We investigated the ring opening polymerization (ROP) of di- and tri-ethylene glycol monomethyl ether functionalized L-glutamate N-carboxyanhydrides (NCAs) using hexamethyldisilazane (HMDS) as primary initiator ...We investigated the ring opening polymerization (ROP) of di- and tri-ethylene glycol monomethyl ether functionalized L-glutamate N-carboxyanhydrides (NCAs) using hexamethyldisilazane (HMDS) as primary initiator and 1,5,7-triazabicyclo-[4.4.0]dec-5-ene (TBD) as co-initiator. The binary initiator system afforded a living ROP for these pegylated NCAs, and a series of homopolypeptides with controlled molecular weight (MW) and low polydispersity were obtained. We then systematically studied the helical content and clouding point (CP) dependence on polypeptide MW using circular dichroism (CD) spectroscopy and turbidity measurements, respectively. We found that the helical content of both homopolypeptides increased with MW, but the triethylene glycol functionalized poly-L-glutamate (poly-L-EG3Glu) intended to form more stable or-helical structure than diethylene glycol functionalized counterpart (poly-L-EG2Glu) at similar MW. Accordingly, the CP of poly-L-EG2Glu with known end group has strong dependence on its helical content, which is essentially determined by MW. Our results suggested that the thermal responsive properties of these unique pegylated poly- L-glutamates not only rely on their chemical structure but also on their secondary structures, wh^ch is different from conventional thermal responsive polymers.展开更多
Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and ele...Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and electrodes as main components of lithium batteries strongly affect the occurrence of safety accidents.Responsive materials,which can respond to external stimuli or environmental change,have triggered extensive attentions recently,holding great promise in facilitating safe and smart batteries.This review thoroughly discusses recent advances regarding the construction of high-safety lithium batteries based on internal thermal-responsive strategies,together with the corresponding changes in electrochemical performance under external stimulus.Furthermore,the existing challenges and outlook for the design of safe batteries are presented,creating valuable insights and proposing directions for the practical implementation of safe lithium batteries.展开更多
A thermo-responsive rewritable plasmonic bio-memory chip has been successfully fabricated on an indium tin oxide(ITO)glass slide by assembling core-satellite gold nanoclusters with different size of gold nanoparticles...A thermo-responsive rewritable plasmonic bio-memory chip has been successfully fabricated on an indium tin oxide(ITO)glass slide by assembling core-satellite gold nanoclusters with different size of gold nanoparticles(AuNPs)using double-strand DNA(dsDNA)linker.And the prepared 70@DNA20@13 gold nanoclusters(AuNCs)exhibited more stable and greater photothermal conversion ability.With short time irradiation by 633 nm microbeam laser,every individual AuNCs could be excited and remove the satellite AuNPs on its surface.Especially,in the dissociation process of AuNCs with 3−5 satellite,its color would change from yellow to green,which showed more significant reduction in the red channel of the dark-field microscopy(DFM)images and could be defined to state“0”and“1”respectively.Besides,this plasmonic nano bio-memory could transform cyclically its state between 0 and 1 which exhibited excellent rewritable ability.展开更多
Hypoxia is a typical feature of solid tumors,which highly limits the application of the oxygen-dependent therapy.Also,the dense and hyperbaric tumor tissues impede the penetration of nanoparticles into the deep tumor....Hypoxia is a typical feature of solid tumors,which highly limits the application of the oxygen-dependent therapy.Also,the dense and hyperbaric tumor tissues impede the penetration of nanoparticles into the deep tumor.Thereby,we designed a novel localized injectable hydrogel combining the photothermal therapy(PTT)and the thermodynamic therapy(TDT),which is based on the generation of free radicals even in the absence of oxygen for hypoxic tumor therapy.In our study,gold nanorods(Au NRs)and 2,2-Azobis[2-(2-imidazalin-2-yl)propane]dihydrochlaride(AIPH)were incorporated into the hydrogel networks,which were formed by the copolymerization of hydrophobic N-isopropyl acrylamide(NIPAM)and hydrophilic glycidyl methacrylate modified hyaluronic acid(HAGMA)to fabricate an injectable and near-infrared(NIR)responsive hydrogel.The crosslinked in situ forming hydrogel could not only realize PTT upon the NIR laser irradiation,but also generate free radicals even in hypoxic condition.Meanwhile the shrink of hydrogels upon thermal could accelerate the generation of free radicals to further damage the tumors,achieving the controlled drug release on demand.The designed hydrogel with a sufficient loading capacity,excellent biocompatibility and negligible systemic toxicity could serve as a long-acting implant for NIR-triggered thermo-responsive free radical generation.The in vitro cytotoxicity result and the in vivo antitumor activity illustrated the excellent therapeutic effect of hydrogels even in the absence of oxygen.Therefore,this innovative oxygen-independent platform combining the antitumor effects of PTT and TDT would bring a new insight into hypoxic tumor therapy by the application of alkyl free radical.展开更多
Thermally responsive liquid crystal elastomers (LCEs) hold great promise in applications of soft robots and actuators because of the induced size and shape change with temperature. Experiments have successfully demons...Thermally responsive liquid crystal elastomers (LCEs) hold great promise in applications of soft robots and actuators because of the induced size and shape change with temperature. Experiments have successfully demonstrated that the LCE based bimorphs can be effective soft robots once integrated with soft sensors and thermal actuators. Here, we present an analytical transient thermo-mechanical model for a bimorph structure based soft robot, which consists of a strip of LCE and a thermal inert polymer actuated by an ultra-thin stretchable open-mesh shaped heater to mimic the unique locomotion behaviors of an inchworm. The coupled mechanical and thermal analysis based on the thermo-mechanical theory is carried out to underpin the transient bending behavior, and a systematic understanding is therefore achieved. The key analytical results reveal that the thickness and the modulus ratio of the LCE and the inert polymer layer dominate the transient bending deformation. The analytical results will not only render fundamental understanding of the actuation of bimorph structures, but also facilitate the rational design of soft robotics.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 20974112 and 51225306)
文摘We investigated the ring opening polymerization (ROP) of di- and tri-ethylene glycol monomethyl ether functionalized L-glutamate N-carboxyanhydrides (NCAs) using hexamethyldisilazane (HMDS) as primary initiator and 1,5,7-triazabicyclo-[4.4.0]dec-5-ene (TBD) as co-initiator. The binary initiator system afforded a living ROP for these pegylated NCAs, and a series of homopolypeptides with controlled molecular weight (MW) and low polydispersity were obtained. We then systematically studied the helical content and clouding point (CP) dependence on polypeptide MW using circular dichroism (CD) spectroscopy and turbidity measurements, respectively. We found that the helical content of both homopolypeptides increased with MW, but the triethylene glycol functionalized poly-L-glutamate (poly-L-EG3Glu) intended to form more stable or-helical structure than diethylene glycol functionalized counterpart (poly-L-EG2Glu) at similar MW. Accordingly, the CP of poly-L-EG2Glu with known end group has strong dependence on its helical content, which is essentially determined by MW. Our results suggested that the thermal responsive properties of these unique pegylated poly- L-glutamates not only rely on their chemical structure but also on their secondary structures, wh^ch is different from conventional thermal responsive polymers.
基金supported by the National Natural Science Foundation of China(22179070,U1932220)the Natural Science Foundation of Jiangsu Province(BK20220073)the Fundamental Research Funds for the Central Universities(RF1028623157)。
文摘Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and electrodes as main components of lithium batteries strongly affect the occurrence of safety accidents.Responsive materials,which can respond to external stimuli or environmental change,have triggered extensive attentions recently,holding great promise in facilitating safe and smart batteries.This review thoroughly discusses recent advances regarding the construction of high-safety lithium batteries based on internal thermal-responsive strategies,together with the corresponding changes in electrochemical performance under external stimulus.Furthermore,the existing challenges and outlook for the design of safe batteries are presented,creating valuable insights and proposing directions for the practical implementation of safe lithium batteries.
基金the National Natural Science Foundation of China(NSFC,Nos.22204081,62075103,and 22374081)Project of State Key Laboratory of Organic Electronics and Information Displays,Nanjing University of Posts and Telecommunications(No.20230112)+1 种基金Natural Science Foundation of Jiangsu Province(No.BK20211271)State Key Laboratory of Analytical Chemistry for Life Science(No.SKLACLS2210).
文摘A thermo-responsive rewritable plasmonic bio-memory chip has been successfully fabricated on an indium tin oxide(ITO)glass slide by assembling core-satellite gold nanoclusters with different size of gold nanoparticles(AuNPs)using double-strand DNA(dsDNA)linker.And the prepared 70@DNA20@13 gold nanoclusters(AuNCs)exhibited more stable and greater photothermal conversion ability.With short time irradiation by 633 nm microbeam laser,every individual AuNCs could be excited and remove the satellite AuNPs on its surface.Especially,in the dissociation process of AuNCs with 3−5 satellite,its color would change from yellow to green,which showed more significant reduction in the red channel of the dark-field microscopy(DFM)images and could be defined to state“0”and“1”respectively.Besides,this plasmonic nano bio-memory could transform cyclically its state between 0 and 1 which exhibited excellent rewritable ability.
基金supported by the National Natural Science Foundation of China(Grant number:81673369/H3008)Science and Technology Program of Guangzhou,China(Grant number:201604020157)。
文摘Hypoxia is a typical feature of solid tumors,which highly limits the application of the oxygen-dependent therapy.Also,the dense and hyperbaric tumor tissues impede the penetration of nanoparticles into the deep tumor.Thereby,we designed a novel localized injectable hydrogel combining the photothermal therapy(PTT)and the thermodynamic therapy(TDT),which is based on the generation of free radicals even in the absence of oxygen for hypoxic tumor therapy.In our study,gold nanorods(Au NRs)and 2,2-Azobis[2-(2-imidazalin-2-yl)propane]dihydrochlaride(AIPH)were incorporated into the hydrogel networks,which were formed by the copolymerization of hydrophobic N-isopropyl acrylamide(NIPAM)and hydrophilic glycidyl methacrylate modified hyaluronic acid(HAGMA)to fabricate an injectable and near-infrared(NIR)responsive hydrogel.The crosslinked in situ forming hydrogel could not only realize PTT upon the NIR laser irradiation,but also generate free radicals even in hypoxic condition.Meanwhile the shrink of hydrogels upon thermal could accelerate the generation of free radicals to further damage the tumors,achieving the controlled drug release on demand.The designed hydrogel with a sufficient loading capacity,excellent biocompatibility and negligible systemic toxicity could serve as a long-acting implant for NIR-triggered thermo-responsive free radical generation.The in vitro cytotoxicity result and the in vivo antitumor activity illustrated the excellent therapeutic effect of hydrogels even in the absence of oxygen.Therefore,this innovative oxygen-independent platform combining the antitumor effects of PTT and TDT would bring a new insight into hypoxic tumor therapy by the application of alkyl free radical.
基金Project supported by the National Basic Research Program(No.2015CB351901)the National Natural Science Foundation of China(Nos.11372272,11622221,11621062,11502009,and 11772030)+2 种基金the Doctoral New Investigator Grant from American Chemical Society Petroleum Research Fund of the National Science Foundation(Nos.1509763 and 1554499)the Opening Fund of State Key Laboratory for Strength and Vibration of Mechanical Structures,Xi’an Jiaotong University(No.SV2018-KF-13)the Fundamental Research Funds for the Central Universities(No.2017XZZX002-11)
文摘Thermally responsive liquid crystal elastomers (LCEs) hold great promise in applications of soft robots and actuators because of the induced size and shape change with temperature. Experiments have successfully demonstrated that the LCE based bimorphs can be effective soft robots once integrated with soft sensors and thermal actuators. Here, we present an analytical transient thermo-mechanical model for a bimorph structure based soft robot, which consists of a strip of LCE and a thermal inert polymer actuated by an ultra-thin stretchable open-mesh shaped heater to mimic the unique locomotion behaviors of an inchworm. The coupled mechanical and thermal analysis based on the thermo-mechanical theory is carried out to underpin the transient bending behavior, and a systematic understanding is therefore achieved. The key analytical results reveal that the thickness and the modulus ratio of the LCE and the inert polymer layer dominate the transient bending deformation. The analytical results will not only render fundamental understanding of the actuation of bimorph structures, but also facilitate the rational design of soft robotics.