Poly(ester amide)s(PEAs)attract much attention as a new kind of biodegradable polymers.However,the synthesis of PEAs with sequence-regulated chain structures is still complicated due to the multistep polymerization,hi...Poly(ester amide)s(PEAs)attract much attention as a new kind of biodegradable polymers.However,the synthesis of PEAs with sequence-regulated chain structures is still complicated due to the multistep polymerization,high monomer purity,as well as the usage of organic solvents,which greatly inhibits its development and applications.Herein,a one-pot strategy without solvent was developed to synthesize the alternating PEA fromα,ω-amino alcohol and dicarboxylic acid by sequential polycondensation,where water was used as the controlling agent for amidation and esterification.Specifically,the amidation and esterification were controlled to proceed in turn by adding or removing water,realizing the one-pot preparation of alternating PEAs.The resultant PEA is characterized by^1H-and^(13)C-NMR,and its chain structure is confirmed to be highly quasi-alternating similar to alternating PEAs prepared by classical methods The evaluations from DSC and DMA demonstrate that the properties of quasi-alternating PEA(T_(m)=102℃,ΔH_(m)=30J·g^(-1))are far superior to those of random PEA(T_(m)=72℃,ΔH_(m)<1 J·g^(-1)).展开更多
The gallium-based eutectic alloy has gained particular attention in various fields due to its natural features of metallic fluids at room temperature.However,these alloy nanoparticles are extremely susceptible to be o...The gallium-based eutectic alloy has gained particular attention in various fields due to its natural features of metallic fluids at room temperature.However,these alloy nanoparticles are extremely susceptible to be oxidized accompanied by de-alloying during the preparation,storage,and application.Here,with the assistance of the macromolecular stabilizer and dopant,sodium dodecylbenzene sulfonate(SDBS),we demonstrate a stable polypyrrole(PPy)layer acts as a protected“armor”on the surface of liquid metal(i.e.,gallium-tin,EGaSn).SDBS enables the EGa Sn to keep well dispersion and protects dispersed EGaSn from being durative oxidized before PPy coating.Furthermore,PPy greatly inhibits the oxidation of EGaSn owing to the strong interface interaction between the lone pair electrons around the N atoms of Py rings and the Ga3+orbit of EGaSn.Consequently,the fabricated EGaSn nanoparticles possess the features of smaller particle size,superior uniform distribution,and stronger antioxidant capacity.The prepared EGaSn@PPy composite exhibits superior stability even after storing in an aqueous solution for up to 100 days.As a proof-of-concept application,the EGaSn@PPy composite displays remarkable photothermal performance with an enhanced photothermal conversion efficiency.This work provides a novel surface engineering strategy to ameliorate liquid metal for photothermal therapy applications.展开更多
Poly(aminoboranes)and poly(phosphinoboranes)have been of interest as inorganic analogues of poly(olefins)as early as the mid-20th century.However,their synthesis was only realised about 15 and 25 years ago,respectivel...Poly(aminoboranes)and poly(phosphinoboranes)have been of interest as inorganic analogues of poly(olefins)as early as the mid-20th century.However,their synthesis was only realised about 15 and 25 years ago,respectively.Initially,poly(aminoboranes)and poly(phosphinoboranes)were accessed via transitionmetal-catalysed dehydropolymerisation of amine-and phosphine-borane adducts.Despite the many advances made using this method,limitations remained,particularly in the conditions required for dehydropolymerisation and in the design of effective catalysts for producing materials with controlled molar mass and specific polymer architectures.Accordingly,new routes to these materials were sought through the synthesis of reactive aminoboranes or phosphinoboranes generated in situ for subsequent polymerisation.In doing so,materials that were previously inaccessible by metal-mediated dehydropolymerisation were unlocked.Mechanistically,there are fundamental differences between the transition-metal-catalysed approaches and transition-metal-free reactions with reactive monomers.Understanding and research of these new mechanisms are the foundation for the development of new polymer syntheses that allow for new polymer designs.This review article discusses the new design principles and polymer synthetic concepts.展开更多
Organic thermoelectric materials have emerged as compelling candidates for harvesting low‐grade heat in flexible and lightweight energy systems.Compared to conventional inorganic thermoelectric materials,organic ther...Organic thermoelectric materials have emerged as compelling candidates for harvesting low‐grade heat in flexible and lightweight energy systems.Compared to conventional inorganic thermoelectric materials,organic ther-moelectric materials offer distinct advantages,including intrinsically low ther-mal conductivity,mechanical flexibility,and compatibility with large‐area and solution‐based processing.While p‐type materials such as poly(3,4‐ethyl-enedioxythiophene):polystyrene sulfonate(PEDOT:PSS)have been exten-sively optimized through solvent treatments and de‐doping strategies,recent advances in air‐stable n‐type polymers such as poly(benzodifurandione)(PBFDO)have greatly narrowed the performance gap and made it feasible to construct fully organic thermoelectric modules.This review highlights recent progress in organic thermoelectric materials with a focus on molecular design,doping mechanisms,and device‐level integration.We examine how novel polymers,dopant formulations,and emerging concepts have been driving improvements in the performance of organic thermoelectric materials toward practical application.Our group's previous contributions to module design such as thermal lamination techniques and integrated circuits are presented as case studies of system‐level implementation.Despite their relatively modest power factors and thermoelectric figures of merit,organic thermoelectric materials possess unique advantages in terms of low weight,processability,and scal-ability that make them especially suited for gram‐scale modules and powering small‐scale electronic devices and Internet‐of‐Things systems using ambient thermal energy.展开更多
基金financially supported by the innovation funding from Wei Qiao Group(Nos.H2872307 and H2872305)Fundamental Research Funds for the Central Universities and Graduate Student Innovation Fund of Donghua University(No.CUSF-DH-D-2024004)。
文摘Poly(ester amide)s(PEAs)attract much attention as a new kind of biodegradable polymers.However,the synthesis of PEAs with sequence-regulated chain structures is still complicated due to the multistep polymerization,high monomer purity,as well as the usage of organic solvents,which greatly inhibits its development and applications.Herein,a one-pot strategy without solvent was developed to synthesize the alternating PEA fromα,ω-amino alcohol and dicarboxylic acid by sequential polycondensation,where water was used as the controlling agent for amidation and esterification.Specifically,the amidation and esterification were controlled to proceed in turn by adding or removing water,realizing the one-pot preparation of alternating PEAs.The resultant PEA is characterized by^1H-and^(13)C-NMR,and its chain structure is confirmed to be highly quasi-alternating similar to alternating PEAs prepared by classical methods The evaluations from DSC and DMA demonstrate that the properties of quasi-alternating PEA(T_(m)=102℃,ΔH_(m)=30J·g^(-1))are far superior to those of random PEA(T_(m)=72℃,ΔH_(m)<1 J·g^(-1)).
基金the National Natural Science Foundation of China(No.51974256)the Science,Technology,and Innovation Commission of Shenzhen Municipality(No.JCYJ20180508151856806)+3 种基金the Fundamental Research Funds for the Central Universities(No.G2020KY05129)the Outstanding Young Scholars of Shaanxi(No.2019JC-12)the Natural Science Basic Research Plan in Shaanxi Province of China(Nos.2019JLZ-01 and 2019JLM-29)the Fundamental Research Funds for the Central Universities(Nos.3102021ZD0401,3102021TS0406,and 3102019JC005)。
文摘The gallium-based eutectic alloy has gained particular attention in various fields due to its natural features of metallic fluids at room temperature.However,these alloy nanoparticles are extremely susceptible to be oxidized accompanied by de-alloying during the preparation,storage,and application.Here,with the assistance of the macromolecular stabilizer and dopant,sodium dodecylbenzene sulfonate(SDBS),we demonstrate a stable polypyrrole(PPy)layer acts as a protected“armor”on the surface of liquid metal(i.e.,gallium-tin,EGaSn).SDBS enables the EGa Sn to keep well dispersion and protects dispersed EGaSn from being durative oxidized before PPy coating.Furthermore,PPy greatly inhibits the oxidation of EGaSn owing to the strong interface interaction between the lone pair electrons around the N atoms of Py rings and the Ga3+orbit of EGaSn.Consequently,the fabricated EGaSn nanoparticles possess the features of smaller particle size,superior uniform distribution,and stronger antioxidant capacity.The prepared EGaSn@PPy composite exhibits superior stability even after storing in an aqueous solution for up to 100 days.As a proof-of-concept application,the EGaSn@PPy composite displays remarkable photothermal performance with an enhanced photothermal conversion efficiency.This work provides a novel surface engineering strategy to ameliorate liquid metal for photothermal therapy applications.
文摘Poly(aminoboranes)and poly(phosphinoboranes)have been of interest as inorganic analogues of poly(olefins)as early as the mid-20th century.However,their synthesis was only realised about 15 and 25 years ago,respectively.Initially,poly(aminoboranes)and poly(phosphinoboranes)were accessed via transitionmetal-catalysed dehydropolymerisation of amine-and phosphine-borane adducts.Despite the many advances made using this method,limitations remained,particularly in the conditions required for dehydropolymerisation and in the design of effective catalysts for producing materials with controlled molar mass and specific polymer architectures.Accordingly,new routes to these materials were sought through the synthesis of reactive aminoboranes or phosphinoboranes generated in situ for subsequent polymerisation.In doing so,materials that were previously inaccessible by metal-mediated dehydropolymerisation were unlocked.Mechanistically,there are fundamental differences between the transition-metal-catalysed approaches and transition-metal-free reactions with reactive monomers.Understanding and research of these new mechanisms are the foundation for the development of new polymer syntheses that allow for new polymer designs.This review article discusses the new design principles and polymer synthetic concepts.
基金Japan Science and Technology Agency,Grant/Award Number:JPMJTR23R6。
文摘Organic thermoelectric materials have emerged as compelling candidates for harvesting low‐grade heat in flexible and lightweight energy systems.Compared to conventional inorganic thermoelectric materials,organic ther-moelectric materials offer distinct advantages,including intrinsically low ther-mal conductivity,mechanical flexibility,and compatibility with large‐area and solution‐based processing.While p‐type materials such as poly(3,4‐ethyl-enedioxythiophene):polystyrene sulfonate(PEDOT:PSS)have been exten-sively optimized through solvent treatments and de‐doping strategies,recent advances in air‐stable n‐type polymers such as poly(benzodifurandione)(PBFDO)have greatly narrowed the performance gap and made it feasible to construct fully organic thermoelectric modules.This review highlights recent progress in organic thermoelectric materials with a focus on molecular design,doping mechanisms,and device‐level integration.We examine how novel polymers,dopant formulations,and emerging concepts have been driving improvements in the performance of organic thermoelectric materials toward practical application.Our group's previous contributions to module design such as thermal lamination techniques and integrated circuits are presented as case studies of system‐level implementation.Despite their relatively modest power factors and thermoelectric figures of merit,organic thermoelectric materials possess unique advantages in terms of low weight,processability,and scal-ability that make them especially suited for gram‐scale modules and powering small‐scale electronic devices and Internet‐of‐Things systems using ambient thermal energy.
