CHINESE JOURNAL OF POLYMER SCIENCE
·
2024
·Vol. 42
·期 6
·826-837
·
IF 4.1
Yin Feng-Ming,Wu Li-Li,Li Shu-Sheng,Pan Xiao-Na,Zhu Xiao-Li,Jiang Xu-Bao,Kong Xiang Zheng
Non-aromatic fluorescent and multi-responsive materials, exhibiting inherent fluorescence emission and controlled phase change, have garnered significant attention in recent years. However, the underlying interaction between their fluorescent properties and phase transition remains unclear. In this study, we synthesized a series of catalyst-free aza-Michael addition-based polyethyleneimine (RFPEI) materials by reacting polyethyleneimine (PEI) with N -isopropyl acrylamide (NIPAM). The resulting RFPEI was comprehensively characterized, and demonstrated dual-phase transition behavior (LCST and UCST) in water, which could be finely tuned by adjusting its composition or external factors such as pH. Notably, upon UV irradiation (365 nm), RFPEI exhibited strong fluorescence emission. We further investigated the effects of NIPAM grafting percentage to PEI, polymer concentration, and pH on the LCST/UCST and fluorescent properties of RFPEI aqueous solutions. Moreover, we showcased the great potential of RFPEI as a versatile tool for physiological cell imaging, trace detection, and controlled release of doxorubicin. Our study presents a novel class of stimuli-responsive fluorescent materials with promising applications in the field of biomedicine.
研究领域:
生物材料学
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医学工程
·
高分子化学
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DOI
高影响因子
Polymers
·
2019
·Vol. 11
·期 5
·895
·
IF 3.164
Xiuzhong Zhu,Xiao Duan,Ting Bai,Xuan Zhang,Tong Wang,Tao Cao,Xiaodong Fan
In this study, a new pH-tunable thermoresponsive hydroxyl-terminated hyperbranched polyether (HTHP 2) was successfully prepared via a one-pot cationic polymerization technique and postmodification. In the first step, hydroxyl-terminated hyperbranched polyether containing double bonds (HTHP 1) were synthesized. Then, through thiol-ene “click” reaction, pH-responsive carboxyl groups were introduced to the target polymer of HTHP 2. The products were characterized via Fourier-transform infrared spectra (FTIR), nuclear magnetic resonance (NMR), and size-exclusion chromatography-multiangle laser light scattering (SEC-MALLS). Moreover, dynamic light scattering (DLS) and UV–Vis spectroscopy was employed to study the pH- and thermoresponsiveness in detail. Results showed that HTHP 2 possessed typical pH-controllable thermoresponsive behavior. By regulating the solution pH value range 3.0–5.4, LCST of HTHP 2 could be changed from 12.8 to 68.0 °C. Meanwhile, the cell viabilities of A549 cells were more than 80% for in vitro cytotoxicity tests of HTHP 2, suggested that HTHP 2 polymers are of good biocompatibility for up to 24 h.Keywords:hydroxyl-terminated hyperbranched polyether;cationic polymerization;thiol-ene “click” reaction;widely tunable LCST
研究领域:
材料科学
·
生物医学工程
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产品关联
DOI
PubMed
高影响因子
Arabian Journal of Chemistry
·
2021
·
IF 5.165
Guangyan Zhang,Chenhui Bao,Hui Yi
Previous works reported that some temperature responsive polyaspartamide derivatives exhibited pH responsiveness, although pH responsive functional groups or pH-cleavable linkages were not introduced during the preparing process, which may be related to the hydroxyl groups of their pendant alkanolamide moieties. In order to investigate whether pH will also affect the temperature responsive behavior of temperature responsive polyaspartamide derivatives without hydroxyl groups, four linear alkyl ether-type amine compounds with one ether oxygen atom and 3 to 6 carbon atoms, denoted as OCx (x represents the number of carbon atoms in alkyl ether-type amine compounds), were selected for the aminolysis reaction of poly(succinimide) to design and synthesize the polyaspartamide derivatives bearing alkyl ether pendants, named PASP-OCx. The chemical structures and molecular weights of the obtained polymers were characterized and confirmed by FTIR, 1 H NMR and SEC-MALLS. The water-solubilities, surface tensions and transmittances of PASP-OCx aqueous solutions were also investigated. Results showed that PASP-OCx can be dissolved in deionized water when x is less than or equal to 5. The surface tensions of PASP-OC4 and PASP-OC5 solutions exhibited obvious turning points. Interestingly, transmittances results showed that PASP-OC5 exhibited temperature responsive behaviors under acidic, neutral or alkaline conditions (pH ≤ 10.0); PASP-OC4 only exhibited temperature responsive behaviors under acidic condition (pH ≤ 3.0); while PASP-OC3 did not exhibit temperature responsive behavior. The LCST value of PASP-OC5 and PASP-OC4 can be turned by adjusting the pH value of their solutions, and decreases with decreasing the pH value. Additionally, the influence of pH on the LCST values of PASP-OC4 and PASP-OC5 was investigated by zeta potential, and the results showed that the decrease of LCST values may be due to the reducing of electrostatic repulsion with pH decreasing. Therefore, results showed that pH can also affect the temperature responsive behavior of temperature-responsive polyaspartamide derivatives that do not contain hydroxyl groups.
研究领域:
高分子化学
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材料科学
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产品关联
DOI
高影响因子
LANGMUIR
·
2014
·
IF 4.384
Jun Yin,Jinming Hu,Guoying Zhang,Shiyong Liu
A variety of slightly cross-linked poly(2-vinylpyridine)–poly(N-isopropylacrylamide) (P2VP–PNIPAM) core–shell microgels with pH- and temperature-responsive characteristic were prepared via seeded emulsion polymerization. Negatively charged sodium 2,6-naphthalenedisulfonate (2,6-NDS) could be internalized into the inner core, followed by formation of (P2VPH+/SO32–) supramolecular complex through the electrostatic attractive interaction in acid condition. The thermoresponsive characteristic feature of the (P2VPH+/SO32–)–PNIPAM core–shell microgels was investigated by laser light scattering and UV–vis measurement, revealing an integration of upper critical solution temperature (UCST) and lower critical solution temperature (LCST) behaviors in the temperature range of 20–55 °C. The UCST performance arised from the compromised electrostatic attractive interaction between P2VPH+ and 2,6-NDS at elevated temperatures, while the subsequent LCST transition is correlated to the thermo-induced collapse of PNIPAM shells. The controlled release of 2,6-NDS was monitored by static fluorescence spectra as a function of temperature change. Moreover, stopped-flow equipped with a temperature-jump accessory was then employed to assess the dynamic process, suggesting a millisecond characteristic relaxation time of the 2,6-NDS diffusion process. Interestingly, the characteristic relaxation time is independent of the shell cross-link density, whereas it was significantly affected by shell thickness. We believe that these dual thermoresponsive core–shell microgels with thermotunable volume phase transition may augur promising applications in the fields of polymer science and materials, particularly for temperature-triggered release.
研究领域:
高分子科学
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材料化学
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智能材料
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胶体与界面科学
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药物递送系统
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DOI
高影响因子
POLYMER
·
2026
·
IF 5.1
Anqi Lin,Tongda Lei,Baixue Jia,Yaya Feng,Zhongying Zhang,Hao Shen,Mengli Jin,Yongheng Wang,Faming Tian,Ruoying Zhu,Jie Fan
Temperature-responsive nanofiber membranes have attracted increasing attention in the biomedical field, particularly in wound management and controlled drug delivery. Bio-based thermoresponsive polymers can integrate the advantages of natural materials with the temperature-responsive properties of poly(N-isopropylacrylamide) (PNIPAM). In this study, a keratin-based temperature-responsive polymer (KTRP) was constructed by grafting the rabbit hair keratin (RHK) with active thiol group (-SH) on the N-isopropylacrylamide (NIPAM) through a one-step thiol-Michael addition reaction. The resulting polymer has a good miscibility with soluble wool keratin (WK) in liquid solution. The mixed spinning solution of KTRP, WK, and poly(ethylene oxide) (PEO) showed good spinnability and was fabricated into temperature-responsive composite nanofiber membranes (KTRP/WK/PEO) by electrospinning. A 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide/ N -hydroxysuccinimide (EDC/NHS)-mediated covalent crosslinking network was introduced to improve the water resistance and structural integrity of the nanofiber membranes. The effects of KTRP content and crosslinking time on the physicochemical properties, temperature-responsive behavior, and drug release performance of the membranes were systematically investigated. The results showed that the incorporation of KTRP effectively tuned the lower critical solution temperature (LCST) of the membranes within the range of 37.2-42.4°C and endowed them with reversible temperature-triggered shrinkage/expansion behavior. Appropriate crosslinking further improved the water resistance and thermal stability of the membranes without weakening their temperature-responsive performance. In addition, drug release experiments showed that the membranes exhibited accelerated release behavior above the LCST, confirming their temperature-responsive controlled-release capability. In vitro cytocompatibility evaluation further demonstrated that the composite nanofiber membranes were non-cytotoxic and supported the adhesion and proliferation of L929 cells. The research provides a simple method to synthesize the keratin-based temperature-sensitive polymer by one-step method. The prepared keratin-based temperature-responsive nanofiber membrane can serve as a promising biomaterial platform for smart wound dressings and temperature-responsive drug delivery.
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DOI
高影响因子
Soft Matter
·
2015
·Vol. 11
·期 14
·2771-2781
·
IF 4.029
Lei Hou,Peiyi Wu
The LCST-transitions of linear, well-defined polymers of N-isopropylacrylamide (NIPAM) and N-vinylcaprolactam (VCL), including a homopolymer mixture, diblock and statistical copolymers, in water are explored and compared by applying turbidity and FTIR measurements in combination with two-dimensional correlation spectroscopy (2Dcos). Only one transition is observed in all polymer systems, suggesting a dependent aggregation of poly(N-isopropylacrylamide) (PNIPAM) and poly(N-vinylcaprolactam) (PVCL) parts in the phase transition processes. With the help of 2Dcos analysis, it is discovered that the hydrophobic interaction among C–H groups is the driving force for simultaneous collapse of the two distinct thermo-responsive segments. Additionally, the delicate differences within the LCST-transitions thereof have been emphasized, where the phase separation temperatures of the homopolymer mixture and the diblock copolymer are close while that of the statistical copolymer is relatively higher. Moreover, both diblock and statistical copolymers exhibit rather sharp phase transitions while the homopolymer mixture demonstrates a moderately continuous one.
研究领域:
高分子化学
·
物理化学
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产品关联
DOI
PubMed
高影响因子
CARBOHYDRATE POLYMERS
·
2016
·
IF 4.219
Cundian Gao,Junli Ren,Cui Zhao,Weiqing Kong,Qingqing Dai,Qifeng Chen,Chuanfu Liu,Runcang Sun
Xylan-based temperature/pH sensitive hydrogels were prepared by the crosslinking copolymerization of xylan with N -isopropylacrylamide (NIPAm) and acrylic acid (AA) using N,Ń -methylenebis-acrylamide (MBA) as a cross-linker and 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator via ultraviolet irradiation. The influence of the NIPAm, AA and MBA amount on properties of xylan-based hydrogels was discussed. The morphology and interactions of hydrogels were characterized by SEM and FTIR. The lower critical solution temperature (LCST) of hydrogels was investigated by DSC. The results indicated that the LCST of hydrogels emerged at around 34 °C and increased with increasing the AA content. The drug encapsulation efficiency of as-prepared hydrogels reached to 97.60% and the cumulative release rate of acetylsalicylic acid was 90.12% and 26.35% in the intestinal and gastric fluid, respectively. Xylan-based hydrogels were proved to be biocompatible with NIH3T3 cell by MTT assay and showed the promising application as drug carriers for the intestinal-targeted oral drug delivery.
研究领域:
材料科学
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生物医学工程
·
药剂学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2022
·
IF 6.633
Xinyu Ma,Yingjuan Zhang,Shuwei Cai,Xianru He
Copolymers of N-vinylpyrrolidone (NVP) and methyl acrylate (MA) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization, which exhibited typical lower critical solution temperature (LCST) behavior in aqueous solution. The molecular structure and composition of copolymer P(NVP-co-MA) were characterized by FTIR and NMR. The response behavior was investigated by UV transmittance tests. The LCST of the copolymer P(NVP-co-MA) can vary from 17 °C to 90 °C by adjusting the ratio of the two monomers, showing a wide tunable range. The dynamic light scattering (DLS) results showed that beyond LCST, the hydrodynamic size increased with increasing temperature, polymer molecular chains aggregated in solution, and solubility deteriorated, confirming its LCST responsiveness. In addition, the copolymer P(NVP-co-MA) is salt responsive as well as pH-responsive. The multi-responsive and biocompatible copolymer has a large potential application in the fields of materials and biomedicine.
研究领域:
材料科学
·
生物医学工程
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产品关联
DOI
高影响因子
ACS Applied Polymer Materials
·
2025
·
IF 4.7
Li Tang,Fang Liu,Yue Xu,Dan Xiao,Zidan Zhang,Haoyu Jiang,Liang Gong,Jianxin Tang
Bilayer hydrogel actuators, with their anisotropic structure akin to biological tissues, are poised to revolutionize the fields of soft robotics and tissue engineering. Despite their promise, achieving a harmonious balance between high bulk toughness, robust interface toughness, and actuating property has been a formidable challenge, significantly hindering their broader application. By employing a dual-strategy approach, we successfully developed a poly(N-isopropylacrylamide-co-acrylamide)-agar/poly(acrylamide-co-acrylic acid) [p(NIPAM-co-AAM)-agar/p(AAM-co-AAC)] (NM–AMC) LCST- and UCST-type double-layer hydrogel actuator. First, the double-network strategy enhanced the mechanical properties of the hydrogel. Second, the synchronous UV polymerization method effectively improved the toughness of the interface between the two layers of hydrogels. The NM–AMC double-layer hydrogel actuator integrates the low-temperature response characteristics of NM (lower critical solution temperature-type) and the high-temperature response characteristics of AMC (upper critical solution temperature-type). This design confers a unique dual-thermal response behavior on the actuator, enabling it to achieve reversible bending angle changes from +361.33 to −417.33° over a temperature range of 5–85 °C. More importantly, after 5 cycles, the NM–AMC bilayer hydrogel actuator did not have obvious delamination, indicating that the NM–AMC bilayer hydrogel shows an excellent interface toughness between the two layers of hydrogels. Inspired by the adaptive mechanisms of plants in nature, a series of NM–AMC biomimetic hydrogel actuators were designed to emulate the morphology of flowers and leaves. This innovation not only substantially expands the actuating range of hydrogel actuators but also offers new insights into the intelligent design and manufacture of responsive hydrogel systems, thereby advancing the development of biomimetic hydrogel technology.
研究领域:
软体机器人学
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生物材料工程
·
组织工程学
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产品关联
DOI
高影响因子
Soft Matter
·
2014
·Vol. 10
·期 16
·2856-2862
·
IF 4.151
Lvdan Liu,Yang Shi,Chang Liu,Tao Wang,Guangming Liu,Guangzhao Zhang
Methylated urea and sugar are chaotropic and kosmotropic osmolytes, respectively. In the present work, we have investigated the specific anion effect on the lower critical solution temperature (LCST) behavior of poly(N-isopropylacrylamide) (PNIPAM) in the presence of methylated urea or sugars. Differential scanning calorimetry studies revealed that tetramethylurea can adsorb onto the PNIPAM surface, but glucose is excluded from the PNIPAM surface. The specific anion effect on the LCST behavior of PNIPAM is amplified by methylated urea but not by sugars. The amplification of the anion specificity by methylated urea is attributed to an increased difference in the anion-specific polarization of hydrogen bonds, induced by the formation of PNIPAM/methylated urea complexes via hydrophobic interactions. As the number of methyl groups on the methylated urea increases, the extent of amplification of the anion specificity increases due to increasing hydrophobic interactions between the PNIPAM and methylated urea. Additionally, no amplification of the anion specificity is observed in the presence of urea because a PNIPAM/urea complex cannot be formed via hydrophobic interactions.
研究领域:
生物化学
·
高分子化学
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DOI
高影响因子
Polymer Chemistry
·
2017
·Vol. 8
·期 24
·3679-3688
·
IF 5.375
Donghao Wang,Shutong Guo,Qiang Zhang,Paul Wilson,David M. Haddleton
In this study, we report on the synthesis of thermoresponsive polymers with different microstructures, a precisely tunable lower critical solution temperature (LCST) and terminal catechol anchors by copper(0) mediated living radical polymerization (Cu(0)-LRP). All the Cu(0)-LRP polymerizations were performed directly from the unprotected dopamine-functionalized initiators at ambient temperature or below in aqueous solution with full or close to full conversion obtained in minutes. The resulting polymers exhibited a designed molecular weight (MW), narrow MW distribution and high end-group fidelity capable of in situ block copolymerization. We demonstrate their application toward the surface modification of titanium dioxide nanoparticles by the successful preparation of smart nanocomposites with a self-flocculation effect. A “one-pot” strategy was then developed for the simultaneous polymerization and surface modification to simplify the multi-step purification and immobilization processes. The subsequent degradation of Rhodamine B under the irradiation of simulated solar light proved the potential application of hybrid nanocomposites in water treatment and a switching effect of photocatalytic ability below or above the LCST was also observed.
研究领域:
材料科学
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化学工程
·
环境科学
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产品关联
DOI
高影响因子
EUROPEAN POLYMER JOURNAL
·
2022
·
IF 5.546
Hangjing Zhang,Tianyuan Gao,Lei Jiang,Xiangqi Meng,Jian Wang,Ning Ma,Hao Wei,Xinyue Zhang
Smart hydrogels have been widely applied in the bionic intelligent devices for the virtues of biocompatibility, well processibility, environmental sensitivity, and so on. Traditional poly(N-isopropylacrylamide) (PNIPAM) hydrogel has the native response to the temperature change, but the weak strength and narrow phase transition point have limited its applications. Moreover, the poor conductivity of PNIPAM has shields the response signals to the outside. In this work, we have put forward a facile strategy by introducing the ionic conductive deep eutectic solvent (DES) composed of acetylcholine chloride (ACh) and acrylamide (AAm). Followed by one-step copolymerization of AAm and NIPAM, the PAAm-DES/PNIPAM hydrogel formed with the tunable lowest critical solution temperature (LCST), high strength, fine transparence, and good conductivity. As a result, the hydrogel showed the high-sensitive, wide-range and stable response on the outer strain and thermal change, which can play as a sensing element in the intelligent devices. This cost-effective method will be a potential way for fabricating the environmental and multifunctional materials.
研究领域:
材料科学
·
生物医学工程
·
化学工程
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）