Negatively thermo-responsive 2D membranes,which mimic the stomatal opening/closing of plants,have drawn substantial interest for tunable molecular separation processes.However,these membranes are still restricted sign...Negatively thermo-responsive 2D membranes,which mimic the stomatal opening/closing of plants,have drawn substantial interest for tunable molecular separation processes.However,these membranes are still restricted significantly on account of low water permeability and poor dynamic tunability of 2D nanochannels under temperature stimulation.Here,we present a biomimetic negatively thermo-responsive MXene membrane by covalently grafting poly(N-isopropylacrylamide)(PNIPAm)onto MXene nanosheets.The uniformly grafted PNIPAm polymer chains can enlarge the interlayer spacings for increasing water permeability while also allowing more tunability of 2D nanochannels for enhancing the capability of gradually separating multiple molecules of different sizes.As expected,the constructed membrane exhibits ultrahigh water permeance of 95.6 L m^(-2) h^(-1) bar^(-1) at 25℃,which is eight-fold higher than the state-of-the-art negatively thermoresponsive 2D membranes.Moreover,the highly temperature-tunable 2D nanochannels enable the constructed membrane to perform excellent graded molecular sieving for dye-and antibiotic-based ternary mixtures.This strategy provides new perspectives in engineering smart 2D membrane and expands the scope of temperature-responsive membranes,showing promising applications in micro/nanofluidics and molecular separation.展开更多
The effect of graft yield on both the thermo-responsive hydraulicpermeability and the therrno-responsive diffusional permeability through porous membranes withplasma-grafted poly(N-isopropylacrylamide) (PNIPAM) gates ...The effect of graft yield on both the thermo-responsive hydraulicpermeability and the therrno-responsive diffusional permeability through porous membranes withplasma-grafted poly(N-isopropylacrylamide) (PNIPAM) gates was investigated. Both thermo-responsiveflat membranes and core-shell microcapsule membranes with a wide range of graft yield of PNIPAM wereprepared using a plasma-graft pore-filling polymerization method. The grafted PNIPAM was formedhomogeneously throughout the entire thickness of both the flat polyethylene membranes and themicrocapsule polyamide membranes. Both the hydraulic permeability and the diffusional permeabilitywere heavily dependent on the PNIPAM graft yield. With increasing the graft yield, the hydraulicpermeability (water flux) decreases rapidly at 25℃ because of the decrease of the pore size;however, the water flux at 40℃ increases firstly to a peak because of the increase ofhydrophobicity of the pore surface, and then decreases and finally tends to zero because of the poresize becoming smaller and smaller. For the diffusional permeability, the temperature showsdifferent effects on the diffusional permeability coefficients of solutes across the membranes. Whenthe graft yield was low, the diffusional coefficient of solute across the membrane was higher attemperature above the lower critical solution temperature (LCST) than that below the LCST; however,when the graft yield was high, the diffusional coefficient was lower at temperature above the LCSTthan that below the LCST. It is very important to choose or design a proper graft yield of PNIPAMfor obtaining a desired thermo-responsive 'on/off' hydraulic or diffusional permeability.展开更多
Halloysite nanotube-composited thermo-responsive hydrogel system has been successfully developed for controlled drug release by copolymerization of N-isopropylacrylamide (NIPAM) with silane-modified halloysite nanot...Halloysite nanotube-composited thermo-responsive hydrogel system has been successfully developed for controlled drug release by copolymerization of N-isopropylacrylamide (NIPAM) with silane-modified halloysite nanotubes (HNT) through thermally initiated free-radical polymerization. With methylene blue as a model drug, thermo-responsive drug release results demonstrate that the drug release from the nanotubes in the composited hy-drogel can^be well controlled by manipulating the environmental temperature. When the hydrogel network is swol- len at temperature below the lower critical solution temperature (LCST), drug releases steadily from lumens of the embedded nanotubes, whereas the drug release stops when hydrogel shrinks at temperature above the LCST. The release of model drug from the HNT-composited hydrogel matches well with its thermo-responsive volume phasetransition, and shows characteristics of well controlled release. The design strategy and release results of the pro- posed novel HNT-composited thermo-responsive hydrogel system provide valuable guidance for designing respon- s_i_ve nanocomposites for controlled-release of active agents.展开更多
The monodisperse Au@Ag bimetallic nanorod is encapsulated by crosslinked poly( N-isopropylacrylamide)( PNIPAM) to produce thermo-responsive composite microgel with well-defined core-shell structure( Au@ Ag NR@ PNIPAM ...The monodisperse Au@Ag bimetallic nanorod is encapsulated by crosslinked poly( N-isopropylacrylamide)( PNIPAM) to produce thermo-responsive composite microgel with well-defined core-shell structure( Au@ Ag NR@ PNIPAM microgel)by seed-precipitation polymerization method using butenoic acid modified Au @ Ag NRs as seeds. When the temperature of the aqueous medium increases from 20℃ to 50℃,the localized surface plasmon resonance( LSPR) band of the entrapped Au @ Ag NR is pronouncedly red-shifted because of the decreased spatial distances between them as a result of shrinkage of the microgels,leading to their plasmonic coupling. The temperature tunable plasmonic coupling is demonstrated by temperature dependence of the surface enhanced Raman spectroscopy( SERS) signal of 1-naphthol in aqueous solution. Different from static plasmonic coupling modes from nanostructured assembly or array system of noble metals,the proposed plasmonic coupling can be dynamically controlled by environmental temperature. Therefore, the thermo responsive hybrid microgels have potential applications in mobile LSPR or SERS microsensors for living tissues or cells.展开更多
Thermo-responsive multiblock polycarbonates were facilely synthesized by covalently binding poly(ethylene glycol)(PEG) and poly(propylene glycol)(PPG) blocks,using triphosgene as coupling agent and pyridine as catalys...Thermo-responsive multiblock polycarbonates were facilely synthesized by covalently binding poly(ethylene glycol)(PEG) and poly(propylene glycol)(PPG) blocks,using triphosgene as coupling agent and pyridine as catalyst.The aqueous solutions of thermo-responsive polycarbonates were investigated by rheological measurements.Steady-state shear measurements reveal that the polycarbonate solutions exhibit shear-thinning behavior and the hydrophilic content has a pronounced effect on the flow behavior of the polycarbonates aqueous solutions.The shear viscosity decreases with increasing poly(ethylene oxide)(PEO) composition.The increase of viscosity with increasing concentration is probably attributed to the formation of stronger network owing to interchain entanglement of PEO block at higher concentration.When the flow curves are fitted to the power law model,flow index is obtained to be less than 1,as exhibiting typical pesudoplastic fluid.The viscoelastic properties of the system also show close dependence on the composition of polycarbonates.Temperature sweep confirms that the multiblock polycarbonates exhibit thermo-responsive properties.For 7% aqueous solution of polycarbonate with composition ratio of EO to PO of 1/1,the sol-gel transition occurs at 37 ℃,which makes the system suitable as an injectable drug delivery system.展开更多
Thermo-respansive chitosan hydrogel system (TRCHS) was prepared and its mierostructure was investigated by scaning electron microscope (SEM) and mercury intrusion poremaster (MIP). Based on analyzing the data, a...Thermo-respansive chitosan hydrogel system (TRCHS) was prepared and its mierostructure was investigated by scaning electron microscope (SEM) and mercury intrusion poremaster (MIP). Based on analyzing the data, a special porosity property was reported at the first time. Its gelling mechanism was studied by a group of contrast experiments. Results may provide experimental and theoretical supports for how to apply it on tissue engineering scaffold and how to influeuee or control its essential properties.展开更多
Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylen...Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.展开更多
As a new concept having emerged in last few years,the“deep eutectic solvents”(DESs)effect integrated into the imprinting technology inevitably exposes design limitations of stimuli-responsive molecularly imprinted p...As a new concept having emerged in last few years,the“deep eutectic solvents”(DESs)effect integrated into the imprinting technology inevitably exposes design limitations of stimuli-responsive molecularly imprinted polymers(MIPs),as well as inadequate analysis of the adsorption performance of MIPs.Herein,a simple yet defined N-isopropylacrylamide/(3-acrylamidopropyl)trimethylammonium chloride(NIPAM/APTMAC)binary DESs system was proposed to prepare intelligent MIPs with thermo-sensitivity.Accordingly,magnetic and thermo-responsive MIPs based on functional monomers-derived DESs(TMDESs-MIPs1)were synthesized,revealing DESs effect-regulated affinity/kinetics for the enhanced adsorption capability,eco-friendly thermo-regulated elution for high release efficiency,and simple magnetic separation,along with superior selectivity to rhein(RH)and good regeneration ability.TM-DESs-MIPs1 were utilized to extract RH from Cassiae semen samples coupled with high performance liquid chromatography(HPLC),yielding satisfactory recoveries(79.47%−110.82%)and low limits of detection(LOD)(16.67μg/L).Another two kinds of MIPs adopting the thermo-responsive moiety-derived DESs effect strategy further demonstrated great applicability of such intelligent MIPs for analyses of complicated samples.展开更多
Recently,metal-organic framework (MOF)@enzyme composites have attracted increasing research interest.However,the fabrication of polymers-modified MOF@enzyme composites with high bio-catalytic performance remains chall...Recently,metal-organic framework (MOF)@enzyme composites have attracted increasing research interest.However,the fabrication of polymers-modified MOF@enzyme composites with high bio-catalytic performance remains challenging.Herein,a stimulus-responsive polymer,poly(acrylate-3',3'-dimethyl-6-nitro-spiro-2H-1-benzopyran-2,2' indoline-1'-ester-co-N-isopropyl acrylamide) (PSPN);was in-situ polymerized in UiO-66-NH2 (UN).The dual-responsive PSPN-UN@L-ASNase composites were constructed following L-asparaginase (L-ASNase) covalently attached to the UN surface.Interestingly,under 365 nm UV irradiation at 45 ℃,the PSP moiety in PSPN underwent a trans-to-cis conformational change and the PN moiety in PSPN transferred from a stretched- to a coiled-state,generating a confinement effect that significantly enhanced the bio-catalytic performance of the composites.Compared with free L-ASNase,the composites showed a 42.0-folds increase in maximum catalytic reaction velocity.Furthermore,the PSPN-UN@L-ASNase composites demonstrated high toxicity for Jurkat leukaemia cells.The stimulus-responsive polymer-MOF@enzyme composites provide a novel avenue for controlled bio-catalysis with great potential for targeted leukaemia therapy.展开更多
The clinical application of triptolide(TPL)in tumor therapy has been greatly limited by its toxicity and inefficient delivery.Herein,a localized and sustained-release thermo-sensitive hydrogel was developed for the in...The clinical application of triptolide(TPL)in tumor therapy has been greatly limited by its toxicity and inefficient delivery.Herein,a localized and sustained-release thermo-sensitive hydrogel was developed for the intra-tumor administration of TPL.Based on the amphiphilic structure of poly(N-isopropylacrylamide-co-acrylic acid)-g-F68 copolymer,it was able to form nano-micelles to efficiently encapsulate TPL,and then turn into a hydrogel at 37C.TPL@nano-gel exhibited a sustained drug release profile in vitro and a stronger anticancer effect caused by"two strikes".The"first strike"was its enhanced cytotoxicity compared to free TPL,due to the enhanced pro-apoptosis effect observed in both MDA-MB-231 and MCF-7 cells caused by the regulation of endogenous mitochondrial pathways.Furthermore,TPL@nano-gel exhibited a"second-strike"through its anti-angiogenesis capabilities mediated through VEGFR-2 signaling inhibition.As expected,after intra-tumoral injection at a 0.45 mg/kg TPL-equivalent dose three times over 14 days in 4 T1 tumor-bearing mice,TPL@nano-gel led to lower systemic toxicity and higher antitumor efficacy compared to multiple injections of TPL.In this regard,these findings indicate that this injectable thermo-responsive hydrogel carries great potential for TPL as a safe and effective cancer therapy.展开更多
Poly(N-isopropylacrylamide)(PNIPAAm)-based thermo-responsive surfaces can switch their wettability(from wettable to non-wettable) and adhesion(from sticky to non-sticky) according to external temperature changes. Thes...Poly(N-isopropylacrylamide)(PNIPAAm)-based thermo-responsive surfaces can switch their wettability(from wettable to non-wettable) and adhesion(from sticky to non-sticky) according to external temperature changes. These smart surfaces with switchable interfacial properties are playing increasingly important roles in a diverse range of biomedical applications; these controlling cell-adhesion behavior has shown great potential for tissue engineering and disease diagnostics. Herein we reviewed the recent progress of research on PNIPAAm-based thermo-responsive surfaces that can dynamically control cell adhesion behavior. The underlying response mechanisms and influencing factors for PNIPAAm-based surfaces to control cell adhesion are described first. Then, PNIPAAm-modified two-dimensional flat surfaces for cell-sheet engineering and PNIPAAm-modified three-dimensional nanostructured surfaces for diagnostics are summarized. We also provide a future perspective for the development of stimuli-responsive surfaces.展开更多
Two-dimensional nanosheet membranes with responsive nanochannels are appealing for controlled mass transfer/separation,but limited by everchanging thicknesses arising from unstable interfaces.Herein,an interfacially s...Two-dimensional nanosheet membranes with responsive nanochannels are appealing for controlled mass transfer/separation,but limited by everchanging thicknesses arising from unstable interfaces.Herein,an interfacially stable,thermo-responsive nanosheet membrane is assembled from twin-chain stabilized metal-organic framework(MOF)nanosheets,which function via two cyclic amide-bearing polymers,thermo-responsive poly(N-vinyl caprolactam)(PVCL)for adjusting channel size,and non-responsive polyvinylpyrrolidone for supporting constant interlayer distance.Owing to the microporosity of MOF nanosheets and controllable interface wettability,the hybrid membrane demonstrates both superior separation performance and stable thermo-responsiveness.Scattering and correlation spectroscopic analyses further corroborate the respective roles of the two polymers and reveal the microenvironment changes of nanochannels are motivated by the dehydration of PVCL chains.展开更多
Although neoantigen-based cancer vaccines show great potential in cancer immunotherapy due to their ability to induce effective and long-lasting anti-tumor immunity,their development is hindered by the limitations of ...Although neoantigen-based cancer vaccines show great potential in cancer immunotherapy due to their ability to induce effective and long-lasting anti-tumor immunity,their development is hindered by the limitations of neoantigens identification,low immunogenicity,and weak immune response.Cyclophosphamide(CTX)not only directly kills tumors but also causes immunogenic cell death,providing a promising source of antigens for cancer vaccines.Herein,a combined immunotherapy strategy based on temperature-sensitive PLEL hydrogel is designed.First,CTX-loaded hydrogel is injected intratumorally into CT26 bearing mice to prime anti-tumor immunity,and then 3 days later,PLEL hydrogels loaded with CpG and tumor lysates are subcutaneously injected into both groins to further promote anti-tumor immune responses.The results confirm that this combined strategy reduces the toxicity of CTX,and produces the cytotoxic T lymphocyte response to effectively inhibit tumor growth,prolong survival,and significantly improve the tumor cure rate.Moreover,a long-lasting immune memory response is observed in the mice.About 90%of the cured mice survive for at least 60 days after being re-inoculated with tumors,and the distant tumor growth is also well inhibited.Hence,this PLEL-based combination therapy may provide a promising reference for the clinical promotion of chemotherapy combined with cancer vaccines.展开更多
A novel hydrophilic nanocomposite additive (TiO2-g-PNIPAAm) was synthesized by the surface modification of titanium dioxide (TiO2) with N-isopropylacrylamide (NIPAAm) via "graft-from" technique. And the nanoco...A novel hydrophilic nanocomposite additive (TiO2-g-PNIPAAm) was synthesized by the surface modification of titanium dioxide (TiO2) with N-isopropylacrylamide (NIPAAm) via "graft-from" technique. And the nanocomposite membrane of poly(vinylidene fluoride) (PVDF)/TiO2-g-PNIPAAm was fabricated by wet phase inversion. The graft degree was obtained by thermo-gravimetric analysis (TGA). Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) characterization results suggested that TiO2-g-PNIPAAm nanoparticles segregated on membrane surface during the phase separation process. Scanning electron microscopy (SEM) was conducted to investigate the surface and cross-section of the modified membranes. The water contact angle measurements confirmed that TiO2-g-PNIPAAm nanoparticles endowed PVDF membranes better hydrophlilicity and thermo-responsive properties compared with those of the pristine PVDF membrane. The water contact angle decreased from 92.8~ of the PVDF membrane to 61.2~ of the nanocompostie membrane. Bovine serum albumin (BSA) static and dynamic adsorption experiments suggested that excellent antifouling properties of membranes was acquired after adding TiO2-g- PNIPAAm. The maximum BSA adsorption at 40℃ was about 3 times than that at 23 ℃. The permeation experiments indicated the water flux recover ratio and BSA rejection ratio were improved at different temperatures.展开更多
Despite the fact that some progress has been made in the self-assembly of H-shaped polymers, the corresponding self-assemblies that respond to external stimulus and are further utilized to adjust the release of drugs ...Despite the fact that some progress has been made in the self-assembly of H-shaped polymers, the corresponding self-assemblies that respond to external stimulus and are further utilized to adjust the release of drugs are still deficient. The stimuli-responsive segments with amphiphilic H-shaped structure are generally expected to enhance the controllability of self-assembly process. The synthesis and self-assembly behavior of thermo-responsive amphiphilic H-shaped polymers with poly(ethylene glycol) (PEG), polytetrahydrofuran (PTHF) and poly(N-isopropyl acrylamide) (PNIPAM) as building blocks are reported in this paper. The inner architecture structure and size of complex micelles formed by H-shaped self-assemblies were effectively adjusted when the solution temperature was increased above the lower critical solution temperature of PNIPAM segments. Furthermore, it was found that the architecture of self-assemblies underwent a transition from the complex micelles based on primary micelles with hybrid PEG/PNIPAM shells to large complex micelles based on primary micelles with hybrid PTHF/PNIPAM cores and PEG shells during the thermal-induced self-assembly process. The adjustable release rate ofdoxorubicin (DOX) from the DOX-loaded complex micelles and basic cell experiments further proved the feasibility of these self-assemblies as the thermal-responsive drug delivery system.展开更多
Wettability of a solid surface is highly important to its practical application,especially for the surface that shows thermoresponsive properties.In this paper,we describe a thermo-responsive stick-slip behavior of wa...Wettability of a solid surface is highly important to its practical application,especially for the surface that shows thermoresponsive properties.In this paper,we describe a thermo-responsive stick-slip behavior of water droplets on the surfaces of poly(N-isopropylacrylamide)(PNIPAM)-grafted polypropylene membranes.Field emission scanning electron microscope(FESEM) images elucidate that the morphology of PNIPAM-grafted membrane surface is thermo-responsive,i.e.,the surface becomes rougher above the lower critical solution temperature(LCST) of PNIPAM.On the surface of nascent polypropylene membranes,the water droplet shows a smooth motion resulting in advancing and receding water contact angles of 111° and ~65°,respectively.On the PNIPAM-grafted membrane surfaces,the water droplet shows a stick-slip pattern above the LCST,whereas it advances smoothly below the LCST.This phenomenon is reproducible and can be ascribed to the energy barriers enhanced by the shrink of PNIPAM chains above the LCST.We also find that the slip contact angle decreases from 102° to 92° after several stick-slip cycles.This decrease is attributed to the water adsorption on the grafted PNIPAM layer,which is confirmed by the continuous decrease of the receding water contact angle.展开更多
Thermo-responsive butyl acrylate/furfuryl methacrylate copolymer-based (PBF backbone) graft (co)polymers with dynamic covalent linkages between their backbones and side chains via the Diels-Alder reaction of furar...Thermo-responsive butyl acrylate/furfuryl methacrylate copolymer-based (PBF backbone) graft (co)polymers with dynamic covalent linkages between their backbones and side chains via the Diels-Alder reaction of furardmaleimide were synthesized. Atom transfer radical polymerization (ATRP) was used to synthesize graft copolymers with thermo-responsive transformation from graft copolymers to linear polymers with bimodal or wide MWD. The NMR measurements indicated that the Diels-Alder reaction and retro- Diels-Alder reaction occurred, depending on the change of the temperature, meaning that the side chains could be cleaved and reformed according to the variation of the temperature. GPC measurements demonstrated that the molecular weights of the polymers were thermo- responsive. Furthermore, three graft copolymers with various branching chains (PBF-g-PBA, PBF-g-P(BMA-co-MA) and PBF-g-PBMA) were compared to study the influence of compatibility between the backbone and the branching chain on the efficiency of Diels-Alder reaction after the cleavage of the DA linkage. The results showed that the ability of the side chains to come back to the main chain was strongly affected by the compatibility between the backbone and the side chains and the flexibility of the polymer chains.展开更多
Therrno-responsive block copolymers poly(ethylene glycol)-block-poly(N-acryloyl-2,2-dimethyl-1,3-oxazolidine), PEG-b-PADMO, based on linear PEG were prepared via a versatile reversible addition-fragmentation chain...Therrno-responsive block copolymers poly(ethylene glycol)-block-poly(N-acryloyl-2,2-dimethyl-1,3-oxazolidine), PEG-b-PADMO, based on linear PEG were prepared via a versatile reversible addition-fragmentation chain transfer (RAFT) polymerization, PEG22 (Mw = 1000) was used as the hydrophilic component, whose dehydration was the main driving force for the phase transition of these copolymers, as demonstrated by the tH-NMR spectra. Their lower critical solution temperatures (LCSTs) could be tuned in the range of 20℃ to 35℃, by adjusting the degree of polymerization (DP) of PADMO between 14-27. Furthermore, a sharp phase transition at ca. 33℃, close to the physiological temperature with minimal hysteresis, was observed for the PEGzz-b-PADMO14 copolymer. Moreover, excellent reversibility and reproducibility were displayed for the same copolymer over 10 cycles of repeated temperature change between 25℃ (below the LCST) and 40℃ (above the LCST).展开更多
In this work,the Hofmeister effects of nine kinds of anions at different concentrations on the lower critical solution temperature(LCST)of the macroporous thermo-responsive poly(N-isopropylacrylamide)grafted poly(viny...In this work,the Hofmeister effects of nine kinds of anions at different concentrations on the lower critical solution temperature(LCST)of the macroporous thermo-responsive poly(N-isopropylacrylamide)grafted poly(vinyl alcohol)formaldehyde(PVF-g-PNIPAM)hydrogels are investigated with differential scanning calorimetry(DSC).Four kinds of anions with strong hydration,including CO3^2–,SO4^2–,S2 O3^2–,and F^–,and four kinds of anions with weak hydration,including Br^–,NO3^–,I^–,and ClO4^–,and Cl^–as a medium anion are systematically studied and found to demonstrate the effects of the residual hydroxyl groups and network structure of PVF on the LCST values of PVF-g-PNIPAM hydrogels in comparison with that of neat PNIPAM.On the one hand,the existence of hydroxyl groups on PVF backbone promotes the solubility of grafted PNIPAM due to their hydrophilicity and hydrogen-bond interactions with water.On the other hand,the network structure of as-prepared samples restricts free movements of grafted PNIPAM chains,which results in the increase of LCST values.In addition,the difference of grafting percentage also influences the variation of LCST values of PVF-g-PNIPAM hydrogels under salt concentration.展开更多
A novel β-cyclodextrin-poly(2-(2-methoxyethoxy)ethyl methacrylate)-co- poly(ethylene glycol) methacrylate (abbreviated as: β-CD-(P(MEO2MA-co-PEGMA))21) was prepared by using the one-step strategy, and t...A novel β-cyclodextrin-poly(2-(2-methoxyethoxy)ethyl methacrylate)-co- poly(ethylene glycol) methacrylate (abbreviated as: β-CD-(P(MEO2MA-co-PEGMA))21) was prepared by using the one-step strategy, and then the star-shaped copolymers were used in the atom transfer radical polymerization (ATRP). The structure of star-shaped β- CD-(P(MEO2MA-co-PEGMA))21 copolymers were studied by FTIR, 1H NMR and gel permeation chromatography (GPC). The star-shaped copolymers could self-assembled into micelles in aqueous solution owing to the outer amphiphilic β-CD as a core and the hydrophilic P(MEO2MA-co-PEGMA) segments as a shell. These thermo-responsive starshaped copolymers micelles exhibited lower critical solution temperature (LCST) in water, which could be finely tuned by changing the feed ratio of MEO2MA to PEGMA. The LCST of star-shaped β-CD-(P(MEO2MA-co-PEGMA))21 copolymer micelles were increased from 35℃ to 58℃ with the increasing content of PEGMA. The results were investigated by DLS and TEM. When the temperature was higher than corresponding LCSTs, the micelles started to associate and form spherical nanoparticles. Therefore, β- CD-(P(MEO2MA-co-PEGMA))21 star-shaped copolymer micelles could be potentially applied in nano-carrier, nano-reactor, smart materials and biomedical fields.展开更多
基金supported by the National Nature Science Foundation of China(No.22278179,U23A20688)the National Key Research and Development Program of China(2021YFB3802600)+3 种基金the Fundamental Research Funds for the Central Universities(JUSRP622035)National First-Class Discipline Program of Light Industry Technology and Engineering(LIFE2018-19)MOE&SAFEA for the 111 Project(B13025)Natural Science Foundation of Xinjiang Uygur Autonomous Region(2022D01D030).
文摘Negatively thermo-responsive 2D membranes,which mimic the stomatal opening/closing of plants,have drawn substantial interest for tunable molecular separation processes.However,these membranes are still restricted significantly on account of low water permeability and poor dynamic tunability of 2D nanochannels under temperature stimulation.Here,we present a biomimetic negatively thermo-responsive MXene membrane by covalently grafting poly(N-isopropylacrylamide)(PNIPAm)onto MXene nanosheets.The uniformly grafted PNIPAm polymer chains can enlarge the interlayer spacings for increasing water permeability while also allowing more tunability of 2D nanochannels for enhancing the capability of gradually separating multiple molecules of different sizes.As expected,the constructed membrane exhibits ultrahigh water permeance of 95.6 L m^(-2) h^(-1) bar^(-1) at 25℃,which is eight-fold higher than the state-of-the-art negatively thermoresponsive 2D membranes.Moreover,the highly temperature-tunable 2D nanochannels enable the constructed membrane to perform excellent graded molecular sieving for dye-and antibiotic-based ternary mixtures.This strategy provides new perspectives in engineering smart 2D membrane and expands the scope of temperature-responsive membranes,showing promising applications in micro/nanofluidics and molecular separation.
基金Supported by the National Natural Science Foundation of China(No.29876022).
文摘The effect of graft yield on both the thermo-responsive hydraulicpermeability and the therrno-responsive diffusional permeability through porous membranes withplasma-grafted poly(N-isopropylacrylamide) (PNIPAM) gates was investigated. Both thermo-responsiveflat membranes and core-shell microcapsule membranes with a wide range of graft yield of PNIPAM wereprepared using a plasma-graft pore-filling polymerization method. The grafted PNIPAM was formedhomogeneously throughout the entire thickness of both the flat polyethylene membranes and themicrocapsule polyamide membranes. Both the hydraulic permeability and the diffusional permeabilitywere heavily dependent on the PNIPAM graft yield. With increasing the graft yield, the hydraulicpermeability (water flux) decreases rapidly at 25℃ because of the decrease of the pore size;however, the water flux at 40℃ increases firstly to a peak because of the increase ofhydrophobicity of the pore surface, and then decreases and finally tends to zero because of the poresize becoming smaller and smaller. For the diffusional permeability, the temperature showsdifferent effects on the diffusional permeability coefficients of solutes across the membranes. Whenthe graft yield was low, the diffusional coefficient of solute across the membrane was higher attemperature above the lower critical solution temperature (LCST) than that below the LCST; however,when the graft yield was high, the diffusional coefficient was lower at temperature above the LCSTthan that below the LCST. It is very important to choose or design a proper graft yield of PNIPAMfor obtaining a desired thermo-responsive 'on/off' hydraulic or diffusional permeability.
基金Supported by the National ]qatural Science Foundation of China (20906064), the National Basic Research Program of China (2009CB623407), the Program for Changjiang Scholars and Innovative Research Team in University (IRTl163), and the Foundation for the Author of National Excellent Doctoral Dissertation of China (201163).
文摘Halloysite nanotube-composited thermo-responsive hydrogel system has been successfully developed for controlled drug release by copolymerization of N-isopropylacrylamide (NIPAM) with silane-modified halloysite nanotubes (HNT) through thermally initiated free-radical polymerization. With methylene blue as a model drug, thermo-responsive drug release results demonstrate that the drug release from the nanotubes in the composited hy-drogel can^be well controlled by manipulating the environmental temperature. When the hydrogel network is swol- len at temperature below the lower critical solution temperature (LCST), drug releases steadily from lumens of the embedded nanotubes, whereas the drug release stops when hydrogel shrinks at temperature above the LCST. The release of model drug from the HNT-composited hydrogel matches well with its thermo-responsive volume phasetransition, and shows characteristics of well controlled release. The design strategy and release results of the pro- posed novel HNT-composited thermo-responsive hydrogel system provide valuable guidance for designing respon- s_i_ve nanocomposites for controlled-release of active agents.
基金National Natural Science Foundation of China(No.51373030)Chinese Universities Scientific Fund(No.CUSF-DH-D-2014023)
文摘The monodisperse Au@Ag bimetallic nanorod is encapsulated by crosslinked poly( N-isopropylacrylamide)( PNIPAM) to produce thermo-responsive composite microgel with well-defined core-shell structure( Au@ Ag NR@ PNIPAM microgel)by seed-precipitation polymerization method using butenoic acid modified Au @ Ag NRs as seeds. When the temperature of the aqueous medium increases from 20℃ to 50℃,the localized surface plasmon resonance( LSPR) band of the entrapped Au @ Ag NR is pronouncedly red-shifted because of the decreased spatial distances between them as a result of shrinkage of the microgels,leading to their plasmonic coupling. The temperature tunable plasmonic coupling is demonstrated by temperature dependence of the surface enhanced Raman spectroscopy( SERS) signal of 1-naphthol in aqueous solution. Different from static plasmonic coupling modes from nanostructured assembly or array system of noble metals,the proposed plasmonic coupling can be dynamically controlled by environmental temperature. Therefore, the thermo responsive hybrid microgels have potential applications in mobile LSPR or SERS microsensors for living tissues or cells.
基金Projects(2006GG2203007) supported by the Scientific Research Project of Shandong Province,China
文摘Thermo-responsive multiblock polycarbonates were facilely synthesized by covalently binding poly(ethylene glycol)(PEG) and poly(propylene glycol)(PPG) blocks,using triphosgene as coupling agent and pyridine as catalyst.The aqueous solutions of thermo-responsive polycarbonates were investigated by rheological measurements.Steady-state shear measurements reveal that the polycarbonate solutions exhibit shear-thinning behavior and the hydrophilic content has a pronounced effect on the flow behavior of the polycarbonates aqueous solutions.The shear viscosity decreases with increasing poly(ethylene oxide)(PEO) composition.The increase of viscosity with increasing concentration is probably attributed to the formation of stronger network owing to interchain entanglement of PEO block at higher concentration.When the flow curves are fitted to the power law model,flow index is obtained to be less than 1,as exhibiting typical pesudoplastic fluid.The viscoelastic properties of the system also show close dependence on the composition of polycarbonates.Temperature sweep confirms that the multiblock polycarbonates exhibit thermo-responsive properties.For 7% aqueous solution of polycarbonate with composition ratio of EO to PO of 1/1,the sol-gel transition occurs at 37 ℃,which makes the system suitable as an injectable drug delivery system.
文摘Thermo-respansive chitosan hydrogel system (TRCHS) was prepared and its mierostructure was investigated by scaning electron microscope (SEM) and mercury intrusion poremaster (MIP). Based on analyzing the data, a special porosity property was reported at the first time. Its gelling mechanism was studied by a group of contrast experiments. Results may provide experimental and theoretical supports for how to apply it on tissue engineering scaffold and how to influeuee or control its essential properties.
基金Fujian External Cooperation project of Natural Science Foundation,China(No.2022I0042)。
文摘Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.
基金National Key Research and Development Project(No.2019YFC1604904)National Natural Science Foundation of China(No.32101212)+1 种基金Natural Science Foundation of Jiangxi(No.20224ACB215009)Research Program of State Key Laboratory of Food Science and Technology in Nanchang University(No.SKLF-ZZB-202127).
文摘As a new concept having emerged in last few years,the“deep eutectic solvents”(DESs)effect integrated into the imprinting technology inevitably exposes design limitations of stimuli-responsive molecularly imprinted polymers(MIPs),as well as inadequate analysis of the adsorption performance of MIPs.Herein,a simple yet defined N-isopropylacrylamide/(3-acrylamidopropyl)trimethylammonium chloride(NIPAM/APTMAC)binary DESs system was proposed to prepare intelligent MIPs with thermo-sensitivity.Accordingly,magnetic and thermo-responsive MIPs based on functional monomers-derived DESs(TMDESs-MIPs1)were synthesized,revealing DESs effect-regulated affinity/kinetics for the enhanced adsorption capability,eco-friendly thermo-regulated elution for high release efficiency,and simple magnetic separation,along with superior selectivity to rhein(RH)and good regeneration ability.TM-DESs-MIPs1 were utilized to extract RH from Cassiae semen samples coupled with high performance liquid chromatography(HPLC),yielding satisfactory recoveries(79.47%−110.82%)and low limits of detection(LOD)(16.67μg/L).Another two kinds of MIPs adopting the thermo-responsive moiety-derived DESs effect strategy further demonstrated great applicability of such intelligent MIPs for analyses of complicated samples.
基金supported by the National Natural Science Foundation of China (No.22274159)。
文摘Recently,metal-organic framework (MOF)@enzyme composites have attracted increasing research interest.However,the fabrication of polymers-modified MOF@enzyme composites with high bio-catalytic performance remains challenging.Herein,a stimulus-responsive polymer,poly(acrylate-3',3'-dimethyl-6-nitro-spiro-2H-1-benzopyran-2,2' indoline-1'-ester-co-N-isopropyl acrylamide) (PSPN);was in-situ polymerized in UiO-66-NH2 (UN).The dual-responsive PSPN-UN@L-ASNase composites were constructed following L-asparaginase (L-ASNase) covalently attached to the UN surface.Interestingly,under 365 nm UV irradiation at 45 ℃,the PSP moiety in PSPN underwent a trans-to-cis conformational change and the PN moiety in PSPN transferred from a stretched- to a coiled-state,generating a confinement effect that significantly enhanced the bio-catalytic performance of the composites.Compared with free L-ASNase,the composites showed a 42.0-folds increase in maximum catalytic reaction velocity.Furthermore,the PSPN-UN@L-ASNase composites demonstrated high toxicity for Jurkat leukaemia cells.The stimulus-responsive polymer-MOF@enzyme composites provide a novel avenue for controlled bio-catalysis with great potential for targeted leukaemia therapy.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.81973662and 8170371)Scientific Development Program of Sichuan Province(2019JDJQ0049,China)+1 种基金China Postdoctoral Science Foundation(Grant Nos.2017M612930 and 2019T120817)Young Elite Scientists Sponsorship Program by CAST(2018QNRC1-01,China)
文摘The clinical application of triptolide(TPL)in tumor therapy has been greatly limited by its toxicity and inefficient delivery.Herein,a localized and sustained-release thermo-sensitive hydrogel was developed for the intra-tumor administration of TPL.Based on the amphiphilic structure of poly(N-isopropylacrylamide-co-acrylic acid)-g-F68 copolymer,it was able to form nano-micelles to efficiently encapsulate TPL,and then turn into a hydrogel at 37C.TPL@nano-gel exhibited a sustained drug release profile in vitro and a stronger anticancer effect caused by"two strikes".The"first strike"was its enhanced cytotoxicity compared to free TPL,due to the enhanced pro-apoptosis effect observed in both MDA-MB-231 and MCF-7 cells caused by the regulation of endogenous mitochondrial pathways.Furthermore,TPL@nano-gel exhibited a"second-strike"through its anti-angiogenesis capabilities mediated through VEGFR-2 signaling inhibition.As expected,after intra-tumoral injection at a 0.45 mg/kg TPL-equivalent dose three times over 14 days in 4 T1 tumor-bearing mice,TPL@nano-gel led to lower systemic toxicity and higher antitumor efficacy compared to multiple injections of TPL.In this regard,these findings indicate that this injectable thermo-responsive hydrogel carries great potential for TPL as a safe and effective cancer therapy.
基金supported by the National Basic Research Program of China(2012CB933800,2011CB935700,2012CB933200)the National Natural Science Foundation of China(21175140,20974113,21121001)the Key Research Program of the Chinese Academy of Sciences(KJZD-EW-M01)
文摘Poly(N-isopropylacrylamide)(PNIPAAm)-based thermo-responsive surfaces can switch their wettability(from wettable to non-wettable) and adhesion(from sticky to non-sticky) according to external temperature changes. These smart surfaces with switchable interfacial properties are playing increasingly important roles in a diverse range of biomedical applications; these controlling cell-adhesion behavior has shown great potential for tissue engineering and disease diagnostics. Herein we reviewed the recent progress of research on PNIPAAm-based thermo-responsive surfaces that can dynamically control cell adhesion behavior. The underlying response mechanisms and influencing factors for PNIPAAm-based surfaces to control cell adhesion are described first. Then, PNIPAAm-modified two-dimensional flat surfaces for cell-sheet engineering and PNIPAAm-modified three-dimensional nanostructured surfaces for diagnostics are summarized. We also provide a future perspective for the development of stimuli-responsive surfaces.
基金support from the National Natural Science Foundation of China(Nos.21991123,51733003,21674025,and 51873035)“Qimingxing”project(No.19QA1400200)of the Shanghai Committee of Science and Technology.
文摘Two-dimensional nanosheet membranes with responsive nanochannels are appealing for controlled mass transfer/separation,but limited by everchanging thicknesses arising from unstable interfaces.Herein,an interfacially stable,thermo-responsive nanosheet membrane is assembled from twin-chain stabilized metal-organic framework(MOF)nanosheets,which function via two cyclic amide-bearing polymers,thermo-responsive poly(N-vinyl caprolactam)(PVCL)for adjusting channel size,and non-responsive polyvinylpyrrolidone for supporting constant interlayer distance.Owing to the microporosity of MOF nanosheets and controllable interface wettability,the hybrid membrane demonstrates both superior separation performance and stable thermo-responsiveness.Scattering and correlation spectroscopic analyses further corroborate the respective roles of the two polymers and reveal the microenvironment changes of nanochannels are motivated by the dehydration of PVCL chains.
基金This work was financially supported by the National Natural Science Foundation of China(31930067,31525009,31800797 and 31771096)the National Key Research and Development Program of China(2017YFC1103502)+1 种基金China Postdoctoral Science Foundation(2018M631094 and 2019M653410)1⋅3⋅5project for disciplines of excellence,West China Hospital,Sichuan University(ZYGD18002).
文摘Although neoantigen-based cancer vaccines show great potential in cancer immunotherapy due to their ability to induce effective and long-lasting anti-tumor immunity,their development is hindered by the limitations of neoantigens identification,low immunogenicity,and weak immune response.Cyclophosphamide(CTX)not only directly kills tumors but also causes immunogenic cell death,providing a promising source of antigens for cancer vaccines.Herein,a combined immunotherapy strategy based on temperature-sensitive PLEL hydrogel is designed.First,CTX-loaded hydrogel is injected intratumorally into CT26 bearing mice to prime anti-tumor immunity,and then 3 days later,PLEL hydrogels loaded with CpG and tumor lysates are subcutaneously injected into both groins to further promote anti-tumor immune responses.The results confirm that this combined strategy reduces the toxicity of CTX,and produces the cytotoxic T lymphocyte response to effectively inhibit tumor growth,prolong survival,and significantly improve the tumor cure rate.Moreover,a long-lasting immune memory response is observed in the mice.About 90%of the cured mice survive for at least 60 days after being re-inoculated with tumors,and the distant tumor growth is also well inhibited.Hence,this PLEL-based combination therapy may provide a promising reference for the clinical promotion of chemotherapy combined with cancer vaccines.
基金financially supported by the National Natural Science Foundation of China(No.51303028)the Natural Science Foundation of Fujian Province(No.2011J01044)
文摘A novel hydrophilic nanocomposite additive (TiO2-g-PNIPAAm) was synthesized by the surface modification of titanium dioxide (TiO2) with N-isopropylacrylamide (NIPAAm) via "graft-from" technique. And the nanocomposite membrane of poly(vinylidene fluoride) (PVDF)/TiO2-g-PNIPAAm was fabricated by wet phase inversion. The graft degree was obtained by thermo-gravimetric analysis (TGA). Fourier transform infrared attenuated reflection spectroscopy (FTIR-ATR) and X-ray photoelectronic spectroscopy (XPS) characterization results suggested that TiO2-g-PNIPAAm nanoparticles segregated on membrane surface during the phase separation process. Scanning electron microscopy (SEM) was conducted to investigate the surface and cross-section of the modified membranes. The water contact angle measurements confirmed that TiO2-g-PNIPAAm nanoparticles endowed PVDF membranes better hydrophlilicity and thermo-responsive properties compared with those of the pristine PVDF membrane. The water contact angle decreased from 92.8~ of the PVDF membrane to 61.2~ of the nanocompostie membrane. Bovine serum albumin (BSA) static and dynamic adsorption experiments suggested that excellent antifouling properties of membranes was acquired after adding TiO2-g- PNIPAAm. The maximum BSA adsorption at 40℃ was about 3 times than that at 23 ℃. The permeation experiments indicated the water flux recover ratio and BSA rejection ratio were improved at different temperatures.
基金financially supported by the National Natural Science Foundation of China(No.21674086)Scientific Research Program Funded by Shaanxi Provincial Education Department(No.17JK0103)
文摘Despite the fact that some progress has been made in the self-assembly of H-shaped polymers, the corresponding self-assemblies that respond to external stimulus and are further utilized to adjust the release of drugs are still deficient. The stimuli-responsive segments with amphiphilic H-shaped structure are generally expected to enhance the controllability of self-assembly process. The synthesis and self-assembly behavior of thermo-responsive amphiphilic H-shaped polymers with poly(ethylene glycol) (PEG), polytetrahydrofuran (PTHF) and poly(N-isopropyl acrylamide) (PNIPAM) as building blocks are reported in this paper. The inner architecture structure and size of complex micelles formed by H-shaped self-assemblies were effectively adjusted when the solution temperature was increased above the lower critical solution temperature of PNIPAM segments. Furthermore, it was found that the architecture of self-assemblies underwent a transition from the complex micelles based on primary micelles with hybrid PEG/PNIPAM shells to large complex micelles based on primary micelles with hybrid PTHF/PNIPAM cores and PEG shells during the thermal-induced self-assembly process. The adjustable release rate ofdoxorubicin (DOX) from the DOX-loaded complex micelles and basic cell experiments further proved the feasibility of these self-assemblies as the thermal-responsive drug delivery system.
基金support from the National Natural Science Foundation of China for Distinguished Young Scholars (Grant No.50625309)The Zhejiang Provincial Natural Science Foundation of China (Grant No.Z406260)supports from the National Postdoctoral Science Foundation of China (Grant Nos.20070421172 & 20081466)
文摘Wettability of a solid surface is highly important to its practical application,especially for the surface that shows thermoresponsive properties.In this paper,we describe a thermo-responsive stick-slip behavior of water droplets on the surfaces of poly(N-isopropylacrylamide)(PNIPAM)-grafted polypropylene membranes.Field emission scanning electron microscope(FESEM) images elucidate that the morphology of PNIPAM-grafted membrane surface is thermo-responsive,i.e.,the surface becomes rougher above the lower critical solution temperature(LCST) of PNIPAM.On the surface of nascent polypropylene membranes,the water droplet shows a smooth motion resulting in advancing and receding water contact angles of 111° and ~65°,respectively.On the PNIPAM-grafted membrane surfaces,the water droplet shows a stick-slip pattern above the LCST,whereas it advances smoothly below the LCST.This phenomenon is reproducible and can be ascribed to the energy barriers enhanced by the shrink of PNIPAM chains above the LCST.We also find that the slip contact angle decreases from 102° to 92° after several stick-slip cycles.This decrease is attributed to the water adsorption on the grafted PNIPAM layer,which is confirmed by the continuous decrease of the receding water contact angle.
基金financially supported by the National Natural Science Foundation of China(Nos.51233005,21374114,and21274152)
文摘Thermo-responsive butyl acrylate/furfuryl methacrylate copolymer-based (PBF backbone) graft (co)polymers with dynamic covalent linkages between their backbones and side chains via the Diels-Alder reaction of furardmaleimide were synthesized. Atom transfer radical polymerization (ATRP) was used to synthesize graft copolymers with thermo-responsive transformation from graft copolymers to linear polymers with bimodal or wide MWD. The NMR measurements indicated that the Diels-Alder reaction and retro- Diels-Alder reaction occurred, depending on the change of the temperature, meaning that the side chains could be cleaved and reformed according to the variation of the temperature. GPC measurements demonstrated that the molecular weights of the polymers were thermo- responsive. Furthermore, three graft copolymers with various branching chains (PBF-g-PBA, PBF-g-P(BMA-co-MA) and PBF-g-PBMA) were compared to study the influence of compatibility between the backbone and the branching chain on the efficiency of Diels-Alder reaction after the cleavage of the DA linkage. The results showed that the ability of the side chains to come back to the main chain was strongly affected by the compatibility between the backbone and the side chains and the flexibility of the polymer chains.
文摘Therrno-responsive block copolymers poly(ethylene glycol)-block-poly(N-acryloyl-2,2-dimethyl-1,3-oxazolidine), PEG-b-PADMO, based on linear PEG were prepared via a versatile reversible addition-fragmentation chain transfer (RAFT) polymerization, PEG22 (Mw = 1000) was used as the hydrophilic component, whose dehydration was the main driving force for the phase transition of these copolymers, as demonstrated by the tH-NMR spectra. Their lower critical solution temperatures (LCSTs) could be tuned in the range of 20℃ to 35℃, by adjusting the degree of polymerization (DP) of PADMO between 14-27. Furthermore, a sharp phase transition at ca. 33℃, close to the physiological temperature with minimal hysteresis, was observed for the PEGzz-b-PADMO14 copolymer. Moreover, excellent reversibility and reproducibility were displayed for the same copolymer over 10 cycles of repeated temperature change between 25℃ (below the LCST) and 40℃ (above the LCST).
基金financially supported by Foundation of State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry
文摘In this work,the Hofmeister effects of nine kinds of anions at different concentrations on the lower critical solution temperature(LCST)of the macroporous thermo-responsive poly(N-isopropylacrylamide)grafted poly(vinyl alcohol)formaldehyde(PVF-g-PNIPAM)hydrogels are investigated with differential scanning calorimetry(DSC).Four kinds of anions with strong hydration,including CO3^2–,SO4^2–,S2 O3^2–,and F^–,and four kinds of anions with weak hydration,including Br^–,NO3^–,I^–,and ClO4^–,and Cl^–as a medium anion are systematically studied and found to demonstrate the effects of the residual hydroxyl groups and network structure of PVF on the LCST values of PVF-g-PNIPAM hydrogels in comparison with that of neat PNIPAM.On the one hand,the existence of hydroxyl groups on PVF backbone promotes the solubility of grafted PNIPAM due to their hydrophilicity and hydrogen-bond interactions with water.On the other hand,the network structure of as-prepared samples restricts free movements of grafted PNIPAM chains,which results in the increase of LCST values.In addition,the difference of grafting percentage also influences the variation of LCST values of PVF-g-PNIPAM hydrogels under salt concentration.
基金Acknowledgements The authors gratefully acknowledge financial supports from the National Natural Science Foundation of China (Grant No. 51662036) and the Bingtuan Innovation Team in Key Areas (2015BD003).
文摘A novel β-cyclodextrin-poly(2-(2-methoxyethoxy)ethyl methacrylate)-co- poly(ethylene glycol) methacrylate (abbreviated as: β-CD-(P(MEO2MA-co-PEGMA))21) was prepared by using the one-step strategy, and then the star-shaped copolymers were used in the atom transfer radical polymerization (ATRP). The structure of star-shaped β- CD-(P(MEO2MA-co-PEGMA))21 copolymers were studied by FTIR, 1H NMR and gel permeation chromatography (GPC). The star-shaped copolymers could self-assembled into micelles in aqueous solution owing to the outer amphiphilic β-CD as a core and the hydrophilic P(MEO2MA-co-PEGMA) segments as a shell. These thermo-responsive starshaped copolymers micelles exhibited lower critical solution temperature (LCST) in water, which could be finely tuned by changing the feed ratio of MEO2MA to PEGMA. The LCST of star-shaped β-CD-(P(MEO2MA-co-PEGMA))21 copolymer micelles were increased from 35℃ to 58℃ with the increasing content of PEGMA. The results were investigated by DLS and TEM. When the temperature was higher than corresponding LCSTs, the micelles started to associate and form spherical nanoparticles. Therefore, β- CD-(P(MEO2MA-co-PEGMA))21 star-shaped copolymer micelles could be potentially applied in nano-carrier, nano-reactor, smart materials and biomedical fields.