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MACROMOLECULES · 2015 · IF 5.8

A New Thermo-, pH-, and CO2-Responsive Homopolymer of Poly[N-[2-(diethylamino)ethyl]acrylamide]: Is the Diethylamino Group Underestimated?

Zefeng Song,Ke Wang,Chengqiang Gao,Shuang Wang,Wangqing Zhang

A new multi-stimuli-responsive homopolymer of poly[N-[2-(diethylamino)ethyl]acrylamide] (PDEAEAM), which combines the thermoresponsive and pH/CO2-responsive moieties of the diethylamino and acrylamide groups, was proposed and synthesized by RAFT polymerization. Well-defined PDEAEAM was synthesized by solution RAFT polymerization as indicated by the linear increase in the polymer molecular weight with the monomer conversion and the narrow molecular weight distribution. The appending diethylamino group in the polymer backbone was found to be crucial to determine the thermoresponse of PDEAEAM in water. The parameters including the polymerization degree, the polymer concentration, the deuterated solvent, the terminal attached on the polymer backbone, the additives of salt and urea, and pH and bubbling CO2 affecting the thermoresponse of PDEAEAM in aqueous solution at the lower critical solution temperature (LCST) were investigated. The temperature-variable 1H NMR analysis suggests that the dehydration of PDEAEAM at temperature above LCST is ascribed to the weakened hydrogen bonding between the CONHCH2 and/or (CH2N(CH2CH3)2) moieties with the solvent of water. The proposed multi-stimuli-responsive homopolymer of PDEAEAM has two advantages of (1) the convenient and controllable RAFT synthesis and (2) the pH/CO2 tunable LCST at ∼36 °C being very close to body temperature.

CAS / MDL: 108-00-9 100-36-7
研究领域: 高分子化学 · 材料科学
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Polymer Chemistry · 2017 ·Vol. 8 ·期 19 ·2997-3005 · IF 5.375

A pH, glucose, and dopamine triple-responsive, self-healable adhesive hydrogel formed by phenylborate–catechol complexation

Meng Shan,Chu Gong,Bingqiang Li,Guolin Wu

An injectable polyethylene glycol (PEG) hydrogel was successfully prepared via borate–catechol complexation using dopamine functionalized 4-armed PEG (4-arm-PEG-DA) and phenylboronic acid modified 4-armed PEG (4-arm-PEG-PBA). The hydrogel was formed within 10 s by mixing 15 wt% 4-arm-PEG-DA with 15 wt% 4-arm-PEG-PBA buffer solutions at pH 9.0. The hydrogel was characterized by Fourier transform infrared (FT-IR) spectroscopy, rheological measurements, scanning electron microscopy (SEM) and lap shear strength tests. Furthermore, pH, glucose and dopamine responsiveness of the hydrogel based on phenylborate–catechol complexation was demonstrated by degradation experiments and drug release tests. The lap shear strength tests indicated that the hydrogel possessed the ability of self-healing which was bestowed by the phenylborate–catechol dynamic covalent bond. Moreover, the hydrogel could serve as a decent bio-adhesive due to its adhesion properties on different substrates especially the porcine skin. In vitro cytotoxicity tests demonstrated the excellent cytocompatibility of the hydrogel. The results of all the experiments indicate that our newly developed multi-functionalized hydrogel can have potential applications in biomedical fields such as drug delivery, tissue engineering, and bio-adhesives.

研究领域: 生物材料 · 药物递送 · 组织工程
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EUROPEAN POLYMER JOURNAL · 2018 · IF 3.741

SO2, temperature, and oxidation multi-responsive homopolypeptide: Synthesis, characterization, and exploration of their potential applications

Minjie Li,Zelai Zheng,Liwei Sun,Ying Ling,Shifang Luan,Haoyu Tang

SO 2 -responsive homopolypeptide with tri(ethylene glycol), 1,2,3-triazole linkages and N -butylimidazolium iodide pendants ( P4 ) were prepared by the ring-opening polymerization of γ- 2-(2-(2-chloroethoxy)ethoxy)ethyl- l -glutamic acid based N -carboxyanhydride then post-polymerization to the side-chain, by the nucleophilic substitution of the chloro group in the presence of NaN 3 , followed by the copper-mediated 1,3-dipolar cycloaddition, and subsequent ion-exchange reaction. 1 H NMR analysis revealed that SO 2 interacted with 1,2,3-triazole group leading to polymer aggregation. The P4 /SO 2 aqueous solution is multi-responsive that can be triggered by gas (N 2 /SO 2 ), temperature, and oxidation (i.e., H 2 O 2 ). Poly(vinyl alcohol) (PVA) hydrogel modified by P4 and BaSO 3 particles were prepared, the resulting hydrogel showed improved mechanical properties in terms of both stiffness and toughness.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 化学 · 生物材料
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JOURNAL OF MATERIALS SCIENCE · 2017 ·Vol. 53 ·期 3 ·1945-1961 · IF 2.599

Preparation and self-assembly of Au nanoparticles coordinated Fe3O4 graft block copolymer multifunctional nanohybrids with pH, electrochemical and magnetic stimuli responsiveness

Xu Jing-Wen,Cui Zhuo-Miao,Xu Feng,Luo Yan-Ling

Multi-component block copolymer nanohybrids consisting of Fe 3 O 4 nanoparticles and poly(acryloyloxyethyloxyl 1-mercaptohemisuccinate) and poly(methacrylic acid) (PMAA) blocks were synthesized via the surface-initiated atom transfer radical polymerization, followed by the esterification with d,l-mercaptosuccinic acid. The block copolymer nanohybrids were coordinated with Au nanoparticles (Au NPs) through pendent thiol groups to form Au NPs coordinated Fe 3 O 4 graft block copolymer nanohybrids. Fluorescent spectrometry, TEM and SEM findings indicated that these block copolymer nanohybrids could self-assembled and form globular core–shell nanomicelles, and their critical micelle concentrations decreased with the decrease in the length of PMAA chains and the incorporation of Au NPs. Zeta potential measurements signified that the copolymer nanohybrids possessed significantly high stability. DLS results indicated that hydrodynamic diameters of the copolymer nanohybrids distributed within the scope of 85–155 nm, hinging on the length of the graft chains and the complexation of Au NPs. The hybrid block copolymer nanomicelles exhibited pH, electrochemical and magnetic responsiveness, with pH transition points at 5.3–5.9. The incorporation and the loading percentage of Au NPs improved the reversibility of the electrochemical response and plasmon resonance. The block copolymer nanohybrids were superparamagnetic and were expected to broaden their applications by virtue of the multi-component combination and the resulting multifunctionality.

CAS / MDL: 7787-70-4
研究领域: 材料科学 · 纳米医学
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JOURNAL OF ORGANOMETALLIC CHEMISTRY · 2019 · IF 2.066

Synthesis of ferrocene and azobenzene-based copolymers P(FHEMA-co-MAZOHE)s and their redox and photo-responsive properties

Amin Khan,Haojie Yu,Li Wang,Pavel A. Zhizhko,Dmitry N. Zarubin,Dmitry A. Lemenovskiy,Fazal Haq,Muhammad Usman,Ahsan Nazir,Kaleem-ur-Rehman Naveed

Herein, poly(2-(methacryloyloxy) ethyl ferrocene carboxylate- co -(methacrylohydroxyhexane azobenzene)s) (P(FHEMA- co -MAZOHE)s) were prepared by random copolymerization and were characterized by proton nuclear magnetic resonance ( 1 H NMR) and gel permeation chromatography (GPC) to confirm the structures and molecular weights respectively. Thermal variations were analyzed by thermogravimetric (TG), differential thermogravimetric (DTG) and differential scanning calorimetry (DSC) techniques. Finally, redox and photo stimuli-responsive properties were confirmed by cyclic voltammetry (CV) and ultraviolet–visible spectroscopy (UV–vis) respectively. The results revealed that (P(FHEMA- co -MAZOHE)s) can be useful as information storage materials.

CAS / MDL: 1271-42-7 78-67-1
研究领域: 高分子化学 · 材料科学
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POLYMER INTERNATIONAL · 2015 ·Vol. 64 ·期 10 ·1415-1424 · IF 2.409

Temperature and pH responsive hydrogels based on polyethylene glycol analogues and poly(methacrylic acid) via click chemistry

Weijuan Sheng,Teng Liu,Shouxin Liu,Qinqin Wang,Xuan Li,Naer Guang

A novel temperature responsive copolymer, poly[2-(2-methoxyethoxy)ethyl methacrylate- co -oligo(ethylene glycol)methacrylate- co-N -hydroxymethyl acrylamide] [P(MEO 2 MA- co -OEGMA- co -HMAM)], was synthesized by atom transfer radical polymerization. pH responsive poly(methacrylic acid) (PMAA) was synthesized by reversible addition-fragmentation chain transfer polymerization. After the hydroxyl groups on P(MEO 2 MA- co -OEGMA- co -HMAM) were transformed into azide groups and the carboxyl groups on PMAA were transformed into alkyne groups respectively, a novel temperature and pH responsive hydrogel was fabricated by click chemistry between the azide-P(MEO 2 MA- co -OEGMA- co -HMAM) and alkyne-PMAA in the presence of CuSO 4 and sodium ascorbate in aqueous solution. The rheological kinetics of gel formation demonstrated that gelation had commenced within 5 min at 25 °C, since then the storage modulus ( G ′) was higher than the loss modulus ( G ″). SEM images of hydrogel morphology and the swelling ratios of hydrogel at different temperatures and pH proved that the formed hydrogel had temperature and pH sensitivities. Bovine serum albumin was used as a model to evaluate the sustained release of the hydrogel; the results indicated that the hydrogel was a promising candidate for controlling protein drug delivery. © 2015 Society of Chemical Industry

CAS / MDL: 134-03-2
研究领域: 材料科学 · 生物医学工程 · 高分子化学
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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 34 ·14551-14559 · IF 3.288

A pH and UCST thermo-responsive tri-block copolymer (PAA-b-PDMA-b-P(AM-co-AN)) with micellization and gelatinization in aqueous media for drug release

Cheng Zhou,Yan Chen,Mingjun Huang,Yi Ling,Liming Yang,Guochen Zhao,Jie Chen

A brand new pH and thermo-responsive amphiphilic ABC triblock copolymer of poly(acrylic acid)-block-poly(N,N-dimethyl acrylamide)-block-poly(acrylamide-co-acrylonitrile) (PAA-b-PDMA-b-P(AM-co-AN)) was synthesized via sequential reversible addition–fragmentation chain transfer (RAFT) polymerization. Due to the pH-responsive blocks of PAA and thermo-responsive blocks of P(AM-co-AN), the properties of the copolymer solution were controlled by varying parameters such as temperature and pH. Specifically, it formed different nanostructures and showed gel behavior under different conditions. In detail, under high temperature alkaline conditions, ADAA was dissolved in an aqueous solution in the form of a molecular chain. Thereafter, when the temperature became lower or pH became acidic, the triblock copolymer self-assembled into different micelle structures, including shell–core, core–shell–core and tighter core–linking–core nanoparticles. In addition, the phase transition temperature of the copolymer was adjusted by pH and concentration. When the copolymer hydrogel was injected into a simulated human body device, it showed sustained drug release behavior and low transient drug concentrations. MTT experiments demonstrated the good biocompatibility of the ADAA hydrogels. This research provides inspiration to develop new polymers which are expected to be promising candidates as part of drug delivery platforms. Compared with traditional responsive hydrogels, its UCST can be easily controlled and is more stable through the feeding ratio, making it more advantageous in human drug delivery applications. In summary, we believe that this UCST and pH-responsive injectable ADAA hydrogel is researchable and applicable in the biomedical field.

研究领域: 材料科学 · 生物医学工程 · 药学
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MACROMOLECULAR BIOSCIENCE · 2013 ·Vol. 13 ·期 4 ·494-502 · IF 3.742

Hollow Multilayer Microcapsules for pH-/Thermally Responsive Drug Delivery using Aliphatic Poly(urethane-amine) as Smart Component

Jun Shi,Chao Du,Jin Shi,Yaming Wang,Shaokui Cao

Hollow multilayer microcapsules made of aliphatic poly(urethane-amine) (PUA) and sodium poly(styrene sulfonate) (PSS), templated on PSS-doped CaCO 3 particles, are prepared for pH-/thermally responsive drug delivery. The electrostatic interaction and hydrogen bonding under weak-acid conditions between aliphatic PUA and PSS contribute to the formation of multilayer microcapsules. Scanning electron microscopy (SEM) results demonstrate an obvious variation of the hollow multilayer microcapsules in response to changes in temperature and pH value. Drug-release behaviors using DOX as a model drug demonstrate that the drug release increases on decreasing the pH value because of the interaction weakness between aliphatic PUA and PSS in acidic conditions. Moreover, the drug release is higher at 55 °C than that at 37 °C for the sake of the shrinkage of aliphatic PUA above its lower critical solution temperature (LCST).

CAS / MDL: 78-96-6
研究领域: 材料科学 · 药学
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Journal of Biobased Materials and Bioenergy · 2016 ·Vol. 10 ·期 4 ·284-289 · IF 0.635

pH- and Temperature-Responsive Chitosan-g-PDMAEMA as an Active Coating Material and Its Effects on the Storing of Grape

Jiang Ping,Jia Shan Shan,Wang Shuang,Xiao Jun Hua,Liu Wenjie,Wu Yiqiang

The pH- and temperature-responsive chitosan-graft-poly(2-(dimethylamino) ethyl methacrylate) (CS-g-PDMAEMA) were synthesized via atom transfer radical polymerization (ATRP) and evidenced by FTIR spectroscopy. Chitosan macroinitiator (CS-Br) was prepared by phthaloylation of amino groups of chitosan and acylation of hydroxyl groups of chitosan with 2-bromoisobutyryl bromide. The pH and temperature responses of the copolymer micelles were characterized by particle diameter and particle size analyzers. The film prepared from CS-g-PDMAEMA was used as a coating film on the surface of the grape. And the film prepared from 1 wt% CS-g-PDMAEMA solution was able to slow the loss of water in grape. The results revealed that the CS-g-PDMAEMA had potential application as active coating materials in the storage of fresh grape.

研究领域: 食品科学 · 高分子化学
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BIOPOLYMERS · 2018 ·Vol. 110 ·期 4 ·e23243 · IF 1.99

Dual-responsive pegylated polypeptoids with tunable cloud point temperatures

Xiaohui Fu,Jiliang Tian,Zheng Li,Jing Sun,Zhibo Li

A series of pegylated polypeptoids have been readily synthesized by a strategy combining ring-opening polymerization (ROP) and thiol-yne photoaddition. The polypeptoids simultaneously incorporated branched oligo(ethylene glycol) (OEG) units and thioether bonds in the side-chains. All the polypeptoids are readily soluble in aqueous solution and show reversible thermo-responsive properties. The cloud points (CPs) were demonstrated to be readily tunable in the range of ~25 °C-60 °C by varying the chemical composition, OEG chain length and the degree of polymerization. Attractively, the chemical compositions of the side chains are readily tunable via adjusting the molar ratios of a mixture of thiol terminated OEG molecules, which avoid synthesizing new monomers or copolymerization of different monomers. Further, the oxidation/reduction of thioether groups shows significant influence on the CPs, providing a second stimulus to tune the phase transition behaviors. Considering the biocompatibility and degradability, the dual-responsive polypeptoids are potential candidates for various biomedical or biotechnological applications. Graphical

研究领域: 生物材料学 · 高分子化学 · 生物医药工程
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EUROPEAN POLYMER JOURNAL · 2014 · IF 3.242

Thermo- and pH-responsive behaviors of aqueous poly(acrylic acid)/poly(4-vinylpyridine) complex material characterized by ATR-FTIR and UV–Vis Spectroscopy

Bolin Li,Xiaolin Lu,Yonghao Ma,Zhan Chen

A novel thermo- and pH-responsive poly(acrylic acid) (PAA)/poly(4-vinylpyridine) (P4VP) aqueous material with an upper critical solution temperature (UCST) was developed in this study. It was found that the formation of the aqueous complex material was caused by the deprotonation of pyridinium groups of P4VP molecules and consequent hydrogen bonding formation between pyridine and carboxylic groups. This aqueous material exhibited significant reversible transition behaviors between the turbid colloidal and transparent solution states upon altering the pH and temperature values. Furthermore, the correlation between the solution pH and the upper critical solution temperature (UCST) enables us to design responsive aqueous materials with a broadly adjustable transition temperature range.

CAS / MDL: 9003-01-4 9003-04-7
研究领域: 高分子化学 · 材料科学
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EUROPEAN POLYMER JOURNAL · 2018 · IF 3.741

A reduction-sensitive thermo-responsive polymer: Synthesis, characterization, and application in controlled drug release

Li Song,Bao Zhang,E Jin,Chunsheng Xiao,Gao Li,Xuesi Chen

Herein, a novel kind of reduction and thermal dual-responsive polymer was synthesized by direct condensation polymerization of poly(ethylene glycol) (PEG) and 3,3′-dithiodipropanoic acid (DTPA). The resulting PEG-DTPA copolymers were soluble in water at room temperature and exhibited reversible thermal-responsive behaviors. The cloud point temperatures of PEG-DTPA copolymers were highly tunable dependent on the polymer concentration and the length of PEG segment. Additionally, the PEG-DTPA copolymers exhibited reduction-responsive behavior due to the presence of disulfide linkage groups in the backbone. This reduction-responsive property allowed the PEG-DTPA copolymers to be used in a drug delivery system. Thus, a triblock copolymer composed of mPEG2k and PEG400-DTPA copolymer was synthesized. The obtained copolymers could self-assemble into spherical micelles and exhibited thermal and reduction dual-responsive structure-variations in aqueous media. Furthermore, the hydrophobic Nile Red was effectively encapsulated into the micelles. The micelles maintained excellent reduction-responsive properties and can release drugs by reduction triggering. These results suggested that the PEG-DTPA copolymer may be promising for use as reduction and thermal dual-responsive drug carriers in cancer therapy.

研究领域: 高分子化学 · 药剂学 · 生物医学工程
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