Recent interest in photocatalytic water splitting has intensified the demand in the development of photocatalysts capable of harnessing the full solar-spectrum.This study introduces a novel WO_(x)/ZnIn_(2)S_(4)Zscheme...Recent interest in photocatalytic water splitting has intensified the demand in the development of photocatalysts capable of harnessing the full solar-spectrum.This study introduces a novel WO_(x)/ZnIn_(2)S_(4)Zscheme heterojunction,prepared by depositing ZnIn_(2)S_(4)(ZIS)nanosheets onto WO_(x)nanorods,enabling efficient photothermal-coupled photocatalytic H_(2)evolution.The success relies on the engineered oxygen vacancies within WO_(x)nanorods,which not only confer excellent photothermal properties lowering the reaction barrier but also create defect levels in WO_(x)facilitating Z-scheme electron transfer from these levels to the valence band of ZIS.Consequently,the optimized WO_(x)/ZIS heterojunction exhibits a remarkable H_(2)evolution rate of 33.91 mmol h^(-1)g^(-1)with an apparent quantum efficiency of 23.6%at 400 nm.This study provides a new strategy for developing efficient Z-scheme heterojunctions with broadspectrum solar hydrogen production capabilities.展开更多
Keeping steps ahead of the bacteria in the race for more efficacious antibacterial strategies is increasingly difficult with the advent of bacterial resistance genes.Herein,we engineered copper sulfide nanoclusters(Cu...Keeping steps ahead of the bacteria in the race for more efficacious antibacterial strategies is increasingly difficult with the advent of bacterial resistance genes.Herein,we engineered copper sulfide nanoclusters(CuS_(x) NCs)with variable sulfur defects for enhanced dual-treatment of bacterial infections by manipulating photothermal effects and Fenton-like activity.Next,by encasing CuS_(x) NCs with a complex mixture of amino acids and short peptides derived from Luria-Bertani bacterial culture media as a protein corona,we managed to coax E.Coli to take up these CuS_(x) NCs.As a whole,Amino-Pep-CuS_(x) NCs was perceived as a food source and actively consumed by bacteria,enhancing their effective uptake by at least 1.5-fold greater than full length BSA protein BSA-corona CuS_(x) NCs.Through strategically using defect-engineering,we successfully fine-tune photothermal effect and Fenton-like capacity of CuS_(x) NCs.Increased sulfur defects lead to reduced but sufficient heat generation under solar-light irradiation and increased production of toxic hydroxyl radicals.By fine-tuning sulfur defects during synthesis,we achieve CuS_(x) NCs with an optimal synergistic effect,significantly enhancing their bactericidal properties.These ultra-small and biodegradable CuS_(x) NCs can rapidly break down after treatment for clearance.Thus,Amino-Pep-CuS_(x) NCs demonstrate effective eradication of bacteria both in vitro and in vivo because of their relatively high uptake,optimal balanced photothermal and chemodynamic outcomes.Our study offers a straightforward and efficient method to enhance bacterial uptake of next generation of antibacterial agents.展开更多
In this work,a versatile strategy of manipulating defective metal organic frameworks(MOFs)with the assistance of the steric hindrance effect was proposed and applied in coatings.The steric hindrance effect was utilize...In this work,a versatile strategy of manipulating defective metal organic frameworks(MOFs)with the assistance of the steric hindrance effect was proposed and applied in coatings.The steric hindrance effect was utilized to construct the defective MOFs with phosphate,gluconate and phytate as examples.The defective MOFs were synthesized in an aqueous solution at room temperature,having a promising future for industrial application.Tailoring specific defects in MOFs can make molecular chains of polymer penetrate into the internal skeleton and form an interlocking structure.The interlocking effect can enhance the mechanical performance of the coating,and the corrosion inhibition performance of anions can synergistically improve the corrosion resistance of the coating.The waterborne acrylic resin(WAR)embedded with phytate-modified MOF has the highest tensile strength of 23.9 MPa,four times higher than pure WAR.Anti-corrosion test results indicated that the corrosion inhibition efficiencies of composite coatings maintained around 97%after 2 months of immersion in seawater.The structure-property relations of defect-engineered MOFs and the anti-corrosion mechanisms were elaborated in detail by both experiments and molecular dynamics simulation.This strategy has excellent environmental friendliness,reduces the cost of MOF materials,and has broad application prospects.展开更多
Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within cova...Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within covalent organic frameworks(COFs),enabling the resulting immobilized enzymes with excellent catalytic activity and stability to construct high performance immunosensors.In this design,by consciously introducing monoaldehyde ligands into the imine-linked COFs structure,we have precisely customized the structural defects to improve enzyme loading capacity and conformational stability.Defect-engineering interaction modulation between enzymes and COFs drives the enhancement of catalytic performance.Compared to the pristine COFs,the enzyme@defective COFs composites with optimally tuned catalytic performance exhibit a 4.49-fold enhancement in enzymatic activity.Furthermore,it is demonstrated that the stable skeletons of COFs provide exceptional protection for the enzymes against external perturbations.Thereafter,the optimized enzyme@defective COFs are employed to fabricate immunosensor.We have successfully established a detection method for prostate-specific antigen(PSA),achieving a low detection limit of 0.09 ng/mL.More importantly,the developed immunosensor has successfully distinguished the prostate cancer patients from healthy individuals.This work establishes a novel paradigm for enzyme immobilization,ultimately empowering the construction of a PSA immunosensor with high sensitivity,remarkable operational stability,and great clinical application potential.展开更多
The use of metal-organic frameworks(MOFs)as solid adsorption materials for carbon capture is promising,but achieving efficient and reversible adsorption with a balance of capacity and selectivity for carbon dioxide(CO...The use of metal-organic frameworks(MOFs)as solid adsorption materials for carbon capture is promising,but achieving efficient and reversible adsorption with a balance of capacity and selectivity for carbon dioxide(CO_(2))over N_(2) remains a challenge.To take full advantage of the strong channel traffic and robustness of MOFs with relatively small pores,it is highly necessary to employ a defect-engineering strategy to construct a broader channel structure that can facilitate the loading of functional motif-rich amino acids(AAs).This strategy can greatly enhance the CO_(2) adsorption performance of MOF.In this study,motif-rich amino acids are loaded into the defective and robust porous frameworks via combined defect-engineering and post-synthetic methods.The defective Zr/Hf-MOF-808s modified with AAs,especially for the 18 mol%4-nitroisophthalic acid,generated defective products allowing for the loading of L-serine(L-Ser).This modification resulted in a significant improvement in both the adsorption capacity(248%improvement at 298 K,100 kPa)and the selectivity of CO_(2)/N_(2) using the ideal adsorbed solution theory(IAST),with the selectivity increasing to 120.55 and 38.27 at 15 and 100 kPa,respectively,while maintaining good cycling performance.Density functional theory(DFT)simulation,CO_(2) temperature-programmed desorption(CO_(2)-TPD),and in situ Fourier transform infrared spectroscopy(FTIR)were further employed to have a better understanding of the enhanced CO_(2) adsorption capacity.Interestingly,unlike the AAs loaded pristine MOF-808s that showed the best CO_(2) adsorption capacity with the loading of short and small glycine(Gly),the broadened channel size in our work enables the loading of functional motif-rich L-serine,which brings more active binding sites,improving CO_(2) adsorption.展开更多
基金supported by the National Key Research and Development Program of China(2022YFB3803600)the National Natural Science Foundation of China(52276212)+4 种基金the Natural Science Foundation of Jiangsu Province(BK20231211)the Suzhou Science and Technology Program(SYG202101)the Key Research and Development Program in Shaanxi Province of China(2023-YBGY-300)the Zhuhai Innovation and Entrepreneurship Team Project(2120004000225)the China Fundamental Research Funds for the Central Universities。
文摘Recent interest in photocatalytic water splitting has intensified the demand in the development of photocatalysts capable of harnessing the full solar-spectrum.This study introduces a novel WO_(x)/ZnIn_(2)S_(4)Zscheme heterojunction,prepared by depositing ZnIn_(2)S_(4)(ZIS)nanosheets onto WO_(x)nanorods,enabling efficient photothermal-coupled photocatalytic H_(2)evolution.The success relies on the engineered oxygen vacancies within WO_(x)nanorods,which not only confer excellent photothermal properties lowering the reaction barrier but also create defect levels in WO_(x)facilitating Z-scheme electron transfer from these levels to the valence band of ZIS.Consequently,the optimized WO_(x)/ZIS heterojunction exhibits a remarkable H_(2)evolution rate of 33.91 mmol h^(-1)g^(-1)with an apparent quantum efficiency of 23.6%at 400 nm.This study provides a new strategy for developing efficient Z-scheme heterojunctions with broadspectrum solar hydrogen production capabilities.
基金the funding provided by the National University of Singapore Reimagine Grant(A-0009179-02-00,A-0009179-03-00)National Natural Science Foundation of China(82303841)+1 种基金Hunan Provincial Natural Science Foundation(2023JJ40800)the program of China Scholarships Council(No.202006090323).
文摘Keeping steps ahead of the bacteria in the race for more efficacious antibacterial strategies is increasingly difficult with the advent of bacterial resistance genes.Herein,we engineered copper sulfide nanoclusters(CuS_(x) NCs)with variable sulfur defects for enhanced dual-treatment of bacterial infections by manipulating photothermal effects and Fenton-like activity.Next,by encasing CuS_(x) NCs with a complex mixture of amino acids and short peptides derived from Luria-Bertani bacterial culture media as a protein corona,we managed to coax E.Coli to take up these CuS_(x) NCs.As a whole,Amino-Pep-CuS_(x) NCs was perceived as a food source and actively consumed by bacteria,enhancing their effective uptake by at least 1.5-fold greater than full length BSA protein BSA-corona CuS_(x) NCs.Through strategically using defect-engineering,we successfully fine-tune photothermal effect and Fenton-like capacity of CuS_(x) NCs.Increased sulfur defects lead to reduced but sufficient heat generation under solar-light irradiation and increased production of toxic hydroxyl radicals.By fine-tuning sulfur defects during synthesis,we achieve CuS_(x) NCs with an optimal synergistic effect,significantly enhancing their bactericidal properties.These ultra-small and biodegradable CuS_(x) NCs can rapidly break down after treatment for clearance.Thus,Amino-Pep-CuS_(x) NCs demonstrate effective eradication of bacteria both in vitro and in vivo because of their relatively high uptake,optimal balanced photothermal and chemodynamic outcomes.Our study offers a straightforward and efficient method to enhance bacterial uptake of next generation of antibacterial agents.
基金financially supported by the National Natural Science Foundation of China(No.U2141251)Taishan Scholars Project of ShandongZhejiang Province High-Level Talent Supporting Program(No.2022R52001).
文摘In this work,a versatile strategy of manipulating defective metal organic frameworks(MOFs)with the assistance of the steric hindrance effect was proposed and applied in coatings.The steric hindrance effect was utilized to construct the defective MOFs with phosphate,gluconate and phytate as examples.The defective MOFs were synthesized in an aqueous solution at room temperature,having a promising future for industrial application.Tailoring specific defects in MOFs can make molecular chains of polymer penetrate into the internal skeleton and form an interlocking structure.The interlocking effect can enhance the mechanical performance of the coating,and the corrosion inhibition performance of anions can synergistically improve the corrosion resistance of the coating.The waterborne acrylic resin(WAR)embedded with phytate-modified MOF has the highest tensile strength of 23.9 MPa,four times higher than pure WAR.Anti-corrosion test results indicated that the corrosion inhibition efficiencies of composite coatings maintained around 97%after 2 months of immersion in seawater.The structure-property relations of defect-engineered MOFs and the anti-corrosion mechanisms were elaborated in detail by both experiments and molecular dynamics simulation.This strategy has excellent environmental friendliness,reduces the cost of MOF materials,and has broad application prospects.
基金supported by the Nanjing Second Hospital talent lifting project(No.RCZD23001)the Jiangsu Province traditional Chinese medicine science and technology development general program(No.MS2023063)+1 种基金Medical Science and Technology Development Foundation,Nanjing Department of Health(No.ZKX20033)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX25_0240).
文摘Enhancing the activity of fragile enzymes is greatly useful for various purposes,including fabrication of enzyme-based immunosensors.Herein,we report a defect-engineering strategy for encapsulating enzymes within covalent organic frameworks(COFs),enabling the resulting immobilized enzymes with excellent catalytic activity and stability to construct high performance immunosensors.In this design,by consciously introducing monoaldehyde ligands into the imine-linked COFs structure,we have precisely customized the structural defects to improve enzyme loading capacity and conformational stability.Defect-engineering interaction modulation between enzymes and COFs drives the enhancement of catalytic performance.Compared to the pristine COFs,the enzyme@defective COFs composites with optimally tuned catalytic performance exhibit a 4.49-fold enhancement in enzymatic activity.Furthermore,it is demonstrated that the stable skeletons of COFs provide exceptional protection for the enzymes against external perturbations.Thereafter,the optimized enzyme@defective COFs are employed to fabricate immunosensor.We have successfully established a detection method for prostate-specific antigen(PSA),achieving a low detection limit of 0.09 ng/mL.More importantly,the developed immunosensor has successfully distinguished the prostate cancer patients from healthy individuals.This work establishes a novel paradigm for enzyme immobilization,ultimately empowering the construction of a PSA immunosensor with high sensitivity,remarkable operational stability,and great clinical application potential.
基金supported by the National Natural Science Foundation of China(Nos.52170119 and 22178357)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2021044).
文摘The use of metal-organic frameworks(MOFs)as solid adsorption materials for carbon capture is promising,but achieving efficient and reversible adsorption with a balance of capacity and selectivity for carbon dioxide(CO_(2))over N_(2) remains a challenge.To take full advantage of the strong channel traffic and robustness of MOFs with relatively small pores,it is highly necessary to employ a defect-engineering strategy to construct a broader channel structure that can facilitate the loading of functional motif-rich amino acids(AAs).This strategy can greatly enhance the CO_(2) adsorption performance of MOF.In this study,motif-rich amino acids are loaded into the defective and robust porous frameworks via combined defect-engineering and post-synthetic methods.The defective Zr/Hf-MOF-808s modified with AAs,especially for the 18 mol%4-nitroisophthalic acid,generated defective products allowing for the loading of L-serine(L-Ser).This modification resulted in a significant improvement in both the adsorption capacity(248%improvement at 298 K,100 kPa)and the selectivity of CO_(2)/N_(2) using the ideal adsorbed solution theory(IAST),with the selectivity increasing to 120.55 and 38.27 at 15 and 100 kPa,respectively,while maintaining good cycling performance.Density functional theory(DFT)simulation,CO_(2) temperature-programmed desorption(CO_(2)-TPD),and in situ Fourier transform infrared spectroscopy(FTIR)were further employed to have a better understanding of the enhanced CO_(2) adsorption capacity.Interestingly,unlike the AAs loaded pristine MOF-808s that showed the best CO_(2) adsorption capacity with the loading of short and small glycine(Gly),the broadened channel size in our work enables the loading of functional motif-rich L-serine,which brings more active binding sites,improving CO_(2) adsorption.
