Thiol-ene click polymerization has become an effective synthetic tool for constructing diverse sulfurcontaining polymers with advanced functions.However,the polymerization of internal alkene and thiol has been rarely ...Thiol-ene click polymerization has become an effective synthetic tool for constructing diverse sulfurcontaining polymers with advanced functions.However,the polymerization of internal alkene and thiol has been rarely used to prepare functional polymers because of large steric hindrance and relatively weak reactivity.In this work,a base-catalyzed click polymerization of thiols and internal olefins was successfully established in air.Notably,the polymerization went smoothly in halogen-containing solvent even without any catalyst via a radical step-growth polymerization.The polymerization enjoys excellent monomer applicability,which affords 16 well-defined polythioethers in high yields(up to 99%)with high molecular weights(Mwup to 19,600),good thermal stability(Td,5%up to 326℃),broadly regulated glass transition temperatures(-24~95℃),and unconventional fluorescence.Via a simple solvent regulation strategy,the vanillin-derived polythioether could be used as a turn-off fluorescence probe for Fe3+ions in DMF/H2O and a turn-on probe for Ag+ions in THF,with low detection limits of 9.15×10^(-7)mol/L and 4.60×10^(-7)mol/L,respectively.Additionally,the detection of Ag+presented a transformation from a clear solution to an emulsion,expanding the application prospects through observing colorimetric and fluorescent dual signals.Thus,this work not only holds significance in establishing an efficient polymerization,but also provides a strategy to prepare sensitive fluorescent probes for multiple metal ions.展开更多
Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes.Polyprodrug micelles can cross-link with other hydrophobic drugs through noncovalent bonds,which ha...Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes.Polyprodrug micelles can cross-link with other hydrophobic drugs through noncovalent bonds,which has the advantage of fixed structure and avoids the use of chemical cross-linking agents.In this study,we prepared a polyprodrug with hydrophobic curcumin(CUR)and hydrophilic poly(ethylene glycol)(PEG)in the main chain through a click reaction between CUR derivatives containing azide groups and di-alkynly-capped PEG.Due to the presence of benzene rings in the structure of CUR,the polyprodrug can form non-covalent cross-linked nanoparticles(NCCL-CUR NPs)through hydrophobic andπ-πstacking interaction.The structure,molecular weight,and self-assembly properties of the polyprodrug were characterized.The anti-cancer drug camptothecin(CPT)was encapsulated in the polyprodrug nanoparticles,producing dual-drug-loaded nanoparticles(abbreviated as CPT@NCCL-CUR NPs).The test results indicate that the NPs have reductive responsiveness and can release the original drugs CUR and CPT in phosphate buffer(PB)solution containing glutathione(GSH),while remaining stability in physiological environment.Cell and in vivo experiments further demonstrate that the dualdrug-loaded CPT@NCCL-CUR NPs can inhibit the growth of tumor through synergistic effects.This work provides a valuable approach for the preparation of amphiphilic polyprodrug with anti-tumor CUR as the backbone,and the stable dual-drug-loaded NPs containing both CUR and CPT through non-covalent cross-linking for synergistic therapy.展开更多
Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this w...Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this work,we reported the synthesis of a novel porous organic polymer,FOSU-POP-1 for the separation of CH_(4)/C_(2)H_(6)/C_(3)H_(8).The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer-Emmett-Teller(BET)surface area of 1038 m^(2)·g^(-1).Exhibiting stronger affinity towards C_(3)H_(8) and C_(2)H_(6) than CH_(4),2.85 mmol·g^(-1) for C_(3)H_(8) and 2.14 mmol·g^(-1) for C_(2)H_(6) were achieved on the FOSU-POP-1 at 0.1 MPa,298 K,with an ideal adsorbed solution theory selectivity of 227 for C_(3)H_(8)/CH_(4).The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH_(4)/C_(2)H_(6)/C_(3)H_(8) ternary mixture.The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C_(3)H_(8) and C_(2)H_(6).This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH_(4)/C_(2)H_(6)/C_(3)H_(8) mixture.展开更多
建立了由一个制造商和一个分销商组成的基于电子市场的二级供应链模型,讨论了分销商采用Bricks and Clicks模式分销产品,并在电子渠道进行季节后销售的情况,分析了供应链的契约协调问题及供应链成员的利润情况.研究发现改进的回购契约...建立了由一个制造商和一个分销商组成的基于电子市场的二级供应链模型,讨论了分销商采用Bricks and Clicks模式分销产品,并在电子渠道进行季节后销售的情况,分析了供应链的契约协调问题及供应链成员的利润情况.研究发现改进的回购契约可以使Bricks and Clicks分销模式下基于电子市场的二级供应链模型达到协调,使分销商的订货量达到供应链最优,并且使供应链成员的利润达到Pareto改进,达到"双赢".最后,通过算例验证了结论.展开更多
Click是一种模块化的软件路由器体系结构,基于该体系结构用户可以根据自己的需求搭建不同功能的路由器。针对Click软件路由器支持静态路由协议的局限性,引入模块化路由器软件协议栈XORP(eXtensible Open Router Platform),实现了动态路...Click是一种模块化的软件路由器体系结构,基于该体系结构用户可以根据自己的需求搭建不同功能的路由器。针对Click软件路由器支持静态路由协议的局限性,引入模块化路由器软件协议栈XORP(eXtensible Open Router Platform),实现了动态路由协议在Click软件路由器上的扩展。通过搭建实验网络拓扑环境,验证了基于Click转发平台的两种不同的动态路由协议RIP和OSPF,并进行了相关测试和性能分析。实验结果表明,Click软件路由器的转发性能与Linux内核基本一致,但相比较而言,Click软件路由器具有灵活、可扩展、模块化等不可比拟的优势。展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22479102,22001078)the Guangdong Talent Program(No.2023TQ07L822)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2024A1515011716)the startup funding of Songshan Lake Materials Laboratory(No.Y1D1031H311)。
文摘Thiol-ene click polymerization has become an effective synthetic tool for constructing diverse sulfurcontaining polymers with advanced functions.However,the polymerization of internal alkene and thiol has been rarely used to prepare functional polymers because of large steric hindrance and relatively weak reactivity.In this work,a base-catalyzed click polymerization of thiols and internal olefins was successfully established in air.Notably,the polymerization went smoothly in halogen-containing solvent even without any catalyst via a radical step-growth polymerization.The polymerization enjoys excellent monomer applicability,which affords 16 well-defined polythioethers in high yields(up to 99%)with high molecular weights(Mwup to 19,600),good thermal stability(Td,5%up to 326℃),broadly regulated glass transition temperatures(-24~95℃),and unconventional fluorescence.Via a simple solvent regulation strategy,the vanillin-derived polythioether could be used as a turn-off fluorescence probe for Fe3+ions in DMF/H2O and a turn-on probe for Ag+ions in THF,with low detection limits of 9.15×10^(-7)mol/L and 4.60×10^(-7)mol/L,respectively.Additionally,the detection of Ag+presented a transformation from a clear solution to an emulsion,expanding the application prospects through observing colorimetric and fluorescent dual signals.Thus,this work not only holds significance in establishing an efficient polymerization,but also provides a strategy to prepare sensitive fluorescent probes for multiple metal ions.
基金supported by the National Natural Science Foundation of China(No.21975169)the Project Fund of the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions+2 种基金the Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function of Soochow Universitythe Research project of China Baoyuan Investment Co.,Ltd.Suzhou Science and Technology Plan Project(No.SKY2023051)。
文摘Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes.Polyprodrug micelles can cross-link with other hydrophobic drugs through noncovalent bonds,which has the advantage of fixed structure and avoids the use of chemical cross-linking agents.In this study,we prepared a polyprodrug with hydrophobic curcumin(CUR)and hydrophilic poly(ethylene glycol)(PEG)in the main chain through a click reaction between CUR derivatives containing azide groups and di-alkynly-capped PEG.Due to the presence of benzene rings in the structure of CUR,the polyprodrug can form non-covalent cross-linked nanoparticles(NCCL-CUR NPs)through hydrophobic andπ-πstacking interaction.The structure,molecular weight,and self-assembly properties of the polyprodrug were characterized.The anti-cancer drug camptothecin(CPT)was encapsulated in the polyprodrug nanoparticles,producing dual-drug-loaded nanoparticles(abbreviated as CPT@NCCL-CUR NPs).The test results indicate that the NPs have reductive responsiveness and can release the original drugs CUR and CPT in phosphate buffer(PB)solution containing glutathione(GSH),while remaining stability in physiological environment.Cell and in vivo experiments further demonstrate that the dualdrug-loaded CPT@NCCL-CUR NPs can inhibit the growth of tumor through synergistic effects.This work provides a valuable approach for the preparation of amphiphilic polyprodrug with anti-tumor CUR as the backbone,and the stable dual-drug-loaded NPs containing both CUR and CPT through non-covalent cross-linking for synergistic therapy.
基金financially supported by the National Natural Science Foundation of China(22208050,22108034)Guangdong Provincial Natural Science Foundation Project(2023A1515012151)Scientific Research Project of Guangdong Provincial Department of Education(2023KTSCX132).
文摘Adsorptive separation holds important prospect for the challenging recovery of C_(2)H_(6) and C_(3)H_(8) from natural gas and the separation efficiency is primarily determined by a high-performance adsorbent.In this work,we reported the synthesis of a novel porous organic polymer,FOSU-POP-1 for the separation of CH_(4)/C_(2)H_(6)/C_(3)H_(8).The FOSU-POP-1 was synthesized from tetrakis(4-azidophenyl)methane and 1,3,5-triethynylbenzene via click reaction with a Brunauer-Emmett-Teller(BET)surface area of 1038 m^(2)·g^(-1).Exhibiting stronger affinity towards C_(3)H_(8) and C_(2)H_(6) than CH_(4),2.85 mmol·g^(-1) for C_(3)H_(8) and 2.14 mmol·g^(-1) for C_(2)H_(6) were achieved on the FOSU-POP-1 at 0.1 MPa,298 K,with an ideal adsorbed solution theory selectivity of 227 for C_(3)H_(8)/CH_(4).The breakthrough experiment confirmed the good dynamic separation performance and recyclability of FOSU-POP-1 for CH_(4)/C_(2)H_(6)/C_(3)H_(8) ternary mixture.The density functional theory calculation further revealed that the N atom in triazole ring interacted strongly with the C_(3)H_(8) and C_(2)H_(6).This work highlighted the promising capability of FOSU-POP-1 for efficiently separating CH_(4)/C_(2)H_(6)/C_(3)H_(8) mixture.
文摘建立了由一个制造商和一个分销商组成的基于电子市场的二级供应链模型,讨论了分销商采用Bricks and Clicks模式分销产品,并在电子渠道进行季节后销售的情况,分析了供应链的契约协调问题及供应链成员的利润情况.研究发现改进的回购契约可以使Bricks and Clicks分销模式下基于电子市场的二级供应链模型达到协调,使分销商的订货量达到供应链最优,并且使供应链成员的利润达到Pareto改进,达到"双赢".最后,通过算例验证了结论.
文摘Click是一种模块化的软件路由器体系结构,基于该体系结构用户可以根据自己的需求搭建不同功能的路由器。针对Click软件路由器支持静态路由协议的局限性,引入模块化路由器软件协议栈XORP(eXtensible Open Router Platform),实现了动态路由协议在Click软件路由器上的扩展。通过搭建实验网络拓扑环境,验证了基于Click转发平台的两种不同的动态路由协议RIP和OSPF,并进行了相关测试和性能分析。实验结果表明,Click软件路由器的转发性能与Linux内核基本一致,但相比较而言,Click软件路由器具有灵活、可扩展、模块化等不可比拟的优势。
