Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation（λ= 365 nm） in good yields.The structures of these compounds synthesized herei...Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation（λ= 365 nm） in good yields.The structures of these compounds synthesized herein were fully confirmed by 1 H NMR.ES1-MS and elemental analysis.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
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
The microstructure of polymer electrolyte membranes plays a key role in ion conductivity and water transport.Herein,fluorinated poly(aryl ether)s with tetra-alkylsulfonate side chains(SFPAEs)have been successfully syn...The microstructure of polymer electrolyte membranes plays a key role in ion conductivity and water transport.Herein,fluorinated poly(aryl ether)s with tetra-alkylsulfonate side chains(SFPAEs)have been successfully synthesized from the copolymerization of a newly developed tetra-allyl-containing bisphenol(TABP)monomer,followed by the thiol-ene addition with sodium 3-mercapto-1-propanesulfonate to attach the ionic groups at the end of the flexible chains.Being the first of its kind,the densely distributed and lengthy alkylsulfonate group possesses the benefit of ease to self-assemble into hydrophilic domains during membrane preparation via solution casting.Indeed,the TEM characterizations revealed that distinct hydrophilic channels of 1-2 nm width had been formed,much larger than those of a home-made control sample where only di-alkylsulfonate side chains were attached.The SFPAE-4-45 with an IECw of 2.0 mmol g^-1 exhibited an enhanced proton conductivity of 143.7 m S cm^-1 at room temperature,which was superior to that of Nafion 212(91.0 m S cm^-1).Furthermore,the oxidative stabilities of SFPAEs were significantly higher than those of non-fluorinated analogs in literature.This study offered a new route to engineering the pendent structure of ionomers for well-defined microscopic morphologies.展开更多
Proton conductivity of proton exchange membranes(PEMs)strongly relies on microscopic morphology,which can be modulated by engineering the distribution of ionic groups.Herein,poly(arylene ether)s with densely distribut...Proton conductivity of proton exchange membranes(PEMs)strongly relies on microscopic morphology,which can be modulated by engineering the distribution of ionic groups.Herein,poly(arylene ether)s with densely distributed allyl functionalities are polymerized from a tetra-allyl bisphenol A monomer.The subsequent thiol-ene addition with sodium 3-mercapto-1-propanesulfonate yields comb-shaped sulfonated fluorinated poly(arylene ether)s(SFPAEs)with ion exchange capacities(lECs)ranging from 1.29 mmol·g^-1 to 1.78 mmol g^-1.These SFPAEs exhibit superior proton conductivity over the whole temperature range,which is attributed to the enhanced hydrophilic/hydrophobic phase separation as evidenced by small angle X-ray scattering characterizations.The SFPAE-4-40 with an IEC of 1.78 mmol·g^-1 shows the largest proton conductivity of 93 mS-crrr1 at room temperature under fully hydrated condition,higher than that of Nafion 212.Furthermore,the vanadium redox flow battery(VRFB)assembled with SFPAE-4-40 separator exhibits higher energy efficiency than the VRFB assembled with Nafion 212.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
Anion-exchange membranes(AEMs)with high conductivity and stability are essential components of hydrogen related water electrolysis and fuel cell applications.During the past decades,polynorbornene(PNB)-based AEMs have...Anion-exchange membranes(AEMs)with high conductivity and stability are essential components of hydrogen related water electrolysis and fuel cell applications.During the past decades,polynorbornene(PNB)-based AEMs have shown excellent performance due to their saturated all-carbon-based backbones and diverse strategies to prepare cross-linked membranes.However,nearly all previously reported PNB-based AEMs rely on the alkyl-substituted norbornene monomers,whose low-yielding synthesis leads to high-cost of the AEMs.In addition,the crosslinked PNB-based AEMs usually suffered from mechanical brittleness.Herein,we propose a novel semi-interpenetrating polymer network(s-IPN)strategy to simultaneously enhance mechanical modulus and ionic conductivity,while using commercial 5-vinyl-2-norbornene(VNB)as the single norbornene derivatives to prepare high-performance AEMs.A diallylphenol quaternary ammonium salt was used for photo-induced crosslinking with poly-VNB and various dithiols to produce AEMs with s-IPN structures.The resultant membranes have excellent hydroxide conductivities and alkaline stability in 1 mol/L KOH at 80℃,and are successfully applied in alkaline anion-exchange membrane water electrolyzers to stably operateforover150h.展开更多
Developing a stable,reliable,and industrially compatible method to control hydrophobicity is crucial for separation,transportation,and the generation of special surfaces.An e-HMS-PDMS silica gel nanoparticle coating w...Developing a stable,reliable,and industrially compatible method to control hydrophobicity is crucial for separation,transportation,and the generation of special surfaces.An e-HMS-PDMS silica gel nanoparticle coating was prepared using a two-step electron beam irradiation(EBI)process,consisting of(i)grafting of two organic groups onto thiol-functionalized hollow mesoporous silica(HMS-SH)with 10 MeV EBI and(ii)curing of polydimethylsiloxane(PDMS)onto silicone rubber using the HMS hybrid materials prepared in step i as an additive with 200 keV EBI.The tuneable grafting of functional groups and the surface properties of the silica,which was embedded in the PDMS layer,allowed us to precisely control the hydrophilicity of the PDMS layer by means of altering the grafting gradient of the silica and the loading ratio of the monomers.A diverse range of vinyl-structured monomers can be used in this method,and the selection of suitable monomers is vital in determining the physical properties of the coating layer.The hydrophilicity of the coating can be linearly controlled within a specific range(50°to 155°)by using suitable monomers,allowing for the design of surfaces with specific hydrophilic and hydrophobic requirements.展开更多
This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene clic...This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene click reaction via facile one-pot method.Hyperbranched poly(amido amine) with vinyl terminals was first synthesized by Michael addition polymerization of N,N'-methylene bisacrylamide (MBA) with 1-(2-aminoethyl) piperazine (AEPZ).Subsequently,thiol-ene click reaction between vinyl units of hyperbranched poly(amido amine) and thio-glucose was performed in situ.Based on the NMR result,all the vinyl groups reacted with thiol-glucose in 120 min.Strong photoluminescence emission was observed from the aqueous solution of HPAA-GLc.展开更多
In this study, a novel approach by combining base-catalyzed epoxide ring-opening and thiol-ene click chemistry is presented for the side-chain modification of dextran. The vinyl-modified dextran is prepared by a basic...In this study, a novel approach by combining base-catalyzed epoxide ring-opening and thiol-ene click chemistry is presented for the side-chain modification of dextran. The vinyl-modified dextran is prepared by a basic epoxide ring opening reaction of allyl glycidyl ether in 0.1 mol/L NaOH, followed by thiol-addition click reaction of three model sulfhydryl compounds using water-soluble Irgacure 2959 as the photoinitiator, leading to side-chain functionalized dextran modified with carboxyl, bidentate dicarboxyl or amino groups. This is the first example of combining epoxide ring-opening and thiol- ene click chemistry for side-chain modification of dextran in aqueous media. Importantly, it may also be extended as a convenient and efficient method for the side-chain modification of other polysaccharides.展开更多
In this study,we investigate the effect of the exposure dose on the mechanical property of the photoresins generated with acrylate self-polymerization and thiol-ene polymerization.The results indicate that the mechani...In this study,we investigate the effect of the exposure dose on the mechanical property of the photoresins generated with acrylate self-polymerization and thiol-ene polymerization.The results indicate that the mechanical performance of the thiol-ene photoresin is highly depended on the exposure dose during the solidification process.With 350-fold exposure dose change,the stiffness of the thiol-ene photoresin reached more that 700-fold change compare to 14-fold of the acrylate photoresin.We developed a TPL photoresist based on our results and show the capability to fabricate microstrucutres with high resolution and variable mechanical performances using this method.展开更多
Gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechan...Gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechanical properties of GPEs usually deteriorate dramatically when polymer matrices are plasticized by a liquid electrolyte, which leads to significant loss of battery performance. Therefore, the long-term structural integrity and good mechanical strength are critical characteristics of GPEs designed for highperformance batteries. Here, an ecologically compatible cellulose-based GPE with a crosslinked structure is synthesized via a facile and effective thiol-ene click chemistry method. The prepared thiol-ene crosslinked GPE possesses enhanced mechanical strength(10.95 MPa) and rigid structure, which enabled us to fabricate Li Fe PO_(4)|Li batteries with ultra-long cycling performance. The capacity retention of the crosslinked cellulose-based GPE can be up to 84% at 0.5 C, even after 350 cycles, which is considerably higher than that of non-crosslinked GPE for which rapid decline in capacity occurs after 200 cycles. In addition, a GPE preparation method described in this work compares favorably well with existing commercial electrolytes for lithium metal batteries.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21072072 and 21102051)PCSIRT(No.IRTO953)+1 种基金Program for New Century Excellent Talent in University(No.NCET-10-0428)Self-determined Research Funds of CCNU from the Colleges Basic Research and Operation of MOE (Nos.CCNU11C01002,CCNU12A01004 and CCNU12A02012)
文摘Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation（λ= 365 nm） in good yields.The structures of these compounds synthesized herein were fully confirmed by 1 H NMR.ES1-MS and elemental analysis.
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supported by the National Natural Science Foundation of China (Grant Nos. 51503038 and 51873037)
文摘The microstructure of polymer electrolyte membranes plays a key role in ion conductivity and water transport.Herein,fluorinated poly(aryl ether)s with tetra-alkylsulfonate side chains(SFPAEs)have been successfully synthesized from the copolymerization of a newly developed tetra-allyl-containing bisphenol(TABP)monomer,followed by the thiol-ene addition with sodium 3-mercapto-1-propanesulfonate to attach the ionic groups at the end of the flexible chains.Being the first of its kind,the densely distributed and lengthy alkylsulfonate group possesses the benefit of ease to self-assemble into hydrophilic domains during membrane preparation via solution casting.Indeed,the TEM characterizations revealed that distinct hydrophilic channels of 1-2 nm width had been formed,much larger than those of a home-made control sample where only di-alkylsulfonate side chains were attached.The SFPAE-4-45 with an IECw of 2.0 mmol g^-1 exhibited an enhanced proton conductivity of 143.7 m S cm^-1 at room temperature,which was superior to that of Nafion 212(91.0 m S cm^-1).Furthermore,the oxidative stabilities of SFPAEs were significantly higher than those of non-fluorinated analogs in literature.This study offered a new route to engineering the pendent structure of ionomers for well-defined microscopic morphologies.
基金the National Natural Science Foundation of China(Nos.51873037 and 51503038).
文摘Proton conductivity of proton exchange membranes(PEMs)strongly relies on microscopic morphology,which can be modulated by engineering the distribution of ionic groups.Herein,poly(arylene ether)s with densely distributed allyl functionalities are polymerized from a tetra-allyl bisphenol A monomer.The subsequent thiol-ene addition with sodium 3-mercapto-1-propanesulfonate yields comb-shaped sulfonated fluorinated poly(arylene ether)s(SFPAEs)with ion exchange capacities(lECs)ranging from 1.29 mmol·g^-1 to 1.78 mmol g^-1.These SFPAEs exhibit superior proton conductivity over the whole temperature range,which is attributed to the enhanced hydrophilic/hydrophobic phase separation as evidenced by small angle X-ray scattering characterizations.The SFPAE-4-40 with an IEC of 1.78 mmol·g^-1 shows the largest proton conductivity of 93 mS-crrr1 at room temperature under fully hydrated condition,higher than that of Nafion 212.Furthermore,the vanadium redox flow battery(VRFB)assembled with SFPAE-4-40 separator exhibits higher energy efficiency than the VRFB assembled with Nafion 212.
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.
基金financially supported by the Ministry of Science and Technology of China under the National Key R&D Program of China (No.2023YFB3811200)the National Natural Science Foundation of China (No.22075292).
文摘Anion-exchange membranes(AEMs)with high conductivity and stability are essential components of hydrogen related water electrolysis and fuel cell applications.During the past decades,polynorbornene(PNB)-based AEMs have shown excellent performance due to their saturated all-carbon-based backbones and diverse strategies to prepare cross-linked membranes.However,nearly all previously reported PNB-based AEMs rely on the alkyl-substituted norbornene monomers,whose low-yielding synthesis leads to high-cost of the AEMs.In addition,the crosslinked PNB-based AEMs usually suffered from mechanical brittleness.Herein,we propose a novel semi-interpenetrating polymer network(s-IPN)strategy to simultaneously enhance mechanical modulus and ionic conductivity,while using commercial 5-vinyl-2-norbornene(VNB)as the single norbornene derivatives to prepare high-performance AEMs.A diallylphenol quaternary ammonium salt was used for photo-induced crosslinking with poly-VNB and various dithiols to produce AEMs with s-IPN structures.The resultant membranes have excellent hydroxide conductivities and alkaline stability in 1 mol/L KOH at 80℃,and are successfully applied in alkaline anion-exchange membrane water electrolyzers to stably operateforover150h.
基金supported by the Program for HUST Academic Frontier Youth Team(2019QYTD06)Natural Science Foundation of Wuhan.
文摘Developing a stable,reliable,and industrially compatible method to control hydrophobicity is crucial for separation,transportation,and the generation of special surfaces.An e-HMS-PDMS silica gel nanoparticle coating was prepared using a two-step electron beam irradiation(EBI)process,consisting of(i)grafting of two organic groups onto thiol-functionalized hollow mesoporous silica(HMS-SH)with 10 MeV EBI and(ii)curing of polydimethylsiloxane(PDMS)onto silicone rubber using the HMS hybrid materials prepared in step i as an additive with 200 keV EBI.The tuneable grafting of functional groups and the surface properties of the silica,which was embedded in the PDMS layer,allowed us to precisely control the hydrophilicity of the PDMS layer by means of altering the grafting gradient of the silica and the loading ratio of the monomers.A diverse range of vinyl-structured monomers can be used in this method,and the selection of suitable monomers is vital in determining the physical properties of the coating layer.The hydrophilicity of the coating can be linearly controlled within a specific range(50°to 155°)by using suitable monomers,allowing for the design of surfaces with specific hydrophilic and hydrophobic requirements.
基金supported by the National Natural Science Foundation of China (20874093,50973102)
文摘This paper reports the production of glycopolymers via a simple and flexible method.A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene click reaction via facile one-pot method.Hyperbranched poly(amido amine) with vinyl terminals was first synthesized by Michael addition polymerization of N,N'-methylene bisacrylamide (MBA) with 1-(2-aminoethyl) piperazine (AEPZ).Subsequently,thiol-ene click reaction between vinyl units of hyperbranched poly(amido amine) and thio-glucose was performed in situ.Based on the NMR result,all the vinyl groups reacted with thiol-glucose in 120 min.Strong photoluminescence emission was observed from the aqueous solution of HPAA-GLc.
基金financially supported by the National Natural Science Foundation of China(Nos.51373168,51390484,51233004 and 51321062)
文摘In this study, a novel approach by combining base-catalyzed epoxide ring-opening and thiol-ene click chemistry is presented for the side-chain modification of dextran. The vinyl-modified dextran is prepared by a basic epoxide ring opening reaction of allyl glycidyl ether in 0.1 mol/L NaOH, followed by thiol-addition click reaction of three model sulfhydryl compounds using water-soluble Irgacure 2959 as the photoinitiator, leading to side-chain functionalized dextran modified with carboxyl, bidentate dicarboxyl or amino groups. This is the first example of combining epoxide ring-opening and thiol- ene click chemistry for side-chain modification of dextran in aqueous media. Importantly, it may also be extended as a convenient and efficient method for the side-chain modification of other polysaccharides.
基金the National Natural Science Foundation of China(Nos.22002015 and 52033002)the Fundamental Research Funding from Jiangsu Province(No.BK20211560)the Fundamental Research Funds for the Central Universities(No.2242018R20011).
文摘In this study,we investigate the effect of the exposure dose on the mechanical property of the photoresins generated with acrylate self-polymerization and thiol-ene polymerization.The results indicate that the mechanical performance of the thiol-ene photoresin is highly depended on the exposure dose during the solidification process.With 350-fold exposure dose change,the stiffness of the thiol-ene photoresin reached more that 700-fold change compare to 14-fold of the acrylate photoresin.We developed a TPL photoresist based on our results and show the capability to fabricate microstrucutres with high resolution and variable mechanical performances using this method.
基金financially supported by National Natural Science Foundation of China (Nos. 21965012, 52003068, 52062012)Research Project of Hainan Province (Nos. ZDYF2021SHFZ263,2019RC038 and ZDYF2020028)+1 种基金Guangdong Province Key Discipline Construction Project (No. 2021ZDJS102)the Innovation Team of Universities of Guangdong Province (No. 2022KCXTD030)。
文摘Gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechanical properties of GPEs usually deteriorate dramatically when polymer matrices are plasticized by a liquid electrolyte, which leads to significant loss of battery performance. Therefore, the long-term structural integrity and good mechanical strength are critical characteristics of GPEs designed for highperformance batteries. Here, an ecologically compatible cellulose-based GPE with a crosslinked structure is synthesized via a facile and effective thiol-ene click chemistry method. The prepared thiol-ene crosslinked GPE possesses enhanced mechanical strength(10.95 MPa) and rigid structure, which enabled us to fabricate Li Fe PO_(4)|Li batteries with ultra-long cycling performance. The capacity retention of the crosslinked cellulose-based GPE can be up to 84% at 0.5 C, even after 350 cycles, which is considerably higher than that of non-crosslinked GPE for which rapid decline in capacity occurs after 200 cycles. In addition, a GPE preparation method described in this work compares favorably well with existing commercial electrolytes for lithium metal batteries.
