The present review aims to highlight the applications of thermoresponsive polymers.Thermo-responsive polymers show a sharp change in properties upon a small or modest change in temperature.This behaviour can be utiliz...The present review aims to highlight the applications of thermoresponsive polymers.Thermo-responsive polymers show a sharp change in properties upon a small or modest change in temperature.This behaviour can be utilized for the preparation of so-called‘smart’drug delivery systems,which mimic biological response behaviour to a certain extent.Such materials are used in the development of several applications,such as drug delivery systems,tissue engineering scaffolds and gene delivery.Advances in this field are particularly relevant to applications in the areas of regenerative medicine and drug delivery.This review addresses summary of the main applications of thermoresponsive polymers which are categorized based on their 3-dimensional structure;hydrogels,interpenetrating networks,micelles,films and particles.The physico-chemical behaviour underlying the phase transition is also discussed in brief.展开更多
Hybrid drug delivery systems(DDS) have been prepared by grafting poly(NIPAM-co-MPS) chains on multimodal porous silica nanoparticles having an inner mesoporous structure and an outer thin layer of micropores. The hybr...Hybrid drug delivery systems(DDS) have been prepared by grafting poly(NIPAM-co-MPS) chains on multimodal porous silica nanoparticles having an inner mesoporous structure and an outer thin layer of micropores. The hybrid thermoresponsive DDS were fully characterized and loaded with a model drug. The in vitro drug release tests are carried out at below and above the lower critical solution temperature(LCST) of the copolymer. The results have revealed that due to the presence of small diameter(~1.3 nm) micropores at the periphery of the particles, the collapsed globules of the thermoresponsive copolymer above its LCST hinders the complete release of the drug which resulted in a reverse thermoresponsive drug release profile by the hybrid DDS.展开更多
Thermoresponsive fluorescent polymers(TFPs) with unique temperature-dependent luminescent properties are of great importance for the development of new functional devices in recent years. Herein, we facilely synthesiz...Thermoresponsive fluorescent polymers(TFPs) with unique temperature-dependent luminescent properties are of great importance for the development of new functional devices in recent years. Herein, we facilely synthesized an efficient blue-emissive polymer, abbreviated as PCB-TPE, using tetraphenylethene(TPE) as the main building block. PCB-TPE is thermally stable with a novel property of aggregation induced emission(AIE). The thermoresponsive property and mechanism of PCB-TPE were investigated. Its emission shows temperature-dependent features and reveals fine details in the thermal transitions from-10 °C to 60 °C. The polymer offers a platform for the development of efficient luminescent materials for further biological and optoelectronic applications.展开更多
Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena...Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.展开更多
Although many material designs or strategic methods have been proposed for treating oil spills and oily wastewater,the complex oily state,dealing with the harsh operating conditions of oil–water separation(such as th...Although many material designs or strategic methods have been proposed for treating oil spills and oily wastewater,the complex oily state,dealing with the harsh operating conditions of oil–water separation(such as the recovery of viscous spilled crude oil,bacteria-containing oily wastewater,and removal of spilled oil under fire),and the autorecycling of oil and absorption materials remain a great challenge.This work proposed an ingenious design strategy of“several birds with one stone”to prepare p H/thermoresponsive flame-retardant/photothermal bactericidal P-Fe_(3)O_(4)-polydopamine(PDA)@melamine–formaldehyde(MF)foams.This design makes the foams remarkably effective in the recovery of spilled viscous crude oil as well as in the separation of bacteria-containing oily emulsions,particularly for instant fire extinguishing by magnetically controlled oil absorption as well as for fire alarms.The photothermal effect and p H response induce a change in the surface wettability of the foams,facilitating excellent autoadsorption/desorption of the spilled oil.The photothermal bactericidal activity and fouling resistance of the foam are beneficial to the separation of bacteria-containing oily wastewater.Outstanding flame-retardant properties and maneuverable magnetic control enable the foam to rapidly recover the spilled oil in a large range of fires,extinguish fires instantly,and facilitate early fire warning.The proposed strategy is expected to inspire further research on treating oil spills under complex conditions.展开更多
Certain amount of primary amine （NH2） groups of hyperbranched polyethylenimine （HPEI） was first protected by Boc groups. Subsequently, the residual reactive amine groups were reacted with isobutyric anhydride to i...Certain amount of primary amine （NH2） groups of hyperbranched polyethylenimine （HPEI） was first protected by Boc groups. Subsequently, the residual reactive amine groups were reacted with isobutyric anhydride to introduce isobutyramide （IBAm） groups to HPEI. Finally, Boc groups were deprotected to result in HPEI-IBAm-NH2 with 18% of primary amine terminals on the periphery and 80% of IBAm terminal groups （abbreviated as HPEI-IBAm0.80-NH2）. 1H-NMR characterization proved the successful preparation of the product in each step. Compared with its spatial isomer HPEI- IBAm0.8o without primary amine groups, IH-NMR spectra verified that more IBAm groups were located in the interior of HPEI-IBAm0.80-NH2. The further modification of HPEI-IBAmo.so-NH2 and HPEI-IBAmo.8o with p-nitrobenzaldehyde demonstrated that HPEI-IBAm0.so-NH2 was more reactive than HPEI-IBAm0.80 due to its possession of primary amines. Turbidimetry measurements showed that HPEI-IBAm0.80-NH2 was thermoresponsive in water. In the pH range of 9.5-10 its cloud point temperature （Top） was constant, and it increased obviously upon decreasing the pH below 9.5. The thermoresponsive HPEI-IBAmo.8 exhibited the similar trend, but the pH threshold to achieve the constant Top was around 8.5. Moreover, HPEI-IBAm0.8-NH2 showed higher Top and broader phase transition than HPEI-IBAm0.8. The mechanism leading to the different thermoresponsive properties between HPEI-IBAm0.8-NH2 and its spatial isomer HPEI-IBAm0.8 was discussed.展开更多
Stimuli-responsive hydrogels hold an irreplaceable statue in intelligent actuation materials because of their reversible stretchability and excellent biocompatibility.However,the poor mechanical performance and compli...Stimuli-responsive hydrogels hold an irreplaceable statue in intelligent actuation materials because of their reversible stretchability and excellent biocompatibility.However,the poor mechanical performance and complicated fabrication process of anisotropic structures severely limit their further applications.Herein,we report a high-strength thermoresponsive wood-PNIPAM composite hydrogel actuator with complex deformations,through a simple in-situ polymerization.In this composite hydrogel actuator,the anisotropic wood and the thermoresponsive PNIPAM hydrogel hydroel can work together to pro-vide bending and even other complex deformations.Owing to strong interfacial interaction,this actuator perfectly realized the combination of good mechanical properties(∼1.1 MPa)and fast actuation speed(∼0.9 s).In addition,by adjusting the orientation direction of wood,this actuator can achieve various complex deformations.Such composite hydrogel actuator could be a good candidate for intelligent appli-cations,such as intelligent actuators,smart valves,manipulators and even soft robots.展开更多
A double thermoresponsive ABC-type triblock copolymer （poly（ethyleneglycol）-block-poly （2-（2-methoxyethoxy）ethyl methacrylate）-block-poly（2-（2-methoxy ethoxy） ethyl methacrylate-co-oligo（ethylene glycol）...A double thermoresponsive ABC-type triblock copolymer （poly（ethyleneglycol）-block-poly （2-（2-methoxyethoxy）ethyl methacrylate）-block-poly（2-（2-methoxy ethoxy） ethyl methacrylate-co-oligo（ethylene glycol） methyl ether methacrylate, PEG-b-PMEO2MA-b-P（MEO2MA-co-OEGMA）） was designed and synthesized by reversible addition- fragmentation chain transfer polymerization （RAFT）. The ABC-type triblock copolymer endowed a thermal-induced two- step phase transition at 29 and 39 ℃corresponding to the thermosensitive properties of PMEOzMA and P（MEO2MA-co- OEGMA） segments, respectively. The two-step self-assembly of copolymer solutions was studied by UV transmittance measurement, dynamic light scattering （DLS）, transmission electron microscopy （TEM） and so on. The triblock copolymers showed the distinct thermosensitive behavior with respect to transition temperatures, aggregate type and size, which was correlated to the degree of polymerization of thermosensitive blocks and the molar fraction of OEGMA in the P（MEO2MA- co-OEGMA） segments. In addition, micelles could further aggregate to form the hydrogel by the self-associate of PEG chains under the abduction of the concentration and temperature. The transition from sol to gel was investigated by a test tube inverting method and dynamic rheological measurement.展开更多
Thermoresponsive biotinylated dendronized copolymers carrying dendritic oligoethylene glycol（OEG）pendants were prepared via free radical polymerization,and their protein recognitions based on biotin-avidin interacti...Thermoresponsive biotinylated dendronized copolymers carrying dendritic oligoethylene glycol（OEG）pendants were prepared via free radical polymerization,and their protein recognitions based on biotin-avidin interaction investigated.Both first（PG1） and second generation（PG2） dendronized copolymers were designed to examine possible thickness effects on the interaction between biotin and avidin.Inherited from the outstanding thermoresponsive properties from OEG dendrons,these biotinylated cylindrical copolymers show characteristic thermoresponsive behavior which provides an envelope to capture avidin through switching temperatures above or below their phase transition temperatures（T_（cp）s）.Thus,the recognition of polymer-supported biotin with avidin was investigated with UV/vis spectroscopy and dynamic laser light scattering.In contrast to the case for PG1,the increased thickness for copolymer PG2 hinders partially and inhibits the recognition of biotin moieties with avidin either below or above its T_（cp）.This demonstrates the significant architecture effects from dendronized polymers on the biotin moieties to shift onto periphery of the collapsed aggregates,which should be a prerequisite for protein recognition.These kinds of novel thermoresponsive copolymers may pave a way for the interesting biological applications in areas such as reversible activity control of enzyme or proteins,and for controlled delivery of drugs or genes.展开更多
To solve the problem of drying gelcast green body, the thermoresponsive gel system which contains macromonomer graft chains was used in gelcasting of ZnO. The effects of the amount and length of graft chains macromono...To solve the problem of drying gelcast green body, the thermoresponsive gel system which contains macromonomer graft chains was used in gelcasting of ZnO. The effects of the amount and length of graft chains macromonomer PIPAAm, the total amount of organic matters, and the solid loading on the rheological properties of suspensions were investigated, and the drying mechanism of gelcast green body was analyzed. The results show that ZnO suspensions with the gel system still display shear- thinning rheological behavior, but its viscosity increases with increasing the addition amount and relative molecular mass of PIPAAm graft chain, and the total organic matter content. The PIPAAm graft chains inhibit or even eliminate the formation of the ＂dense layer” on the surface of gelcast ZnO green bodies, and accelerate the drying of green bodies. The introduction of PIPAAm graft chains facilitates the shrinkage of the gelcast ZnO green bodies, which is a feasible method to increase the relative density of green bodies.展开更多
Acetamide （C2）, propionamide （C3）, butyramide （C4）, isobutyramide （i-C4）, isovaleramide （i-C5） and trimethylacetamide （t-C5） groups each were introduced to the terminals of hyperbranched polyethylenimine ...Acetamide （C2）, propionamide （C3）, butyramide （C4）, isobutyramide （i-C4）, isovaleramide （i-C5） and trimethylacetamide （t-C5） groups each were introduced to the terminals of hyperbranched polyethylenimine （HPEI） through the amidation reaction between HPEI and the corresponding anhydride. Moreover, HPEIs terminated with two kinds of amides were also prepared. The first amide was fixed to be i-C4 with 52% degree of amidation （DA）, and the second amide varied from C2, C3, C4, i-C5 to t-C5. All the polymers were characterized by 1H-NMR. Turbidimetry measurements were performed for these polymers in water at different temperatures. With respect to the polymers bearing only one kind of amide group, except C2, all the other amide groups could render thermoresponsive properties to HPEI. The specific ordering of these amide groups to reduce the cloud point temperature （Top） was as follows： i-C5 〉 t-C5 〉 C4 〉 i-C4 〉 C3. Moreover, the more branched i-C4 and t-C5 were better groups than their less branched isomers C4 and i-C5 in the Tcp range of 12-51 ~C to render the sharper phase transition to the thermoresponsive polymers. As for the polymers bearing two kinds of amide groups, the further introduction of C2, C3, C4, i-C5 or t-C5 could effectively endow HPEI bearing 52% of i-C4 with thermoresponsive properties. The specific ordering of these second amide groups to reduce the Top was as follows： i-C5 〉 C4 〉 i-C4 〉 C3 〉 C2. C4, i-C5 and t-C5 were all effective second amide groups to prepare the thermoresponsive polymers with sharper phase transition.展开更多
A series of thermoresponsive cationic dendronized copolymers and their corresponding nano gels containing den dritic oligoethylene glycol(OEG)units and guanidine groups were prepared,and their complexation,protect!on,...A series of thermoresponsive cationic dendronized copolymers and their corresponding nano gels containing den dritic oligoethylene glycol(OEG)units and guanidine groups were prepared,and their complexation,protect!on,and release of nucleic acids were investigated.The dendritic OEGs endow these copolymer materials with good biocompatibility and characteristic thermoresponsiveness,while cationic guanidine groups can efficiently bind with the nucleic acids.The dendritic topology also affords the copolymers specific shielding effect which plays an essential role in protecting the activity of nucleic acids.At room temperature,dendronized copolymers and the corresponding nanogels could efficiently capture and condense the nucleic acids,while above their cloud points(Tcps),more than 75%of siRNA could be released in 1 h triggered by ATP.More importantly,the copolymer showed protective capability to siRNA,while nano gels exhibit even better protection when compared to the copolymers due to the synergetic effect from the three-dimensional cross-linked network and high density of dendritic units in vicinity.This kind of smart dendr on ized copolymer nano gels form a no vel class of scaffolds as promisi ng materials for biomedical applicatio ns.展开更多
The monomer 6-O-vinyladipoyl-D-glucopyranose( VAG)was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly( diethyleneglycol methacr...The monomer 6-O-vinyladipoyl-D-glucopyranose( VAG)was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly( diethyleneglycol methacrylate-co-6-Ovinyladipoyl-D-glucopyranose)( P( DEGMA-co-VAG)) with narrow polydispersity( PDI) and thermosensitivity was prepared by reversible addition-fragmentation chain transfer( RAFT)polymerization. P( DEGMA-co-VAG) was characterized by1 H NMR,FTIR and gel permeation chromatography( GPC). The characterization of UV-visible spectroscopy showed that the micelles from glycopolymer P( DEGMA-co-VAG) were thermo-responsive and the low critical solution temperature( LCST) could be controlled by the molar ratio of monomers. When the molar ratio of DEGMA and VAG was 2∶ 1,the LCST of P( DEGMA-co-VAG) was36 ℃ in aqueous solution,which could form nano micelles in the human body environment. It was found that P( DEGMA-co-VAG)was non-toxic at 0. 1-1 mg / m L concentrations when incubated with pig iliac endothelial cells( PIECs) for 24 h. Thus,the synthesized glycopolymers has great potential as drug delivery carriers.展开更多
Thermoresponsive luminescent organic materials have great potential for intelligent optical devices,but their applicability remains limited due to formidable challenges in achieving tunable response temperature and di...Thermoresponsive luminescent organic materials have great potential for intelligent optical devices,but their applicability remains limited due to formidable challenges in achieving tunable response temperature and different colors.In this study,we developed a thermoresponsive polymer/lanthanide ion(Ln^(3+))complex system,enabling precise regulation of luminescence color and response temperature.The polymer was synthesized via copolymerization of acrylamide(Am)with 6-(3-(2-(methacryloyloxy)ethyl)ureido)picolinate(MAUP).The MAUP unit incorporates ligands capable of coordinating with Ln^(3+)and functions as an“antenna”,absorbing incident light and efficiently transferring energy to Ln^(3+),leading to diverse luminescent emissions.The thermoresponsive property of the poly(Am-co-MAUP)/Ln^(3+)complexes,based on the synergy of ionic coordination and hydrogen bonding,imparts the precise regulation of luminescence with temperature.The response temperature of the poly(Amco-MAUP)/Ln^(3+)complexes can be finely tuned by various factors synergistically,including polymer composition and Ln^(3+)concentrations.Moreover,these thermoresponsive luminescent complexes enable potential applications in multi-level information encryption and visual temperature sensing.展开更多
Helical poly(arylacetylene)s have formed an intriguing class of polymers;whose chiralities are dynamic and liable to external stimuli.By combining dendronized polymer topology with dendritic oligoethylene glycols(OEGs...Helical poly(arylacetylene)s have formed an intriguing class of polymers;whose chiralities are dynamic and liable to external stimuli.By combining dendronized polymer topology with dendritic oligoethylene glycols(OEGs);we here report on synthesis of a homologous series of thermoresponsive dendronized poly(arylacetylene)s with either poly(phenyl acetylene)or poly(naphthalene acetylene)as the backbones;and investigate tunability of their helical conformations.These polymers carry dendritic OEG pendants with either methoxyl-or ethoxyl-terminals to tune their unprecedent thermoresponsive behaviors;and at the same time;dendritic shielding plays an important role in mediating their thermal phase transition temperatures.Helicity of these polymers is originated from the chiral alanine or phenylalanine moieties within the dendritic pendants;which can be tailored through manipulating solvation in different organic solvents or via thermal dehydration and collapse in water.Furthermore;achiral additives such as linear or dendritic OEGs and benzene derivatives can act similarly as thermal dehydration to induce chirality transitions of these polymers in aqueous phase through interplay competitions between the additives and the polymers against their hydration.展开更多
CONSPECTUS:Thermoresponsive hydrogels possess an inherent capacity for autonomous adjustment of their properties in response to temperature variations,eliminating the requirement for external power sources and renderi...CONSPECTUS:Thermoresponsive hydrogels possess an inherent capacity for autonomous adjustment of their properties in response to temperature variations,eliminating the requirement for external power sources and rendering them suitable for diverse environmental applications.Our discourse commences by establishing a foundational comprehension of the two principal categories governing thermal transitions in thermoresponsive hydrogels,namely,the Lower Critical Solution Temperature(LCST)and the Upper Critical Solution Temperature(UCST).展开更多
The dynamic regulation of circularly polarized luminescence(CPL)holds profound significance in various fields,such as highlevel information storage and encryption.Here we developed a chiral amphiphilic molecule,CPSB-G...The dynamic regulation of circularly polarized luminescence(CPL)holds profound significance in various fields,such as highlevel information storage and encryption.Here we developed a chiral amphiphilic molecule,CPSB-GLU-PEG350(CGP),composed of aggregation-induced emission(AIE)chromophores(Z)-4-(1-cyano-2-phenylvinyl)benzoic acid(CPSB),a chiral linker Glutamic acid and polyethylene glycol(PEG)thermoresponsive segments.Within the self-assembled supramolecular system formed by CGP,we have achieved in-situ temperature-responsive chiral structures,facilitating the thermal control switch of the CPL signal.Molecular dynamics simulations demonstrate the distinct behaviors of AIE and PEG units during the temperature-variable assembly process.Furthermore,by co-assembling achiral dye molecules with CGP,we have expanded the color range of the temperature-responsive CPL assembly system in situ and confirmed the occurrence of circularly polarizedF?rster resonance energy transfer(C-FRET)phenomenon in this process,which successfully enriched the strategies for in-situ CPL control in aqueous phases.In addition,the contactless radiative energy transfer of CPL can also be realized in this system,exhibiting more flexible temperature regulation of the CPL signal.This study provides a convenient and universal strategy for the construction of dynamically smart chiroptical materials.展开更多
Stimuli-responsive shape-changing materials,particularly hydrogel and liquid crystal elastomer(LCE),have demonstrated significant potential for applications across various fields.Although intricate deformation and act...Stimuli-responsive shape-changing materials,particularly hydrogel and liquid crystal elastomer(LCE),have demonstrated significant potential for applications across various fields.Although intricate deformation and actuation behaviors have been obtained in either hydrogels or LCEs,they typically undergo reversible shape change only once(e.g.,one expansion plus one contraction)during one heating/cooling cycle.Herein,we report a study of a novel liquid crystalline hydrogel(LCH)and the achievement of dual actuation in a single heating/cooling cycle by integrating the characteristics of thermoresponsive hydrogel and LCE.The dual actuation behavior arises from the reversible volume phase transition of poly(N-isopropylacrylamide)(PNIPAM)and the reversible order-disorder phase transition of LC mesogens in the LCH.Due to a temperature window separating the two transitions belonging to PNIPAM and LCE,LCH actuator can sequentially execute their respective actuation,thus deforming reversibly twice,during a heating/cooling cycle.The relative actuation degree of the two mechanisms is influenced by the mass ratio of PNIPAM to LCE in the LCH.Moreover,the initial shape of a bilayer actuator made with an active LCH layer and a passive polymer layer can be altered through hydration or dehydration of PNIPAM,which further modifies the dual actuation induced deformation.This work provides an example that shows the interest of developing LCH actuators.展开更多
Plants are capable of coordination of their growth and development with ambient temperatures.EARLY FLOWERING3(ELF3), an essential component of the plant circadian clock, is also involved in ambient temperature sensing...Plants are capable of coordination of their growth and development with ambient temperatures.EARLY FLOWERING3(ELF3), an essential component of the plant circadian clock, is also involved in ambient temperature sensing, as well as in inhibiting the expression and protein activity of the thermoresponsive regulator phytochrome interacting factor4(PIF4). The ELF3 activity is subjected to attenuation in response to warm temperature;however,how the protein level of ELF3 is regulated at warm temperature remains less understood. Here, we report that the E3 ligase XB3 ORTHOLOG 5 IN ARABIDOPSIS THALIANA, XBAT35, mediates ELF3 degradation. XBAT35 interacts with ELF3 and ubiquitinates ELF3. Loss-of-function mutation of XBAT35 increases the protein level of ELF3 and confers a short-hypocotyl phenotype under warm temperature conditions. Thus, our findings establish that XBAT35 mediates ELF3 degradation to lift the inhibition of ELF3 on PIF4 for promoting thermoresponsive hypocotyl growth in plants.展开更多
Thermoresponsive polymers with simultaneous biodegradability and signal“self-reporting”outputs that meet for advanced applications are hard to obtain.To address this issue,we developed fluorescence signal“self-repo...Thermoresponsive polymers with simultaneous biodegradability and signal“self-reporting”outputs that meet for advanced applications are hard to obtain.To address this issue,we developed fluorescence signal“self-reporting”biodegradable thermoresponsive polycarbonates through the immortal copolymerization of CO_(2)and oligoethylene glycol monomethyl ether-functionalized epoxides in the presence of hydroxyl-modified tetraphenylethylene(TPE-OH).TPE-OH was used as chain transfer agent to afford well-defined polycarbonates with controlled molecular weight(6000—17000 g·mol^(–1))and aggregation-induced emission characteristics.Through temperature-dependent fluorescence intensity study,low critical solution transition of TPE-labeled polycarbonates were determined and the fine details of thermal-induced phase transition process were monitored.Further research indicated that temperature-controlled aggregation and dissociation of TPE moieties are the main reason for fluorescence intensity variations.We anticipate that this work could offer a method to visualize the thermal transition process of thermoresponsive polycarbonates and broaden their application fields as smart materials.展开更多
文摘The present review aims to highlight the applications of thermoresponsive polymers.Thermo-responsive polymers show a sharp change in properties upon a small or modest change in temperature.This behaviour can be utilized for the preparation of so-called‘smart’drug delivery systems,which mimic biological response behaviour to a certain extent.Such materials are used in the development of several applications,such as drug delivery systems,tissue engineering scaffolds and gene delivery.Advances in this field are particularly relevant to applications in the areas of regenerative medicine and drug delivery.This review addresses summary of the main applications of thermoresponsive polymers which are categorized based on their 3-dimensional structure;hydrogels,interpenetrating networks,micelles,films and particles.The physico-chemical behaviour underlying the phase transition is also discussed in brief.
文摘Hybrid drug delivery systems(DDS) have been prepared by grafting poly(NIPAM-co-MPS) chains on multimodal porous silica nanoparticles having an inner mesoporous structure and an outer thin layer of micropores. The hybrid thermoresponsive DDS were fully characterized and loaded with a model drug. The in vitro drug release tests are carried out at below and above the lower critical solution temperature(LCST) of the copolymer. The results have revealed that due to the presence of small diameter(~1.3 nm) micropores at the periphery of the particles, the collapsed globules of the thermoresponsive copolymer above its LCST hinders the complete release of the drug which resulted in a reverse thermoresponsive drug release profile by the hybrid DDS.
基金financially supported by the National Natural Science Foundation of China (No. 21374136)the Fundamental Research Funds for the Central Universities (Nos. 17lgjc03 and 18lgpy04)the Opening Project of the Key Laboratory of Polymer Processing Engineering (South China University of Technology, Ministry of Education, No. KFKT1703)
文摘Thermoresponsive fluorescent polymers(TFPs) with unique temperature-dependent luminescent properties are of great importance for the development of new functional devices in recent years. Herein, we facilely synthesized an efficient blue-emissive polymer, abbreviated as PCB-TPE, using tetraphenylethene(TPE) as the main building block. PCB-TPE is thermally stable with a novel property of aggregation induced emission(AIE). The thermoresponsive property and mechanism of PCB-TPE were investigated. Its emission shows temperature-dependent features and reveals fine details in the thermal transitions from-10 °C to 60 °C. The polymer offers a platform for the development of efficient luminescent materials for further biological and optoelectronic applications.
基金financially supported by the National Natural Science Foundation of China(Nos.21274030,51473038 and 21604024)the Natural Science Foundation of Shanghai(No.17ZR1440400)+1 种基金the Open Project of State Key Laboratory of Chemical Engineering(No.SKL-Ch E-16C02)“Chenguang Plan”
文摘Generalized two-dimensional correlation spectroscopy （2DCOS） and its derivate technique, perturbation correlation moving window （PCMW）, have found great potential in studying a series of physico-chemical phenomena in stimuli-responsive polymeric systems. By spreading peaks along a second dimension, 2DCOS can significantly enhance spectral resolution and discern the sequence of group dynamics applicable to various external perturbation-induced spectroscopic changes, especially in infrared （IR）, near-infrared （NIR） and Raman spectroscopy. On the basis of 2DCOS synchronous power spectra changing, PCMW proves to be a powerful tool to monitor complicated spectral variations and to find transition points and ranges. This article reviews the recent work of our research group in the application of 2DCOS and PCMW in thermoresponsive polymers, mainly focused on liquid crystalline polymers and lower critical solution temperature （LCST）-type polymers. Details of group motions and chain conformational changes upon temperature perturbation can thus be elucidated at the molecular level, which contribute to the understanding of their phase transition nature.
基金financially supported by the National Natural Science Foundation of China(No.22078077)the National Science Foundation of Guangdong Province(No.2021A1515010078)financial support of Taif University Researchers Supporting Project(No.TURSP-2020/14),Taif University,Taif,Saudi Arabia。
文摘Although many material designs or strategic methods have been proposed for treating oil spills and oily wastewater,the complex oily state,dealing with the harsh operating conditions of oil–water separation(such as the recovery of viscous spilled crude oil,bacteria-containing oily wastewater,and removal of spilled oil under fire),and the autorecycling of oil and absorption materials remain a great challenge.This work proposed an ingenious design strategy of“several birds with one stone”to prepare p H/thermoresponsive flame-retardant/photothermal bactericidal P-Fe_(3)O_(4)-polydopamine(PDA)@melamine–formaldehyde(MF)foams.This design makes the foams remarkably effective in the recovery of spilled viscous crude oil as well as in the separation of bacteria-containing oily emulsions,particularly for instant fire extinguishing by magnetically controlled oil absorption as well as for fire alarms.The photothermal effect and p H response induce a change in the surface wettability of the foams,facilitating excellent autoadsorption/desorption of the spilled oil.The photothermal bactericidal activity and fouling resistance of the foam are beneficial to the separation of bacteria-containing oily wastewater.Outstanding flame-retardant properties and maneuverable magnetic control enable the foam to rapidly recover the spilled oil in a large range of fires,extinguish fires instantly,and facilitate early fire warning.The proposed strategy is expected to inspire further research on treating oil spills under complex conditions.
基金financially supported by the financial support from the Program for New Century Excellent Talents in Universitiesthe National Natural Science Foundation of China(Nos.20804027 and 21274106)
文摘Certain amount of primary amine （NH2） groups of hyperbranched polyethylenimine （HPEI） was first protected by Boc groups. Subsequently, the residual reactive amine groups were reacted with isobutyric anhydride to introduce isobutyramide （IBAm） groups to HPEI. Finally, Boc groups were deprotected to result in HPEI-IBAm-NH2 with 18% of primary amine terminals on the periphery and 80% of IBAm terminal groups （abbreviated as HPEI-IBAm0.80-NH2）. 1H-NMR characterization proved the successful preparation of the product in each step. Compared with its spatial isomer HPEI- IBAm0.8o without primary amine groups, IH-NMR spectra verified that more IBAm groups were located in the interior of HPEI-IBAm0.80-NH2. The further modification of HPEI-IBAmo.so-NH2 and HPEI-IBAmo.8o with p-nitrobenzaldehyde demonstrated that HPEI-IBAm0.so-NH2 was more reactive than HPEI-IBAm0.80 due to its possession of primary amines. Turbidimetry measurements showed that HPEI-IBAm0.80-NH2 was thermoresponsive in water. In the pH range of 9.5-10 its cloud point temperature （Top） was constant, and it increased obviously upon decreasing the pH below 9.5. The thermoresponsive HPEI-IBAmo.8 exhibited the similar trend, but the pH threshold to achieve the constant Top was around 8.5. Moreover, HPEI-IBAm0.8-NH2 showed higher Top and broader phase transition than HPEI-IBAm0.8. The mechanism leading to the different thermoresponsive properties between HPEI-IBAm0.8-NH2 and its spatial isomer HPEI-IBAm0.8 was discussed.
基金supported by the National Natural Science Foundation of China(Nos.51803093,51903123)Natu-ral Science Foundation of Jiangsu Province(No.BK20190760)+1 种基金Open Project of Chemistry Department of Qingdao University of Science and Technology(No.QUSTHX201921)Open Fund of Fujian Provincial Key Laboratory of Eco-Industrial Green Technology,China(Nos.WYKF-EIGT2020–3,WYKF-GC2021–1).
文摘Stimuli-responsive hydrogels hold an irreplaceable statue in intelligent actuation materials because of their reversible stretchability and excellent biocompatibility.However,the poor mechanical performance and complicated fabrication process of anisotropic structures severely limit their further applications.Herein,we report a high-strength thermoresponsive wood-PNIPAM composite hydrogel actuator with complex deformations,through a simple in-situ polymerization.In this composite hydrogel actuator,the anisotropic wood and the thermoresponsive PNIPAM hydrogel hydroel can work together to pro-vide bending and even other complex deformations.Owing to strong interfacial interaction,this actuator perfectly realized the combination of good mechanical properties(∼1.1 MPa)and fast actuation speed(∼0.9 s).In addition,by adjusting the orientation direction of wood,this actuator can achieve various complex deformations.Such composite hydrogel actuator could be a good candidate for intelligent appli-cations,such as intelligent actuators,smart valves,manipulators and even soft robots.
基金financially supported by the National Natural Science Foundation of China(No.20973106)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT_14R33)
文摘A double thermoresponsive ABC-type triblock copolymer （poly（ethyleneglycol）-block-poly （2-（2-methoxyethoxy）ethyl methacrylate）-block-poly（2-（2-methoxy ethoxy） ethyl methacrylate-co-oligo（ethylene glycol） methyl ether methacrylate, PEG-b-PMEO2MA-b-P（MEO2MA-co-OEGMA）） was designed and synthesized by reversible addition- fragmentation chain transfer polymerization （RAFT）. The ABC-type triblock copolymer endowed a thermal-induced two- step phase transition at 29 and 39 ℃corresponding to the thermosensitive properties of PMEOzMA and P（MEO2MA-co- OEGMA） segments, respectively. The two-step self-assembly of copolymer solutions was studied by UV transmittance measurement, dynamic light scattering （DLS）, transmission electron microscopy （TEM） and so on. The triblock copolymers showed the distinct thermosensitive behavior with respect to transition temperatures, aggregate type and size, which was correlated to the degree of polymerization of thermosensitive blocks and the molar fraction of OEGMA in the P（MEO2MA- co-OEGMA） segments. In addition, micelles could further aggregate to form the hydrogel by the self-associate of PEG chains under the abduction of the concentration and temperature. The transition from sol to gel was investigated by a test tube inverting method and dynamic rheological measurement.
基金the National Natural Science Foundation of China(Nos.21374058,21474060 and 21574078)the Ph.D. Programs Foundation of Ministry of Education of China(No 201331081100166)the Shanghai Rising-Star Program(No.16QA1401800)
文摘Thermoresponsive biotinylated dendronized copolymers carrying dendritic oligoethylene glycol（OEG）pendants were prepared via free radical polymerization,and their protein recognitions based on biotin-avidin interaction investigated.Both first（PG1） and second generation（PG2） dendronized copolymers were designed to examine possible thickness effects on the interaction between biotin and avidin.Inherited from the outstanding thermoresponsive properties from OEG dendrons,these biotinylated cylindrical copolymers show characteristic thermoresponsive behavior which provides an envelope to capture avidin through switching temperatures above or below their phase transition temperatures（T_（cp）s）.Thus,the recognition of polymer-supported biotin with avidin was investigated with UV/vis spectroscopy and dynamic laser light scattering.In contrast to the case for PG1,the increased thickness for copolymer PG2 hinders partially and inhibits the recognition of biotin moieties with avidin either below or above its T_（cp）.This demonstrates the significant architecture effects from dendronized polymers on the biotin moieties to shift onto periphery of the collapsed aggregates,which should be a prerequisite for protein recognition.These kinds of novel thermoresponsive copolymers may pave a way for the interesting biological applications in areas such as reversible activity control of enzyme or proteins,and for controlled delivery of drugs or genes.
基金Project(51202296)supported by the National Natural Science Foundation of ChinaProject supported by the State Key Laboratory of Powder Metallurgy,Central South University,China
文摘To solve the problem of drying gelcast green body, the thermoresponsive gel system which contains macromonomer graft chains was used in gelcasting of ZnO. The effects of the amount and length of graft chains macromonomer PIPAAm, the total amount of organic matters, and the solid loading on the rheological properties of suspensions were investigated, and the drying mechanism of gelcast green body was analyzed. The results show that ZnO suspensions with the gel system still display shear- thinning rheological behavior, but its viscosity increases with increasing the addition amount and relative molecular mass of PIPAAm graft chain, and the total organic matter content. The PIPAAm graft chains inhibit or even eliminate the formation of the ＂dense layer” on the surface of gelcast ZnO green bodies, and accelerate the drying of green bodies. The introduction of PIPAAm graft chains facilitates the shrinkage of the gelcast ZnO green bodies, which is a feasible method to increase the relative density of green bodies.
基金financially supported by the Program for New Century Excellent Talents in Universitiesthe National Natural Science Foundation of China(Nos.20804027 and 21274106)
文摘Acetamide （C2）, propionamide （C3）, butyramide （C4）, isobutyramide （i-C4）, isovaleramide （i-C5） and trimethylacetamide （t-C5） groups each were introduced to the terminals of hyperbranched polyethylenimine （HPEI） through the amidation reaction between HPEI and the corresponding anhydride. Moreover, HPEIs terminated with two kinds of amides were also prepared. The first amide was fixed to be i-C4 with 52% degree of amidation （DA）, and the second amide varied from C2, C3, C4, i-C5 to t-C5. All the polymers were characterized by 1H-NMR. Turbidimetry measurements were performed for these polymers in water at different temperatures. With respect to the polymers bearing only one kind of amide group, except C2, all the other amide groups could render thermoresponsive properties to HPEI. The specific ordering of these amide groups to reduce the cloud point temperature （Top） was as follows： i-C5 〉 t-C5 〉 C4 〉 i-C4 〉 C3. Moreover, the more branched i-C4 and t-C5 were better groups than their less branched isomers C4 and i-C5 in the Tcp range of 12-51 ~C to render the sharper phase transition to the thermoresponsive polymers. As for the polymers bearing two kinds of amide groups, the further introduction of C2, C3, C4, i-C5 or t-C5 could effectively endow HPEI bearing 52% of i-C4 with thermoresponsive properties. The specific ordering of these second amide groups to reduce the Top was as follows： i-C5 〉 C4 〉 i-C4 〉 C3 〉 C2. C4, i-C5 and t-C5 were all effective second amide groups to prepare the thermoresponsive polymers with sharper phase transition.
基金the National Natural Science Foundation of China(Nos.21971161,21971160,and 21574078)Shanghai Pujiang Program(No.19PJ1403700)Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.
文摘A series of thermoresponsive cationic dendronized copolymers and their corresponding nano gels containing den dritic oligoethylene glycol(OEG)units and guanidine groups were prepared,and their complexation,protect!on,and release of nucleic acids were investigated.The dendritic OEGs endow these copolymer materials with good biocompatibility and characteristic thermoresponsiveness,while cationic guanidine groups can efficiently bind with the nucleic acids.The dendritic topology also affords the copolymers specific shielding effect which plays an essential role in protecting the activity of nucleic acids.At room temperature,dendronized copolymers and the corresponding nanogels could efficiently capture and condense the nucleic acids,while above their cloud points(Tcps),more than 75%of siRNA could be released in 1 h triggered by ATP.More importantly,the copolymer showed protective capability to siRNA,while nano gels exhibit even better protection when compared to the copolymers due to the synergetic effect from the three-dimensional cross-linked network and high density of dendritic units in vicinity.This kind of smart dendr on ized copolymer nano gels form a no vel class of scaffolds as promisi ng materials for biomedical applicatio ns.
基金National Natural Science Foundation of China(No.21303014)
文摘The monomer 6-O-vinyladipoyl-D-glucopyranose( VAG)was synthesized by lipase catalyzed trans-esterification of divinyladipate with D-glucopyranose. A novel double hydrophilic glycopolymer poly( diethyleneglycol methacrylate-co-6-Ovinyladipoyl-D-glucopyranose)( P( DEGMA-co-VAG)) with narrow polydispersity( PDI) and thermosensitivity was prepared by reversible addition-fragmentation chain transfer( RAFT)polymerization. P( DEGMA-co-VAG) was characterized by1 H NMR,FTIR and gel permeation chromatography( GPC). The characterization of UV-visible spectroscopy showed that the micelles from glycopolymer P( DEGMA-co-VAG) were thermo-responsive and the low critical solution temperature( LCST) could be controlled by the molar ratio of monomers. When the molar ratio of DEGMA and VAG was 2∶ 1,the LCST of P( DEGMA-co-VAG) was36 ℃ in aqueous solution,which could form nano micelles in the human body environment. It was found that P( DEGMA-co-VAG)was non-toxic at 0. 1-1 mg / m L concentrations when incubated with pig iliac endothelial cells( PIECs) for 24 h. Thus,the synthesized glycopolymers has great potential as drug delivery carriers.
基金supported by the Ningbo Youth Leading Talent Project(2024QL020)the National Natural Science Foundation of China(52373118 and 22075154)+1 种基金the“Mechanics+”Interdisciplinary Top Innovative Youth Fund Project of Ningbo University(LJ2024006)the Ningbo Major Science and Technology Project(2024Z205)。
文摘Thermoresponsive luminescent organic materials have great potential for intelligent optical devices,but their applicability remains limited due to formidable challenges in achieving tunable response temperature and different colors.In this study,we developed a thermoresponsive polymer/lanthanide ion(Ln^(3+))complex system,enabling precise regulation of luminescence color and response temperature.The polymer was synthesized via copolymerization of acrylamide(Am)with 6-(3-(2-(methacryloyloxy)ethyl)ureido)picolinate(MAUP).The MAUP unit incorporates ligands capable of coordinating with Ln^(3+)and functions as an“antenna”,absorbing incident light and efficiently transferring energy to Ln^(3+),leading to diverse luminescent emissions.The thermoresponsive property of the poly(Am-co-MAUP)/Ln^(3+)complexes,based on the synergy of ionic coordination and hydrogen bonding,imparts the precise regulation of luminescence with temperature.The response temperature of the poly(Amco-MAUP)/Ln^(3+)complexes can be finely tuned by various factors synergistically,including polymer composition and Ln^(3+)concentrations.Moreover,these thermoresponsive luminescent complexes enable potential applications in multi-level information encryption and visual temperature sensing.
基金supported by the National Natural Science Foundation of China(22271183,22371179,21971160).
文摘Helical poly(arylacetylene)s have formed an intriguing class of polymers;whose chiralities are dynamic and liable to external stimuli.By combining dendronized polymer topology with dendritic oligoethylene glycols(OEGs);we here report on synthesis of a homologous series of thermoresponsive dendronized poly(arylacetylene)s with either poly(phenyl acetylene)or poly(naphthalene acetylene)as the backbones;and investigate tunability of their helical conformations.These polymers carry dendritic OEG pendants with either methoxyl-or ethoxyl-terminals to tune their unprecedent thermoresponsive behaviors;and at the same time;dendritic shielding plays an important role in mediating their thermal phase transition temperatures.Helicity of these polymers is originated from the chiral alanine or phenylalanine moieties within the dendritic pendants;which can be tailored through manipulating solvation in different organic solvents or via thermal dehydration and collapse in water.Furthermore;achiral additives such as linear or dendritic OEGs and benzene derivatives can act similarly as thermal dehydration to induce chirality transitions of these polymers in aqueous phase through interplay competitions between the additives and the polymers against their hydration.
基金funding support from the Global STEM Professorship Scheme sponsored by the Government of Hong Kong Special Administrative RegionStart-up funding from The Chinese University of Hong Kong.
文摘CONSPECTUS:Thermoresponsive hydrogels possess an inherent capacity for autonomous adjustment of their properties in response to temperature variations,eliminating the requirement for external power sources and rendering them suitable for diverse environmental applications.Our discourse commences by establishing a foundational comprehension of the two principal categories governing thermal transitions in thermoresponsive hydrogels,namely,the Lower Critical Solution Temperature(LCST)and the Upper Critical Solution Temperature(UCST).
基金supported by the National Natural Science Foundation of China(22301206,22301208 and 92356305)the Natural Science Foundation of Anhui Province(2308085J15)+3 种基金the China Postdoctoral Science Foundation(2022M722312)the Jiangsu Natural Science Foundation(BK20230505)the Jiangsu Funding Program for Excellent Postdoctoral Talentthe Natural Science Foundation of Anhui Provincial Higher Education Institutions(2023AH010012)。
文摘The dynamic regulation of circularly polarized luminescence(CPL)holds profound significance in various fields,such as highlevel information storage and encryption.Here we developed a chiral amphiphilic molecule,CPSB-GLU-PEG350(CGP),composed of aggregation-induced emission(AIE)chromophores(Z)-4-(1-cyano-2-phenylvinyl)benzoic acid(CPSB),a chiral linker Glutamic acid and polyethylene glycol(PEG)thermoresponsive segments.Within the self-assembled supramolecular system formed by CGP,we have achieved in-situ temperature-responsive chiral structures,facilitating the thermal control switch of the CPL signal.Molecular dynamics simulations demonstrate the distinct behaviors of AIE and PEG units during the temperature-variable assembly process.Furthermore,by co-assembling achiral dye molecules with CGP,we have expanded the color range of the temperature-responsive CPL assembly system in situ and confirmed the occurrence of circularly polarizedF?rster resonance energy transfer(C-FRET)phenomenon in this process,which successfully enriched the strategies for in-situ CPL control in aqueous phases.In addition,the contactless radiative energy transfer of CPL can also be realized in this system,exhibiting more flexible temperature regulation of the CPL signal.This study provides a convenient and universal strategy for the construction of dynamically smart chiroptical materials.
基金financial support from the Natural Sciences and Engineering Research Council of Canada(NSERC),le Fonds de recherche du Québec:Nature et technologies(FRQNT),and The Centre québécois sur les matériaux fonctionnels.
文摘Stimuli-responsive shape-changing materials,particularly hydrogel and liquid crystal elastomer(LCE),have demonstrated significant potential for applications across various fields.Although intricate deformation and actuation behaviors have been obtained in either hydrogels or LCEs,they typically undergo reversible shape change only once(e.g.,one expansion plus one contraction)during one heating/cooling cycle.Herein,we report a study of a novel liquid crystalline hydrogel(LCH)and the achievement of dual actuation in a single heating/cooling cycle by integrating the characteristics of thermoresponsive hydrogel and LCE.The dual actuation behavior arises from the reversible volume phase transition of poly(N-isopropylacrylamide)(PNIPAM)and the reversible order-disorder phase transition of LC mesogens in the LCH.Due to a temperature window separating the two transitions belonging to PNIPAM and LCE,LCH actuator can sequentially execute their respective actuation,thus deforming reversibly twice,during a heating/cooling cycle.The relative actuation degree of the two mechanisms is influenced by the mass ratio of PNIPAM to LCE in the LCH.Moreover,the initial shape of a bilayer actuator made with an active LCH layer and a passive polymer layer can be altered through hydration or dehydration of PNIPAM,which further modifies the dual actuation induced deformation.This work provides an example that shows the interest of developing LCH actuators.
基金project was financially supported by grants from the National Natural Science Foundation of China(31625004 and 31872653)the Zhejiang Provincial Talent Program(2019R52005)+1 种基金the BBSRC(BB/N018540/1)the 111 Project(B14027)。
文摘Plants are capable of coordination of their growth and development with ambient temperatures.EARLY FLOWERING3(ELF3), an essential component of the plant circadian clock, is also involved in ambient temperature sensing, as well as in inhibiting the expression and protein activity of the thermoresponsive regulator phytochrome interacting factor4(PIF4). The ELF3 activity is subjected to attenuation in response to warm temperature;however,how the protein level of ELF3 is regulated at warm temperature remains less understood. Here, we report that the E3 ligase XB3 ORTHOLOG 5 IN ARABIDOPSIS THALIANA, XBAT35, mediates ELF3 degradation. XBAT35 interacts with ELF3 and ubiquitinates ELF3. Loss-of-function mutation of XBAT35 increases the protein level of ELF3 and confers a short-hypocotyl phenotype under warm temperature conditions. Thus, our findings establish that XBAT35 mediates ELF3 degradation to lift the inhibition of ELF3 on PIF4 for promoting thermoresponsive hypocotyl growth in plants.
基金the financial support from the Fundamental Science Center projector in National Natural Science Foundation of China(Grant No.51988102)Key Research Program of Frontier Sciences,CAS(Grant No.QYZDJ-SSW-JSC017).
文摘Thermoresponsive polymers with simultaneous biodegradability and signal“self-reporting”outputs that meet for advanced applications are hard to obtain.To address this issue,we developed fluorescence signal“self-reporting”biodegradable thermoresponsive polycarbonates through the immortal copolymerization of CO_(2)and oligoethylene glycol monomethyl ether-functionalized epoxides in the presence of hydroxyl-modified tetraphenylethylene(TPE-OH).TPE-OH was used as chain transfer agent to afford well-defined polycarbonates with controlled molecular weight(6000—17000 g·mol^(–1))and aggregation-induced emission characteristics.Through temperature-dependent fluorescence intensity study,low critical solution transition of TPE-labeled polycarbonates were determined and the fine details of thermal-induced phase transition process were monitored.Further research indicated that temperature-controlled aggregation and dissociation of TPE moieties are the main reason for fluorescence intensity variations.We anticipate that this work could offer a method to visualize the thermal transition process of thermoresponsive polycarbonates and broaden their application fields as smart materials.
