The postsynthetic modification （PSM） of metal-organic frameworks （MOFs） has emerged as a powerful tool to chemically tailor the interior of MOFs. In this review, we summarize the research progress of PSM of MOFs t...The postsynthetic modification （PSM） of metal-organic frameworks （MOFs） has emerged as a powerful tool to chemically tailor the interior of MOFs. In this review, we summarize the research progress of PSM of MOFs through click chemistry, including azide-alkyne click reaction and thiol-ene reaction.展开更多
A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisopren...A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisoprene was synthesized by anionic polymerization using n-butyl lithium as initiator,and the pendant hydroxyl groups were introduced by the thiol-ene reaction of mercaptoethanol with the double bond of 1,2-addition units of PI backbone in the presence of radical initiator azobisisobutyronitrile. Isocyanate end group capped poly（ethylene glycol）（mPEG-NCO） was grafted onto the PI backbone through alcoholisocyanate reaction between the pendant hydroxyl groups and isocyanate group of mPEG-NCO.The structure of the graft copolymer were characterized and confirmed by means of size-exclusion chromatography,~1H NMR and FTIR spectroscopy.展开更多
Vascular endothelial growth factor(VEGF)plays a vital role in promoting attachment and proliferation of endothelial cells,and induces angiogenesis.In recent years,much research has been conducted on the functionalizat...Vascular endothelial growth factor(VEGF)plays a vital role in promoting attachment and proliferation of endothelial cells,and induces angiogenesis.In recent years,much research has been conducted on the functionalization of tissue engineering scaffolds with VEGF or a VEGF-mimetic peptide to promote angiogenesis.However,most chemical reactions are nonspecific and require organic solvents,which can compromise control over functionalization and alter peptide/protein activity.An attractive alternative is the fabrication of functionalizable electrospun fibers,which can overcome these hurdles.In this study,we used thiol-ene chemistry for the conjugation of a VEGF-mimetic peptide to the surface of poly(ε-caprolactone)(PCL)fibrous scaffolds with varying amounts of a functional PCL-diacrylate(PCL-DA)polymer.30%PCL-DA was selected due to homogeneous fiber morphology.A VEGF-mimetic peptide was then immobilized on PCL-DA fibrous scaffolds by a light-initiated thiol-ene reaction.7-Mercapto-4-methylcoumarin,RGD-FITC peptide and VEGF-TAMRA mimetic peptide were used to validate the thiol-ene reaction on the fibrous scaffolds.Tensile strength and elastic modulus of the 30%PCL-DA fibrous scaffolds were significantly increased after the reaction.Conjugation of the 30%PCL-DA fibrous scaffolds with the VEGF peptide increased the surface water wettability of the scaffolds.Patterned structures could be obtained after using a photomask on the fibrous film.Moreover,in vitro studies indicated that scaffolds functionalized with the VEGF-mimetic peptide were able to induce phosphorylation of the VEGF receptor and enhanced HUVECs survival,proliferation and adhesion.A chick chorioallantoic membrane(CAM)assay further indicated that the VEGF peptide functionalized scaffolds were able to promote angiogenesis in vivo.These results show that scaffold functionalization can be controlled via a simple polymer mixing approach,and that the functionalized VEGF peptide-scaffolds have potential for vascular tissue regeneration.展开更多
Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic am...Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.展开更多
Poly(vinyl alcohol)(PVA)has been widely used in industrial and consumer products.In this study,we aimed to address this challenge by synthesizing well-defined multiarm poly(vinyl acetate)(PVAc)through the use of nonhy...Poly(vinyl alcohol)(PVA)has been widely used in industrial and consumer products.In this study,we aimed to address this challenge by synthesizing well-defined multiarm poly(vinyl acetate)(PVAc)through the use of nonhydrolyzable vinyl ethertype multifunctional RAFT agents.The control over molecular weights was achieved by the RAFT process to afford polymers with dominant head-to-head linkages at the terminal.Especially,quantitative end-functionalization of the synthesized PVAc was performed using Michael thiol−ene or disulfide exchange reactions.Consequently,saponification of the PVAc enabled the synthesis of end-functionalized multiarm PVA in an efficient manner.This straightforward approach afforded well-defined functional PVAs,which enable further chemical modification,thus widening the utility of PVA in a range of applications,such as precisely controlled network synthesis and bioconjugation.展开更多
Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance,dimensional stability,and unique sensitivity to external stimuli.In this work,we synthesized thiol-functiona...Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance,dimensional stability,and unique sensitivity to external stimuli.In this work,we synthesized thiol-functionalized tetraphenylethylene(TPE)and constructed polymer gels through thiol-ene click reaction.The synthetic process of the polymer gels could be monitored by fluorescence emission of TPE moieties based on aggregation-induced emission mechanism.In addition,due to the dual redox-and acid responsiveness of the polymer gels,in the presence of dithiothreitol and trifluoroacetic acid,fluorescence quenching of the polymer gels can be observed.This stimuli-responsive characteristics endows the polymer gels with potential applications in fluorescent sensing and imaging,cancer diagnosis and selfhealing materials.展开更多
Octavinyl polyhedral oligomeric silsesquioxane (POSS) was polymerized on the surface of Fe3O4 nanoparticles (NPs) and then the NPs were functionalized with carboxylic acid groups using thiol-ene click reactions with t...Octavinyl polyhedral oligomeric silsesquioxane (POSS) was polymerized on the surface of Fe3O4 nanoparticles (NPs) and then the NPs were functionalized with carboxylic acid groups using thiol-ene click reactions with thioglycolic acid.The as-prepared Fe3O4@POSS-COOH magnetic hybrid NPs had mesoporous structures with an average particle diameter of 15 nm and a relatively high specific surface area of 447 m^2· g^-1.Experimental results showed that 4 mg of Fe3O4@POSS-COOH NPs efficiently adsorbed and removed methylene blue from water at 5 min.This is due to the presence of both carboxylic acid and pendant vinyl groups on the Fe3O4@POSS-COOH NPs.These NPs could be easily withdrawn from water within a few seconds under moderate magnetic field and showed high stability in acid and alkaline aqueous mediums.展开更多
基金We thank the funding supported by National Natural Science Foundation of China （No. 21572170）, the Research Fund for the Doctoral Program of Higher Education of China （No. 20130141110008）, and the Outstanding Youth Foundation of Hubei Province （No. 2015CFA045）.
文摘The postsynthetic modification （PSM） of metal-organic frameworks （MOFs） has emerged as a powerful tool to chemically tailor the interior of MOFs. In this review, we summarize the research progress of PSM of MOFs through click chemistry, including azide-alkyne click reaction and thiol-ene reaction.
基金supports of the Special Funds for Major Basic Research Projects (NoG2011CB606001)Zhejiang Provincial Top Key Discipline of New Materials and Process Engineering(No 20110926)
文摘A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene＂click＂reaction and alcohol-isocyanate reactions.Polyisoprene was synthesized by anionic polymerization using n-butyl lithium as initiator,and the pendant hydroxyl groups were introduced by the thiol-ene reaction of mercaptoethanol with the double bond of 1,2-addition units of PI backbone in the presence of radical initiator azobisisobutyronitrile. Isocyanate end group capped poly（ethylene glycol）（mPEG-NCO） was grafted onto the PI backbone through alcoholisocyanate reaction between the pendant hydroxyl groups and isocyanate group of mPEG-NCO.The structure of the graft copolymer were characterized and confirmed by means of size-exclusion chromatography,~1H NMR and FTIR spectroscopy.
基金supported in part by China Scholarship Council(No.201508610081 to T.Y.)by the National Natural Science Foundation of China(No.32071360,No.31900976 to H.C.)。
文摘Vascular endothelial growth factor(VEGF)plays a vital role in promoting attachment and proliferation of endothelial cells,and induces angiogenesis.In recent years,much research has been conducted on the functionalization of tissue engineering scaffolds with VEGF or a VEGF-mimetic peptide to promote angiogenesis.However,most chemical reactions are nonspecific and require organic solvents,which can compromise control over functionalization and alter peptide/protein activity.An attractive alternative is the fabrication of functionalizable electrospun fibers,which can overcome these hurdles.In this study,we used thiol-ene chemistry for the conjugation of a VEGF-mimetic peptide to the surface of poly(ε-caprolactone)(PCL)fibrous scaffolds with varying amounts of a functional PCL-diacrylate(PCL-DA)polymer.30%PCL-DA was selected due to homogeneous fiber morphology.A VEGF-mimetic peptide was then immobilized on PCL-DA fibrous scaffolds by a light-initiated thiol-ene reaction.7-Mercapto-4-methylcoumarin,RGD-FITC peptide and VEGF-TAMRA mimetic peptide were used to validate the thiol-ene reaction on the fibrous scaffolds.Tensile strength and elastic modulus of the 30%PCL-DA fibrous scaffolds were significantly increased after the reaction.Conjugation of the 30%PCL-DA fibrous scaffolds with the VEGF peptide increased the surface water wettability of the scaffolds.Patterned structures could be obtained after using a photomask on the fibrous film.Moreover,in vitro studies indicated that scaffolds functionalized with the VEGF-mimetic peptide were able to induce phosphorylation of the VEGF receptor and enhanced HUVECs survival,proliferation and adhesion.A chick chorioallantoic membrane(CAM)assay further indicated that the VEGF peptide functionalized scaffolds were able to promote angiogenesis in vivo.These results show that scaffold functionalization can be controlled via a simple polymer mixing approach,and that the functionalized VEGF peptide-scaffolds have potential for vascular tissue regeneration.
基金the National Natural Science Foundation of China(Grant no.51973073)the Fel owship of China Postdoctoral Science Foundation(2021M701303)the analytical and testing assistance from the Analysis and Testing Center of HUST for support of this work
文摘Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.
文摘Poly(vinyl alcohol)(PVA)has been widely used in industrial and consumer products.In this study,we aimed to address this challenge by synthesizing well-defined multiarm poly(vinyl acetate)(PVAc)through the use of nonhydrolyzable vinyl ethertype multifunctional RAFT agents.The control over molecular weights was achieved by the RAFT process to afford polymers with dominant head-to-head linkages at the terminal.Especially,quantitative end-functionalization of the synthesized PVAc was performed using Michael thiol−ene or disulfide exchange reactions.Consequently,saponification of the PVAc enabled the synthesis of end-functionalized multiarm PVA in an efficient manner.This straightforward approach afforded well-defined functional PVAs,which enable further chemical modification,thus widening the utility of PVA in a range of applications,such as precisely controlled network synthesis and bioconjugation.
基金supported by the National Natural Science Foundation of China (No.51773190 and No.51973206)。
文摘Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance,dimensional stability,and unique sensitivity to external stimuli.In this work,we synthesized thiol-functionalized tetraphenylethylene(TPE)and constructed polymer gels through thiol-ene click reaction.The synthetic process of the polymer gels could be monitored by fluorescence emission of TPE moieties based on aggregation-induced emission mechanism.In addition,due to the dual redox-and acid responsiveness of the polymer gels,in the presence of dithiothreitol and trifluoroacetic acid,fluorescence quenching of the polymer gels can be observed.This stimuli-responsive characteristics endows the polymer gels with potential applications in fluorescent sensing and imaging,cancer diagnosis and selfhealing materials.
文摘Octavinyl polyhedral oligomeric silsesquioxane (POSS) was polymerized on the surface of Fe3O4 nanoparticles (NPs) and then the NPs were functionalized with carboxylic acid groups using thiol-ene click reactions with thioglycolic acid.The as-prepared Fe3O4@POSS-COOH magnetic hybrid NPs had mesoporous structures with an average particle diameter of 15 nm and a relatively high specific surface area of 447 m^2· g^-1.Experimental results showed that 4 mg of Fe3O4@POSS-COOH NPs efficiently adsorbed and removed methylene blue from water at 5 min.This is due to the presence of both carboxylic acid and pendant vinyl groups on the Fe3O4@POSS-COOH NPs.These NPs could be easily withdrawn from water within a few seconds under moderate magnetic field and showed high stability in acid and alkaline aqueous mediums.
