairpins, multiple nanomaterials with desired functions are assembled by DNA, exhibiting great potential in biomedical applications. Herein, the recent progress of HCR-based DNA nanomaterials for biosensing, bioimaging and therapeutics are summarized. Representative works are exemplified to demonstrate how HCR-based DNA nanomaterials are designed and constructed. The challenges and prospects of the development of HCR-based DNA nanomaterials are discussed. We envision that rationally designing HCR-based DNA nanomaterials will facilitate the development of biomedical applications.
2024, 35(2): 108645
doi: 10.1016/j.cclet.2023.108645
Abstract:
Due to its simplicity, high efficiency, and chemo-selectivity, bioorthogonal chemistry has shown a great application potential in pre-targeting. Currently, four bioorthogonal pairs as targeting tools, including (strept)avidin/biotin, antibody/antigen, oligonucleotide hybridization and IEDDA tools, have been developed and applied in targeted delivery. Nevertheless, all of these tools still suffer from some limitations, such as difficult modification, biochemical fragility and larger molecular weight for biological association tools, as well as chemical instability for IEDDA tools. Synthetic host-guest pairs with relatively small molecular sizes not only possess strong chemical stability, but also have the features of fast conjugation rate, tunable binding affinity, easy modification, and high chemo-selectivity. Consequently, they can be used as a novel non-covalent bioorthogonal tool for pre-targeting. In order to further promote the development of host-guest pairs as novel bioorthogonal tools for pre-targeted delivery, we firstly calculate their conversion rate to make researcher aware of their unique advantages; next, we summarize the recent research progress in this area. The future perspectives and limitations of these unique tools will be discussed. This review will provide a systemic overview of the development of synthetic host-guest pairs as novel bioorthogonal tools for pre-targeting, and may serve as a "go for" resort for researchers who are interested in searching for new synthetic tools to improve pre-targeting.
Due to its simplicity, high efficiency, and chemo-selectivity, bioorthogonal chemistry has shown a great application potential in pre-targeting. Currently, four bioorthogonal pairs as targeting tools, including (strept)avidin/biotin, antibody/antigen, oligonucleotide hybridization and IEDDA tools, have been developed and applied in targeted delivery. Nevertheless, all of these tools still suffer from some limitations, such as difficult modification, biochemical fragility and larger molecular weight for biological association tools, as well as chemical instability for IEDDA tools. Synthetic host-guest pairs with relatively small molecular sizes not only possess strong chemical stability, but also have the features of fast conjugation rate, tunable binding affinity, easy modification, and high chemo-selectivity. Consequently, they can be used as a novel non-covalent bioorthogonal tool for pre-targeting. In order to further promote the development of host-guest pairs as novel bioorthogonal tools for pre-targeted delivery, we firstly calculate their conversion rate to make researcher aware of their unique advantages; next, we summarize the recent research progress in this area. The future perspectives and limitations of these unique tools will be discussed. This review will provide a systemic overview of the development of synthetic host-guest pairs as novel bioorthogonal tools for pre-targeting, and may serve as a "go for" resort for researchers who are interested in searching for new synthetic tools to improve pre-targeting.
2024, 35(2): 108647
doi: 10.1016/j.cclet.2023.108647
Abstract:
Exosomes are membrane-bound nanoscale extracellular vesicles, which produced by almost all organisms. Due to the excellent biocompatibility, long circulation time as well as low immunogenicity, exosomes as naturally-derived drug delivery carriers have experienced explosive growth over the past decades. However, issues such as insufficient loading efficiency, heterogeneous delivery efficiency, uncontrollable targeting ability, and low production limit their wide application. Recently, the emerging exosome–liposome fusion strategy has become a potential approach to solve such issues. Thus, this review mainly focuses on the currently developed exosome–liposome fusion strategy and their application in drug delivery as well as disease treatment. This review aims to shed light on the advantages of fusion strategy in drug delivery and provides a better understanding for more rational design. The current challenge and future perspective regarding their clinical translation and application will also be discussed.
Exosomes are membrane-bound nanoscale extracellular vesicles, which produced by almost all organisms. Due to the excellent biocompatibility, long circulation time as well as low immunogenicity, exosomes as naturally-derived drug delivery carriers have experienced explosive growth over the past decades. However, issues such as insufficient loading efficiency, heterogeneous delivery efficiency, uncontrollable targeting ability, and low production limit their wide application. Recently, the emerging exosome–liposome fusion strategy has become a potential approach to solve such issues. Thus, this review mainly focuses on the currently developed exosome–liposome fusion strategy and their application in drug delivery as well as disease treatment. This review aims to shed light on the advantages of fusion strategy in drug delivery and provides a better understanding for more rational design. The current challenge and future perspective regarding their clinical translation and application will also be discussed.
2024, 35(2): 108710
doi: 10.1016/j.cclet.2023.108710
Abstract:
Nanoemulsions are widely used as advanced pharmaceutical delivery systems in biomedical field, due to their high encapsulation efficiency and good therapy efficacy. Nanoemulsification techniques that produce nanoemulsions with controllable sizes and compositions are promising for creating advanced nanoemulsion systems for pharmaceutical delivery. This review summarizes recent advances on low-energy emulsification techniques for producing nanoemulsions, and the use of these nanoemulsions as advanced pharmaceutical delivery systems and as templates to create drug-loaded functional particles for biomedical application. First, nanoemulsification techniques that utilize elaborate interfacial physics/chemistry and micro-/nano-fluidics, featured with relatively-low energy input, to produce nanoemulsions with controllable sizes and compositions, are introduced. Uses of these nanoemulsions to create nanoemulsion-incorporated milli-particles, drug-loaded nanoparticles and nanoparticle-incorporated microparticles with sizes ranging from several millimeters to sub-10 nm are emphasized. Flexible and efficient use of the nanoemulsions, functional nanoparticles and milli-/micro-particles integrated with nanoemulsions or nanoparticles for advanced pharmaceutical delivery in biomedical field are highlighted, with focus on how the interplay between their sizes and compositions achieve desired pharmaceutical-delivery performances. Finally, perspectives on further advances on the controllable production of nanoemulsions are provided.
Nanoemulsions are widely used as advanced pharmaceutical delivery systems in biomedical field, due to their high encapsulation efficiency and good therapy efficacy. Nanoemulsification techniques that produce nanoemulsions with controllable sizes and compositions are promising for creating advanced nanoemulsion systems for pharmaceutical delivery. This review summarizes recent advances on low-energy emulsification techniques for producing nanoemulsions, and the use of these nanoemulsions as advanced pharmaceutical delivery systems and as templates to create drug-loaded functional particles for biomedical application. First, nanoemulsification techniques that utilize elaborate interfacial physics/chemistry and micro-/nano-fluidics, featured with relatively-low energy input, to produce nanoemulsions with controllable sizes and compositions, are introduced. Uses of these nanoemulsions to create nanoemulsion-incorporated milli-particles, drug-loaded nanoparticles and nanoparticle-incorporated microparticles with sizes ranging from several millimeters to sub-10 nm are emphasized. Flexible and efficient use of the nanoemulsions, functional nanoparticles and milli-/micro-particles integrated with nanoemulsions or nanoparticles for advanced pharmaceutical delivery in biomedical field are highlighted, with focus on how the interplay between their sizes and compositions achieve desired pharmaceutical-delivery performances. Finally, perspectives on further advances on the controllable production of nanoemulsions are provided.
2024, 35(2): 108802
doi: 10.1016/j.cclet.2023.108802
Abstract:
In recent years, with the emergence of non-fullerene fused-ring acceptors, power conversion efficiencies (PCEs) of organic solar cells (OSCs) have exceeded 19%. However, compared to inorganic or perovskite photovoltaic cells, a higher voltage loss has become one of the key factors limiting further improvement in the PCEs of OSCs. The ternary/quaternary strategy has been identified as a feasible and effective way to obtain high-efficiency OSCs. In this review, a brief outline is given of the key roles that guest materials played in reducing voltage losses in solar cell devices and a brief look at the future material design and the design of ternary/quaternary systems.
In recent years, with the emergence of non-fullerene fused-ring acceptors, power conversion efficiencies (PCEs) of organic solar cells (OSCs) have exceeded 19%. However, compared to inorganic or perovskite photovoltaic cells, a higher voltage loss has become one of the key factors limiting further improvement in the PCEs of OSCs. The ternary/quaternary strategy has been identified as a feasible and effective way to obtain high-efficiency OSCs. In this review, a brief outline is given of the key roles that guest materials played in reducing voltage losses in solar cell devices and a brief look at the future material design and the design of ternary/quaternary systems.
2024, 35(2): 108977
doi: 10.1016/j.cclet.2023.108977
Abstract:
Enaminones, which possesses both the nucleophilic enamine as well as electrophilic enone structures, are well known versatile building blocks in organic synthesis. Meanwhile, visible light-mediated reactions have emerged as useful synthetic strategy with enhanced sustainability. Around the last decade, various photochemical transformations of enaminones have been developed to construct cyclic or acyclic compounds. In this review, we describe the recent advances in visible light-mediated chemical transformations of enaminones. Detailed discussion on the reaction mechanism of the related reactions is given to provide guide to the reader. Finally, a summary on the existing challenges and the future outlook towards the development of practical photocatalytic reactions of enaminones is also presented.
Enaminones, which possesses both the nucleophilic enamine as well as electrophilic enone structures, are well known versatile building blocks in organic synthesis. Meanwhile, visible light-mediated reactions have emerged as useful synthetic strategy with enhanced sustainability. Around the last decade, various photochemical transformations of enaminones have been developed to construct cyclic or acyclic compounds. In this review, we describe the recent advances in visible light-mediated chemical transformations of enaminones. Detailed discussion on the reaction mechanism of the related reactions is given to provide guide to the reader. Finally, a summary on the existing challenges and the future outlook towards the development of practical photocatalytic reactions of enaminones is also presented.
2024, 35(2): 109008
doi: 10.1016/j.cclet.2023.109008
Abstract:
Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities. However, it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure. In this review, research progress in the development of porphyrin-based saccharide sensors is described with representative examples. We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability, long emission wavelength, and multiple structural modification strategies. Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules. In the first section, recognition unit, design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed. While in the second section, development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized. Looking through the design strategy and sensing performance of reported achievements, it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.
Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities. However, it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure. In this review, research progress in the development of porphyrin-based saccharide sensors is described with representative examples. We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability, long emission wavelength, and multiple structural modification strategies. Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules. In the first section, recognition unit, design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed. While in the second section, development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized. Looking through the design strategy and sensing performance of reported achievements, it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.
2024, 35(2): 109074
doi: 10.1016/j.cclet.2023.109074
Abstract:
Ulcerative colitis (UC) is a common progressive inflammatory disease whose incidence has increased rapidly in recent years, and can develop into colorectal cancer in severe cases. There are currently no adequate or effective treatments for UC due to the fact that some patients have found suboptimal results after repeated administration, while others have experienced adverse effects. With the rapid development of nanotechnology, developing innovative colon-targeting platforms is essential to improving efficacy, reducing side effects, and improving patient compliance. In this review, we summarize the pathophysiological characteristics of UC and the most recent status of numerous nanodrug delivery systems based on different targeting mechanisms in treating UC. Oral, intravenous, and rectal drug delivery nanoparticles targeting the colon are discussed, which can provide ideas for the design of colon-targeting nanoparticles for the treatment of colon diseases, especially for the treatment of UC. Last but not least, we provide a glimpse into the future of colon-targeted delivery systems, as well as future advancements in the field.
Ulcerative colitis (UC) is a common progressive inflammatory disease whose incidence has increased rapidly in recent years, and can develop into colorectal cancer in severe cases. There are currently no adequate or effective treatments for UC due to the fact that some patients have found suboptimal results after repeated administration, while others have experienced adverse effects. With the rapid development of nanotechnology, developing innovative colon-targeting platforms is essential to improving efficacy, reducing side effects, and improving patient compliance. In this review, we summarize the pathophysiological characteristics of UC and the most recent status of numerous nanodrug delivery systems based on different targeting mechanisms in treating UC. Oral, intravenous, and rectal drug delivery nanoparticles targeting the colon are discussed, which can provide ideas for the design of colon-targeting nanoparticles for the treatment of colon diseases, especially for the treatment of UC. Last but not least, we provide a glimpse into the future of colon-targeted delivery systems, as well as future advancements in the field.
2024, 35(2): 109092
doi: 10.1016/j.cclet.2023.109092
Abstract:
Due to their excellent fluorescence properties and biological function, cyanine dyes have been widely applied in biological imaging. Heptamethine cyanine (Cy7) dyes, as a type of classic near-infrared (NIR) fluorescent dyes, are considered as one of the effective fluorescent tools in the living organisms due to their good biocompatibility and very low background interference. Bioorthogonal reactions performed in living cells and tissues have developed by leaps and bounds in recent years. The NIR fluorescent labeling technique involving cyanine has attracted widespread attention. This review summarizes their recent application in the field of bioorthogonal imaging, mainly concluding Cy7-type dyes, labeling strategy, bioimaging application, etc. We expect this work can provide some helps for the studies of NIR bioorthogonal reaction in vivo.
Due to their excellent fluorescence properties and biological function, cyanine dyes have been widely applied in biological imaging. Heptamethine cyanine (Cy7) dyes, as a type of classic near-infrared (NIR) fluorescent dyes, are considered as one of the effective fluorescent tools in the living organisms due to their good biocompatibility and very low background interference. Bioorthogonal reactions performed in living cells and tissues have developed by leaps and bounds in recent years. The NIR fluorescent labeling technique involving cyanine has attracted widespread attention. This review summarizes their recent application in the field of bioorthogonal imaging, mainly concluding Cy7-type dyes, labeling strategy, bioimaging application, etc. We expect this work can provide some helps for the studies of NIR bioorthogonal reaction in vivo.
2024, 35(2): 109096
doi: 10.1016/j.cclet.2023.109096
Abstract:
Enzyme prodrug therapies (EPTs) have been intensively explored as attractive approaches to selective activation of systemically administered benign prodrugs by the exogenous enzymes or enzymes expressed at the desired target site, thus achieving localized, site-specific therapeutic effect. Many effective strategies (e.g., antibody-, viral-, gene-, as well as polymer-directed EPT) have been developed for enzyme localization to locally activate systemically administered benign prodrugs. Nevertheless, intrinsic limitations (e.g., complex intracellular environment and catalyst instability) make the practical application of EPT strategies a task that presents itself as highly challenging. As a promising alternative to natural enzyme, nanozyme has attracted substantial attention since its discovery in 2007, mainly due to the advantages of robust catalytic activity, high stability, low cost, and facile synthesis. Recently, nanozyme-activated prodrug strategies bring a new opportunity for targeted therapy, referred to as nanozyme-activating prodrug therapies. This review focuses on recently reported nanozyme-activated prodrug strategies, aiming to provide some new insights into the potential applications in site-specific drug synthesis.
Enzyme prodrug therapies (EPTs) have been intensively explored as attractive approaches to selective activation of systemically administered benign prodrugs by the exogenous enzymes or enzymes expressed at the desired target site, thus achieving localized, site-specific therapeutic effect. Many effective strategies (e.g., antibody-, viral-, gene-, as well as polymer-directed EPT) have been developed for enzyme localization to locally activate systemically administered benign prodrugs. Nevertheless, intrinsic limitations (e.g., complex intracellular environment and catalyst instability) make the practical application of EPT strategies a task that presents itself as highly challenging. As a promising alternative to natural enzyme, nanozyme has attracted substantial attention since its discovery in 2007, mainly due to the advantages of robust catalytic activity, high stability, low cost, and facile synthesis. Recently, nanozyme-activated prodrug strategies bring a new opportunity for targeted therapy, referred to as nanozyme-activating prodrug therapies. This review focuses on recently reported nanozyme-activated prodrug strategies, aiming to provide some new insights into the potential applications in site-specific drug synthesis.
2024, 35(2): 109149
doi: 10.1016/j.cclet.2023.109149
Abstract:
Ischemic stroke (IS) represents a significant threat to brain health due to its elevated mortality and disability rates. The efficacy of small-molecule neuroprotective agents has been impeded by challenges associated with traversing the blood-brain barrier (BBB) and limited bioavailability. Conversely, advanced nano drug delivery systems hold promise for overcoming these obstacles by facilitating efficient transportation across the BBB and maintaining optimal drug concentrations. This review aims to explore advanced neuroprotective nano drug delivery systems as a means of effectively administering neuroprotective agents to the brain using pharmaceutical approaches in the treatment of IS. By examining these systems, researchers and clinicians can gain valuable insights and innovative concepts, illuminating the potential of advanced neuroprotective nano drug delivery systems. Leveraging these advancements can drive the progress of pioneering and efficacious therapeutic interventions for IS.
Ischemic stroke (IS) represents a significant threat to brain health due to its elevated mortality and disability rates. The efficacy of small-molecule neuroprotective agents has been impeded by challenges associated with traversing the blood-brain barrier (BBB) and limited bioavailability. Conversely, advanced nano drug delivery systems hold promise for overcoming these obstacles by facilitating efficient transportation across the BBB and maintaining optimal drug concentrations. This review aims to explore advanced neuroprotective nano drug delivery systems as a means of effectively administering neuroprotective agents to the brain using pharmaceutical approaches in the treatment of IS. By examining these systems, researchers and clinicians can gain valuable insights and innovative concepts, illuminating the potential of advanced neuroprotective nano drug delivery systems. Leveraging these advancements can drive the progress of pioneering and efficacious therapeutic interventions for IS.
2024, 35(2): 109152
doi: 10.1016/j.cclet.2023.109152
Abstract:
Diversity-oriented synthesis is a powerful and interesting synthetic tool for the rapid construction of structurally complex and privileged scaffolds from readily accessible starting materials. To date, diversity-oriented synthesis mostly relies on the employment of versatile reagents. Versatile reagents can be regulated as controllable and flexible building blocks for multipurpose utilizations. Over the past decade, a variety of multifunctional reagents have been developed. However, most versatile reagents usually need multi-step synthesis, thus restricting their wide application to a large extent. In terms of the practicalities and universalities, we prefer to pay more attention to the utilization of simple and practical versatile reagents with multiple reactivities, mainly including atropaldehyde acetals, aryl methyl ketones, vinylene carbonate, vinyl azides, aryldiazonium salts, rongalite, halodifluoromethyl compounds. Most importantly, these versatile reagents can also play different roles simultaneously in the same reaction, in which their different reactivities are converged into the final target products. Such strategy can not only offer more possibilities for the synthesis of several active pharmaceutical ingredients, but also minimize the occurrence of some side reactions by lessening the varieties of materials. Also, a perspective is given at the end of this review.
Diversity-oriented synthesis is a powerful and interesting synthetic tool for the rapid construction of structurally complex and privileged scaffolds from readily accessible starting materials. To date, diversity-oriented synthesis mostly relies on the employment of versatile reagents. Versatile reagents can be regulated as controllable and flexible building blocks for multipurpose utilizations. Over the past decade, a variety of multifunctional reagents have been developed. However, most versatile reagents usually need multi-step synthesis, thus restricting their wide application to a large extent. In terms of the practicalities and universalities, we prefer to pay more attention to the utilization of simple and practical versatile reagents with multiple reactivities, mainly including atropaldehyde acetals, aryl methyl ketones, vinylene carbonate, vinyl azides, aryldiazonium salts, rongalite, halodifluoromethyl compounds. Most importantly, these versatile reagents can also play different roles simultaneously in the same reaction, in which their different reactivities are converged into the final target products. Such strategy can not only offer more possibilities for the synthesis of several active pharmaceutical ingredients, but also minimize the occurrence of some side reactions by lessening the varieties of materials. Also, a perspective is given at the end of this review.
2024, 35(2): 109159
doi: 10.1016/j.cclet.2023.109159
Abstract:
Colorectal cancer causes the third most common type of malignant tumors with high morbidity and mortality. Chemotherapy is currently one of the most effective and common treatments for colorectal cancer. However, the poor water solubility of some chemotherapeutics, untargeted drug delivery, and the undesirable systemic side effects of conventional treatment remain the major issues for colorectal cancer chemotherapy. Fortunately, drug delivery systems (DDS) based on biomaterials have been widely investigated and found to be capable of resolving those issues with good performance. Therefore, the main goal of this review is to summarize and discuss the progress and potential advantages of different DDS for colorectal cancer chemotherapy. We not only reviewed the nanocarriers used to improve the solubility of chemotherapeutics, including liposomes, micelles, and nanoparticles, but also discussed targeted DDS based on specific ligand-receptor recognition and tumor microenvironmental stimulus responses. Furthermore, locally administered systems based on hydrogels and microspheres, which have been shown to increase drug accumulation at the tumor site while decreasing systemic toxicity, were also emphasized. DDS provides a good option for improving the efficacy of chemotherapy in the treatment of colorectal cancer.
Colorectal cancer causes the third most common type of malignant tumors with high morbidity and mortality. Chemotherapy is currently one of the most effective and common treatments for colorectal cancer. However, the poor water solubility of some chemotherapeutics, untargeted drug delivery, and the undesirable systemic side effects of conventional treatment remain the major issues for colorectal cancer chemotherapy. Fortunately, drug delivery systems (DDS) based on biomaterials have been widely investigated and found to be capable of resolving those issues with good performance. Therefore, the main goal of this review is to summarize and discuss the progress and potential advantages of different DDS for colorectal cancer chemotherapy. We not only reviewed the nanocarriers used to improve the solubility of chemotherapeutics, including liposomes, micelles, and nanoparticles, but also discussed targeted DDS based on specific ligand-receptor recognition and tumor microenvironmental stimulus responses. Furthermore, locally administered systems based on hydrogels and microspheres, which have been shown to increase drug accumulation at the tumor site while decreasing systemic toxicity, were also emphasized. DDS provides a good option for improving the efficacy of chemotherapy in the treatment of colorectal cancer.
Theoretical and experimental design in the study of sulfide-based solid-state battery and interfaces
2024, 35(2): 109173
doi: 10.1016/j.cclet.2023.109173
Abstract:
In recent years, due to the increasing demand for portable electronic devices, rechargeable solid-state battery technology has developed rapidly. Lithium-ion batteries are the systems of choice, offering high energy density, flexible and lightweight design, and longer lifespan than comparable battery technologies. Therefore, a better understanding of the relationship between electrochemical mechanism and structural properties from theory and experiment will enable us to accelerate the development of high-performance and security batteries. This review discusses the interplay between theoretical calculation and experiment in the study of lithium ion battery materials. We introduce the application of theoretical calculation method in solid-state batteries through the combination of theory and experiment. We present the concept and assembly technology of solid-state batteries are reviewed. The basic parameters of solid-state electrolytes, especially sulfide-based solid-state electrolytes and their interface mechanisms with high-voltage cathode materials, are analyzed by theoretical methods. We present an overview on the scientific challenges, fundamental mechanisms, and design strategies for solid-state batteries, especially focusing on the issues of stability on solid-state electrolytes and the associated interfaces with both cathode and electrolyte. Owing to the theoretical models, we can not only reveal the unprecedented mechanism from the atomic scale, but also analyze the interface problems in the battery thoroughly, thus effectively designing more promising electrolyte and interface coating materials. It blazed a new trial for engineering an interphase with improved interfacial compatibility for a long-term cyclability.
In recent years, due to the increasing demand for portable electronic devices, rechargeable solid-state battery technology has developed rapidly. Lithium-ion batteries are the systems of choice, offering high energy density, flexible and lightweight design, and longer lifespan than comparable battery technologies. Therefore, a better understanding of the relationship between electrochemical mechanism and structural properties from theory and experiment will enable us to accelerate the development of high-performance and security batteries. This review discusses the interplay between theoretical calculation and experiment in the study of lithium ion battery materials. We introduce the application of theoretical calculation method in solid-state batteries through the combination of theory and experiment. We present the concept and assembly technology of solid-state batteries are reviewed. The basic parameters of solid-state electrolytes, especially sulfide-based solid-state electrolytes and their interface mechanisms with high-voltage cathode materials, are analyzed by theoretical methods. We present an overview on the scientific challenges, fundamental mechanisms, and design strategies for solid-state batteries, especially focusing on the issues of stability on solid-state electrolytes and the associated interfaces with both cathode and electrolyte. Owing to the theoretical models, we can not only reveal the unprecedented mechanism from the atomic scale, but also analyze the interface problems in the battery thoroughly, thus effectively designing more promising electrolyte and interface coating materials. It blazed a new trial for engineering an interphase with improved interfacial compatibility for a long-term cyclability.
2024, 35(2): 109197
doi: 10.1016/j.cclet.2023.109197
Abstract:
Bone damage caused by trauma and tumors is a serious problem for human health, therefore, three-dimensional (3D) scaffolding materials that stimulate and promote the regeneration of broken bone tissues have become the focus of current research in the field of bone damage repair. To this regard, a preferential combination of materials and preparation techniques is considered crucial for the preparation of advanced bone tissue engineering scaffolds to better facilitate the regeneration of broken bone. In this review, current research advances and challenges in bone tissue engineering scaffolds are discussed and analyzed in detail. First, we elucidated the structure and self-healing mechanism of bone tissue. Subsequently, the main applications of different materials, including inorganic and organic materials, in bone tissue engineering scaffolds are summarized. Moreover, we overview the latest research progress of the mainstream preparation strategies of bone tissue engineering scaffolds, and provide an in-depth analysis of the different advantages of each method. Finally, promising future directions and challenges of bone tissue engineering scaffolds are systematically discussed.
Bone damage caused by trauma and tumors is a serious problem for human health, therefore, three-dimensional (3D) scaffolding materials that stimulate and promote the regeneration of broken bone tissues have become the focus of current research in the field of bone damage repair. To this regard, a preferential combination of materials and preparation techniques is considered crucial for the preparation of advanced bone tissue engineering scaffolds to better facilitate the regeneration of broken bone. In this review, current research advances and challenges in bone tissue engineering scaffolds are discussed and analyzed in detail. First, we elucidated the structure and self-healing mechanism of bone tissue. Subsequently, the main applications of different materials, including inorganic and organic materials, in bone tissue engineering scaffolds are summarized. Moreover, we overview the latest research progress of the mainstream preparation strategies of bone tissue engineering scaffolds, and provide an in-depth analysis of the different advantages of each method. Finally, promising future directions and challenges of bone tissue engineering scaffolds are systematically discussed.
2024, 35(2): 108973
doi: 10.1016/j.cclet.2023.108973
Abstract:
2024, 35(2): 109299
doi: 10.1016/j.cclet.2023.109299
Abstract:
