A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,h...A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.展开更多
For the purpose of overcoming the lack of durability problems associated with superhydrophobic surfaces which hitherto has limited their use;we prepared multi-stimuli wettability response coatings using a mixture of f...For the purpose of overcoming the lack of durability problems associated with superhydrophobic surfaces which hitherto has limited their use;we prepared multi-stimuli wettability response coatings using a mixture of fluorocarbon resin and urea-formaldehyde microcapsules filled with fluorosilane via interfacial polymerization process.The microcapsules are of good thermal stability and can be triggered to release their core content on exposure to atmospheric conditions resulting in the increase in the water contact angle from 97°to 151°.The prepared coatings gave good adhesion strength,and also showed an increase in the hydrophobic property after undergoing scratch,solvent and UV accelerated aging test.In addition,they offered good self-healing of the hydrophobic property after an initial loss due to alkaline immersion and oxygen plasma etching.The electrochemical measurements revealed a remarkable impedance recovery and suppression of corrosion activities,suggesting them to be a potential candidate material for corrosion protection.展开更多
A novel smart metal-organic gel（MOG） formed from biscarboxyl-functionalized benzimidazole derivative（D11） in the presence of lead nitrate has been investigated.The critical gel concentration for the formation of M...A novel smart metal-organic gel（MOG） formed from biscarboxyl-functionalized benzimidazole derivative（D11） in the presence of lead nitrate has been investigated.The critical gel concentration for the formation of MOG was just 0.36 wt%,which exhibits a super gelation capability of D11.The coordination of the metal to the ligand D11 was found to play a vital role in the construction of the supramolecular MOG.Microstructures determined by SEM observation demonstrated that the MOG was formed by intertwined fibrils.Interestingly,the MOG exhibits pH-induced,thermo-induced,and chemical-induced reversible gel-sol transition.Meanwhile,this supramolecular MOG shows desirable absorption ability of methyl orange dye molecules in aqueous solution.展开更多
Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches,memories,and molecular machines.The exploration of the material is currentl...Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches,memories,and molecular machines.The exploration of the material is currently focused on the pure organic system,which limits the development o such materials greatly.In this work,we present a new chiral organic-inorganic hybrid salt,(R-3hydroxypyrrolidinium)_(2)[Fe(CN)_(5)(NO)](1),which exhibits rare multi-stimuli responsive behaviors in ther mal,mechanical and optical channels.In detail,1 undergoes a C2-P2_(1)22_(1) phase transition deriving from the thermal motion of organic cations with the increase of temperature,but the reverse transition can only be induced by mechanical pressure.Moreover,polycrystalline hybrid salt showed photo-responsive performance,i.e.,the ground-state N-bound nitrosyl ligand adopts two configurations in excited state caused by light in 532 nm irradiation,accompanying with a photo-induced structural transformation o the anionic framework.Namely,the thermal motion characteristics of organic cations,the photoresponse characteristics of anionic inorganic skeleton and the pressure characteristics from hydrogen bonds are si multaneously integrated in 1.This unprecedented coupling mechanism of multi-stimuli responses make1 a potential candidate for future multichannel data storage applications.展开更多
A viologen-bearing Zn(Ⅱ) coordination polymer,[Zn(Bpybc)SO_(4)]·H_(2)O,has been successfully synthesized and structurally characterized.The title compound exhibits sunlight and UV-induced photochromism,thermosch...A viologen-bearing Zn(Ⅱ) coordination polymer,[Zn(Bpybc)SO_(4)]·H_(2)O,has been successfully synthesized and structurally characterized.The title compound exhibits sunlight and UV-induced photochromism,thermoschromism,and amine-selective chemochromism.展开更多
Multi-stimuli-responsive field-effect transistors(FETs)with organic/polymeric semiconductors have received increasing attention.Herein,we report a novel strategy for fabricating multi-stimuliresponsive polymeric semic...Multi-stimuli-responsive field-effect transistors(FETs)with organic/polymeric semiconductors have received increasing attention.Herein,we report a novel strategy for fabricating multi-stimuliresponsive polymeric semiconductors through the incorporation of spiropyran(SP)groups in the polymer side chains.The semiconducting performances of resultant FETs with a diketopyrrolopyrroles(DPP)-based conjugated donor–acceptor(D–A)polymer,that entails SP units in the side chains(pDSP-1),could be modulated reversibly through UV and visible light irradiations,or UV light irradiation and heating,or acid treatment and heating.Our studies reveal that during the reversible transformations of closed,open,and the protonated forms of spiropyran,achieved by light irradiations,heating,and under acidic conditions,a large dipole moment changes occur,which triggers the reversible variation of semiconducting performance of the FETs.展开更多
Hyperbranched polymers have attracted increasing interests due to their unique structure-related advantages and have been utilized as drug carriers for controlled delivery.However,it is still challenging to prepare mu...Hyperbranched polymers have attracted increasing interests due to their unique structure-related advantages and have been utilized as drug carriers for controlled delivery.However,it is still challenging to prepare multi stimuli-responsive hyperbranched polymers to sense and response the complex yet delicate changes in physiological environment.Herein,we propose a triple-stimuli backbone-breakable hyperbranched polymer(HBP(OEG-IB)),which is prepared via the convenient iminoboronate multicomponent reaction ofα,ω-di(1,2-diol)s oligo(ethylene glycol),tris(3-aminopropyl)amine and 2-formylphenylboronic acid.Upon the stimulation of CO2,lactic acid and glutathione,micelles formed by HBP(OEG-IB)could be disrupted via the dissociation of iminoboronate ester bond to subsequent release incorporated camptothecin(CPT).Cell experiments show that the HBP(OEG-IB)is non-toxic but can enhance the therapeutic effect of CPT thanks to the effect of the protonated tertiary amino groups.The demonstration made in this work can enrich the design of responsive HBPs and can be readily applied to other systems with tunable responsive properties and functions.展开更多
A biopolymer-inorganic hybrid system(MSN@PBLGF) is designed and fabricated from mesoporous silica nanoparticles(MSNs) and folic acid(FA)-terminated temperature-sensitive synthetic polypeptide,i.e.,poly(γ-benzyl-L-glu...A biopolymer-inorganic hybrid system(MSN@PBLGF) is designed and fabricated from mesoporous silica nanoparticles(MSNs) and folic acid(FA)-terminated temperature-sensitive synthetic polypeptide,i.e.,poly(γ-benzyl-L-glutamate)(PBLG) derivative,through a thiol-disulfide exchange reaction,where MSNs with high drug loading capacity serve as drug nanocarriers and the biocompatible PBLG biopolymer brushes installed on MSN surface through disulfide bonds endow the system with tumor-specific recognition ability and GSH/temperature dual-stimuli responsiveness.Controlled drug release experiments indicate that DOX can be tightly hosted in the system with limited premature release,but efficiently released in response to an increased concentration of GSH and/or an elevated temperature.Intracellular experiments demonstrate that the DOX-loaded MSN@PBLGF nanohybrid shows outstanding cellular uptake and cell-growth inhibition effects on human lung cancer cell line A549 in comparison with healthy human cells such as hepatocyte cells LO2.展开更多
基金supported by the National Natural Science Foundation of China(No.22271202 to L.Yuan,No.22201193 to X.Li)the Sichuan Science and Technology Program(No.2023NSFSC0109 to X.Li)+2 种基金the Fundamental Research Funds for the Central Universities and the Hundred Talent Program of Sichuan University(No.YJ2021158 to X.Li)Sichuan University Interdisciplinary Innovation Fund(X.Li)Open Project of State Key Laboratory of Supramolecular Structure and Materials(No.SKLSSM2024037)。
文摘A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
基金financial support from the Shenyang Science and Technology Plan Project(Y17-1-039)。
文摘For the purpose of overcoming the lack of durability problems associated with superhydrophobic surfaces which hitherto has limited their use;we prepared multi-stimuli wettability response coatings using a mixture of fluorocarbon resin and urea-formaldehyde microcapsules filled with fluorosilane via interfacial polymerization process.The microcapsules are of good thermal stability and can be triggered to release their core content on exposure to atmospheric conditions resulting in the increase in the water contact angle from 97°to 151°.The prepared coatings gave good adhesion strength,and also showed an increase in the hydrophobic property after undergoing scratch,solvent and UV accelerated aging test.In addition,they offered good self-healing of the hydrophobic property after an initial loss due to alkaline immersion and oxygen plasma etching.The electrochemical measurements revealed a remarkable impedance recovery and suppression of corrosion activities,suggesting them to be a potential candidate material for corrosion protection.
基金supported by the National Natural Science Foundation of China(Nos.21064006,21161018 and 21262032)the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China(No.IRT1177)+2 种基金the Natural Science Foundation of Gansu Province(No. 1010RJZA018)the Youth Foundation of Gansu Province(No.1208RJYA048)NWNU-LKQN-11-32
文摘A novel smart metal-organic gel（MOG） formed from biscarboxyl-functionalized benzimidazole derivative（D11） in the presence of lead nitrate has been investigated.The critical gel concentration for the formation of MOG was just 0.36 wt%,which exhibits a super gelation capability of D11.The coordination of the metal to the ligand D11 was found to play a vital role in the construction of the supramolecular MOG.Microstructures determined by SEM observation demonstrated that the MOG was formed by intertwined fibrils.Interestingly,the MOG exhibits pH-induced,thermo-induced,and chemical-induced reversible gel-sol transition.Meanwhile,this supramolecular MOG shows desirable absorption ability of methyl orange dye molecules in aqueous solution.
基金supported by the National Natural Science Foundation of China(Nos.22071273 and 21821003)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.23lgzy001)。
文摘Multi-stimuli responsive materials controlled and coupled by two or more channels have a broad range of applications in the field of switches,memories,and molecular machines.The exploration of the material is currently focused on the pure organic system,which limits the development o such materials greatly.In this work,we present a new chiral organic-inorganic hybrid salt,(R-3hydroxypyrrolidinium)_(2)[Fe(CN)_(5)(NO)](1),which exhibits rare multi-stimuli responsive behaviors in ther mal,mechanical and optical channels.In detail,1 undergoes a C2-P2_(1)22_(1) phase transition deriving from the thermal motion of organic cations with the increase of temperature,but the reverse transition can only be induced by mechanical pressure.Moreover,polycrystalline hybrid salt showed photo-responsive performance,i.e.,the ground-state N-bound nitrosyl ligand adopts two configurations in excited state caused by light in 532 nm irradiation,accompanying with a photo-induced structural transformation o the anionic framework.Namely,the thermal motion characteristics of organic cations,the photoresponse characteristics of anionic inorganic skeleton and the pressure characteristics from hydrogen bonds are si multaneously integrated in 1.This unprecedented coupling mechanism of multi-stimuli responses make1 a potential candidate for future multichannel data storage applications.
基金Financially supported by the National Natural Science Foundation of China (21871027)。
文摘A viologen-bearing Zn(Ⅱ) coordination polymer,[Zn(Bpybc)SO_(4)]·H_(2)O,has been successfully synthesized and structurally characterized.The title compound exhibits sunlight and UV-induced photochromism,thermoschromism,and amine-selective chemochromism.
基金the National Natural Science Foundation of China(NSFC)(nos.21790360,21661132006,and 61890943)the National Key R&D Program of China(2017YFA0204701)+2 种基金the Youth Innovation Promotion Association CAS(no.2015024)for their financial supportWealso thank Dr.Joseph Strzalka and Dr.Zhang Jiang for their assistance with GIWAXS measurementsThe usage of the advanced photon source(APS)at Argonne National Laboratory was supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences under contract no.DE-AC02-06CH11357.
文摘Multi-stimuli-responsive field-effect transistors(FETs)with organic/polymeric semiconductors have received increasing attention.Herein,we report a novel strategy for fabricating multi-stimuliresponsive polymeric semiconductors through the incorporation of spiropyran(SP)groups in the polymer side chains.The semiconducting performances of resultant FETs with a diketopyrrolopyrroles(DPP)-based conjugated donor–acceptor(D–A)polymer,that entails SP units in the side chains(pDSP-1),could be modulated reversibly through UV and visible light irradiations,or UV light irradiation and heating,or acid treatment and heating.Our studies reveal that during the reversible transformations of closed,open,and the protonated forms of spiropyran,achieved by light irradiations,heating,and under acidic conditions,a large dipole moment changes occur,which triggers the reversible variation of semiconducting performance of the FETs.
基金supported by the National Natural Science Foundation of China(51203138,51273179,51573165,51406030)Natural Science Foundation of Zhejiang Province,China(LY15E030006,LY15E030002)+1 种基金Natural Science Foundation of Zhejiang University of Technology,China(1401101002408)Natural Science Foundation of Huzhou,China(2014YZ02)~~
基金the Nature Science Foundation of China(Nos.51803115,81773686 and 21636006)the Nature Science Foundation of Shaanxi Province(No.2019JQ-528)+3 种基金the Fundamental Research Funds for the Central Universities(Nos.2017TS024,GK201801003,GK201802009 and GK201901001)the China Postdoctoral Science Foundation Funded Project(No.2017M623106)Young Talent Fund of University Association for Science and Technology in Shaanxi,China(No.20180602)the Program of Introducing Talents of Discipline to Universities(No.B14041)。
文摘Hyperbranched polymers have attracted increasing interests due to their unique structure-related advantages and have been utilized as drug carriers for controlled delivery.However,it is still challenging to prepare multi stimuli-responsive hyperbranched polymers to sense and response the complex yet delicate changes in physiological environment.Herein,we propose a triple-stimuli backbone-breakable hyperbranched polymer(HBP(OEG-IB)),which is prepared via the convenient iminoboronate multicomponent reaction ofα,ω-di(1,2-diol)s oligo(ethylene glycol),tris(3-aminopropyl)amine and 2-formylphenylboronic acid.Upon the stimulation of CO2,lactic acid and glutathione,micelles formed by HBP(OEG-IB)could be disrupted via the dissociation of iminoboronate ester bond to subsequent release incorporated camptothecin(CPT).Cell experiments show that the HBP(OEG-IB)is non-toxic but can enhance the therapeutic effect of CPT thanks to the effect of the protonated tertiary amino groups.The demonstration made in this work can enrich the design of responsive HBPs and can be readily applied to other systems with tunable responsive properties and functions.
基金the Jilin Province-University Cooperative Construction Project-Special Funds for New Materials (No. SXGJSF2017-3) for financial support
文摘A biopolymer-inorganic hybrid system(MSN@PBLGF) is designed and fabricated from mesoporous silica nanoparticles(MSNs) and folic acid(FA)-terminated temperature-sensitive synthetic polypeptide,i.e.,poly(γ-benzyl-L-glutamate)(PBLG) derivative,through a thiol-disulfide exchange reaction,where MSNs with high drug loading capacity serve as drug nanocarriers and the biocompatible PBLG biopolymer brushes installed on MSN surface through disulfide bonds endow the system with tumor-specific recognition ability and GSH/temperature dual-stimuli responsiveness.Controlled drug release experiments indicate that DOX can be tightly hosted in the system with limited premature release,but efficiently released in response to an increased concentration of GSH and/or an elevated temperature.Intracellular experiments demonstrate that the DOX-loaded MSN@PBLGF nanohybrid shows outstanding cellular uptake and cell-growth inhibition effects on human lung cancer cell line A549 in comparison with healthy human cells such as hepatocyte cells LO2.
