MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2023
·Vol. 225
·期 5
·2300361
·
IF 2.5
Dan Liu,Hui Liang,Jiang Lu
A novel monomer, N -(2-((3-morpholine-3-isopropyl)thio)ethyl)methacrylamide (MTMA), is synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization to give a thermoresponsive polymer poly[ N -(2-((3-morpholino-3-oxopropyl)thio)ethyl)methacrylamide] (PMTMA). PMTMA exhibits reversible thermoresponsive phase transitions of the lower critical solution temperature (LCST) type in water and the upper critical solution temperature (UCST) type in ethanol and methanol. The degree of polymerization and concentration of PMTMA, and solvent type have a significant influence on the transition temperature. PMTMA shows complicated thermoresponse in water–alcohol mixtures. In water–ethanol mixtures, the phase diagram of PMTMA can be divided into three regions according to ethanol volume percentages, φ : 0 ≤ φ < 15% for an LCST region; 15% ≤ φ < 91.5% for a complete dissolution region; 91.5% ≤ φ ≤ 100% for a UCST region. At high water content, the LCST increases with increasing ethanol content; and at high ethanol content, the UCST decreases with increasing water content. In water–methanol mixtures, PMTMA shows more complex thermoresponse. In the range of 0–50 °C, the phase diagram can be divided into five regions, depending on the methanol volume percentages φ : 0 ≤ φ < 15% for LCST region; 15% ≤ φ < 25% for immiscible region; 25% ≤ φ < 85% for UCST region; 85% ≤ φ < 95% for fully dissolved region; 95% ≤ φ ≤ 100% for another UCST region.
研究领域:
高分子化学
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材料科学
·
物理化学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Yi Zhang,Yu Deng,Weidong Guo,Donghao Liu,Yigang Ding
Developing the efficient ionic liquid (IL)-based extractants for the solvent extraction of the rare earth elements (REEs) is crucial but still facing challenges. In this study, two carboxylic acid-functionalized upper critical solution temperature (UCST)-type ILs, N-carboxymethylpyridinium bis(trifluoromethylsulfonyl)imide ([HbetPy][Tf2N]) and N-carboxymethyl-N-methylmorpholinium bis(trifluoromethylsulfonyl)imide ([HbetMor][Tf2N]), are successfully synthesized and characterized. The extraction and separation performance toward scandium [denoted as Sc(III)] in nitrate medium aqueous solution have been carefully investigated in the homogeneous liquid–liquid extraction system under different conditions (e.g., equilibrium time, initial acidity, salting-out agent concentration, and REE concentration). The results reveal that the enhanced extractabilities of Sc(III) can be observed in homogeneous extraction compared to the biphasic system owing to the improved metal ion transfer and accelerated extraction kinetics. Meanwhile, [HbetPy][Tf2N] and [HbetMor][Tf2N] both illustrate high selectivity for Sc(III) separated from another five REEs (including La, Nd, Eu, Ho, and Yb), with the separation factors of 749 and 499 for Sc(III)/Yb(III), respectively. Moreover, the mechanism investigation indicates the formation of the Sc(III) complex via a proton exchange, evolved from the slope analysis and Fourier-transform infrared results. This study provides a prototype for the construction of the homogeneous liquid–liquid extraction system via the novel UCST-type ILs for highly efficient REE extraction and supplies the future application for the recovery of REEs from wastes.
研究领域:
化学工程
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材料科学
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环境科学
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产品关联
DOI
高影响因子
LANGMUIR
·
2026
·
IF 3.9
Qiurui Lin,Die Luo,Pan Du,Wei Zhang,Huiru Feng,Xinyu Ma,Xianru He
Polymers composed of zwitterionic monomer units generally exhibit upper critical solution temperature (UCST)-type thermoresponsive behavior. However, these monomers possess specialized structures, involve complex synthesis, and have limited varieties available. Herein, we report a novel polyelectrolyte that exhibits UCST behavior in aqueous solutions, achieved by regulating the content and sequence distribution of anionic and cationic monomers. The effects of ionic group content and counterion incorporation on the molecular chain conformation and UCST behavior are investigated. Meanwhile, the polymer solution demonstrates clusteroluminescence with aggregation-enhanced and temperature-dependent emission. As the temperature decreases, intermolecular electrostatic interactions are enhanced, which rigidifies the chain conformation and increases the clusteroluminescence. This work provides a facile approach for preparing polymers with UCST behavior by copolymerizing two ionic monomers with opposite charges. This broadens the selection of monomers, which promises the development of these thermoresponsive luminescent polymers exhibit potential for applications in fields such as visualization sensing.
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产品关联
DOI
PubMed
高影响因子
Polymer Chemistry
·
2024
·Vol. 15
·期 27
·2780-2789
·
IF 4.1
Ke Wang,Zilong Wang,Meiyu Si,Xiaofang Liu,Guiyan Liu,Yongfei Zeng
Three novel temperature/pH/CO2-triple-responsive homopolymers namely P(Et-N-EO2MA), P(THP-N-EO2MA) and P(Ph-N-EO2MA) were prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization. They have the same backbone structure but different types of end substituents i.e., ethyl, tetrahydropyran, and the benzene ring, respectively. Subsequently, their responsive properties were studied. P(Et-N-EO2MA) has a lower critical solution temperature (LCST)-type cloud point (CP) in aqueous solution and is affected by many factors such as the molecular structure and weight, concentration, additives, pH and CO2. P(THP-N-EO2MA) is soluble in water, but in different buffer solutions, it shows a soluble–LCST–insoluble transition, and its LCST-type CP can also be adjusted by molecular weight and concentration. P(Ph-N-EO2MA) is insoluble in water, but reversible phase transformation can be achieved by adjusting the pH of the solution or injecting CO2, and it also shows different properties in buffer solutions and an upper critical solution temperature (UCST)-type CP in n-butanol. In addition, since P(Ph-N-EO2MA) is amphiphilic, it can be self-assembled in solution, and the release of Nile Red (NR) can be achieved under the stimulation of acid. The different properties of these homopolymers show the effect of substituents on the responsiveness of multistimuli-responsive polymers, which provides ideas for the design of stimuli-responsive polymers, and have good application prospects in the fields of self-assembly and controlled release.
研究领域:
高分子化学
·
材料科学
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DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
·
2015
·Vol. 53
·期 21
·2469-2480
·
IF 3.113
Yong Deng,Xi Wang,Qiulin Yuan,Mengxiang Zhu,Ying Ling,Haoyu Tang
A series of side-chain-functionalized α-helical polypeptides, i.e., poly(γ-4-(3-chloropropoxycarbonyl)benzyl- L -glutamate) (6) have been prepared from n-butylamine initiated ring-opening polymerization (ROP) of γ-4-(3-chloropropoxycarbonyl)benzyl- L -glutamic acid-based N -carboxyanhydride. Polypeptides bearing oligo-ethylene-glycol (OEG) groups or 1-butylimidazolium salts were prepared from 6 via copper-mediated [2+3] alkyne-azide 1,3-dipolar cycloaddition or nuleophilic substitution, respectively. CD and FTIR analysis revealed that the polymers adopt α-helical conformations both in solution and the solid state. Polymers bearing OEG (m = 3) side-chains showed reversible LCST-type phase transition behaviors in water while polymers bearing 1-butylimidazolium and I − counter-anions exhibited reversible UCST-type transitions in water. Variable-temperature UV-vis analysis revealed that the phase transition temperatures ( T pt s) were dependent on the main-chain length and polymeric concentration. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53 , 2469–2480
研究领域:
高分子化学
·
生物材料
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产品关联
DOI
高影响因子
Gels
·
2025
·Vol. 12
·期 1
·8
·
IF 5.3
Mingliang Du,Huifeng He,Qingchen Wang,Keming Sheng,Guancheng Jiang,Yinbo He
Conventional polymer-based plugging materials often fail in deep-well environments due to passive thermal softening and network relaxation, which significantly compromise mechanical integrity and interfacial retention. To address this challenge, a novel smart Upper Critical Solution Temperature (UCST)-responsive hybrid microgel (SUPA) was synthesized for adaptive plugging in complex formations. The distinctive UCST responsiveness was conferred by incorporating N-(2-amino-2-oxoethyl)acrylamide (NAGA) and N-(2-hydroxypropyl) methacrylamide (HPMA) functional units into a robust dual-crosslinked network. Particle size analysis and oscillatory rheology in saline solution revealed the thermal activation mechanism: surpassing the critical temperature triggers the dissociation of intramolecular hydrogen bonds, driving polymer chain extension and volumetric expansion. This conformational transition induces dynamic network reinforcement, quantified by a significant ~7.5-fold increase in the storage modulus (G′). Consequently, the SUPA-enhanced fluid exhibited superior rheological performance, including a 4.4-fold increase in low-shear viscosity and rapid thixotropic recovery (ratio of 1.06). Crucially, lost circulation tests confirmed reliable and highly efficient sealing performance under harsh conditions of 150 °C and 5 MPa, even in fractured models. This study validates a design strategy centered on UCST-activated network reinforcement, offering a robust, mechanism-driven solution for severe lost circulation control in deep-well drilling.
研究领域:
石油工程
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智能材料
·
高分子科学
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胶体与界面科学
·
钻井液
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DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2022
·
IF 7.968
Zhaohui Chen,Jiacong Wu,Wenrui Huang,Yuanyuan Li,Yanli Mao,Juan Han,Yun Wang,Liang Ni
Horseradish peroxidase (HRP) is a kind of enzyme commonly used in clinical trials that is rich in the plant horseradish. It has a wide range of applications in the fields of pharmacy and pollution control . However, free enzymes are easily denatured and inactivated by environmental influences, which is not conducive to the normal progress of the reaction. At the same time, the cost of enzymes is relatively high, and it is difficult to separate and recover during the reaction. In this study, the UCST-type temperature- responsive polymer was combined with HRP under the optimal immobilization reaction conditions of 3% polymer solution concentration, 60 ℃, and pH= 8 through affinity interaction to produce UCST-type smart polymerase. The smart polymerase has stronger temperature stability, pH stability and storage stability than free enzymes. In the simulated pollutant degradation experiment, under the molar ratio of phenol to H 2 O 2 is 1:1, the temperature of 60 ℃, and pH= 7, smart polymerase can degrade 91% of phenol in a 100 mg/L phenol solution within 1 h. After five cycles of catalytic reaction , 68% of smart polymerase was recovered through cooling precipitation. In the phenol degradation experiments of two different real water samples, 88% and 90% of the phenol in the water were removed, respectively, and most of the highly active immobilized enzymes were recovered at the same time. Finally, the biotoxicity of the catalyzed reaction product is significantly reduced was demonstrated.
研究领域:
生物化学
·
环境科学
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产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2021
·Vol. 45
·期 13
·5925-5932
·
IF 3.591
Cheng Zhou,Yan Chen,Mingjun Huang,Yi Ling,Liming Yang,Guochen Zhao,Jie Chen
A dual temperature-responsive triblock polymer (poly(N-isopropyl acrylamide)-block-poly(N,N-dimethyl acrylamide)-block-poly(acrylamide-co-acrylonitrile)) (P(AM-co-AN)-b-PDMA-b-PNIPAM) (NDAA) was obtained by sequential reversible addition–fragmentation chain transfer (RAFT) polymerization,with the uncharged UCST temperature-sensitive block P(AM-co-AN) and the classic LCST-type temperature-sensitive block PNIPAM. This well-defined thermo-responsive copolymer with tunable compositions exhibits a dual thermal response behavior in water. Properly designing the length of the block can make the block copolymer undergo a phase transition within the envisaged temperature range. When the concentration is 5 wt%, the UCST of the NDAA polymer is around 20 °C, and the LCST is around 31 °C. All three blocks of these polymers are soluble in water within 20–31 °C. At high temperature, PNIPAM hydrophobically aggregates into a core, and NDAA self-assembles into a core1 (PNIPAM)–shell (PDMA)–corona1 (P(AM-co-AN)) structure. In contrast, at low temperatures, P(AM-co-AN) forms hydrogen bonds and is insoluble in water, and NDAA self-assembles into a core2–shell–corona2 structure. In this way, it is possible to prepare spontaneously reversible micellar aggregates in water. After the concentration reaches the lowest critical concentration, the NDAA polymer can undergo a reversible gel behavior, that is, a phase transition occurs near the UCST and LCST. This change in the polarity of the micelle core opens up the possibility of dissolving different compounds in water just by changing the temperature.
研究领域:
高分子化学
·
材料科学
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DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
·
2025
·
IF 3.7
Feiyun Li,Huinan Liang,Helin Li,Yanjun Tang
The high cost of enzymatic glycolysis has seriously restricted the industrialization of lignocellulose-based sugar platform technology. Recovering and recycling cellulase can reduce the cost. Here, a thermo-responsive claw-type polysulfobetaine (PSPA) was constructed for hydrophobic grasping and efficient recycling of cellulase. Compared with the linear sulfobetaine homopolymer (PSPE), PSPA had more sensitive temperature response and strong cellulase recovery ability. PSPE-3 (Mw=355.1 kDa) was added to the hydrolysis system of corncob residue (CCR) (50 °C), at 0.4 mass ratio of PSPE-3 to cellulase, and after enzymatic hydrolysis, 50% of the cellulase was saved when cooling to 25 °C. But only 0.05 times PSPA-1 (Mw=30.0 kDa) was added to the CCR system, and 70% of the cellulase was saved when cooling to 25 °C. This work presents a claw shaped protein-capture agent, polysulfobetaine for capturing cellulase, which is of great significance to reduce the lignocellulosic hydrolysis cost, and efficiently separate enzyme proteins.
研究领域:
生物化学
·
工业酶学
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产品关联
DOI
PubMed
高影响因子
COLLOID AND POLYMER SCIENCE
·
2020
·Vol. 298
·期 8
·1053-1061
·
IF 1.536
Cai Shuwei,Gu Shiyu,Li Xian,Wan Songhan,Chen Songbo,He Xianru
A controlled grafting modification starch exhibited tunable phase transition temperature in aqueous solution was prepared via reversible addition–fragmentation chain transfer (RAFT) polymerization and esterification reaction under mild condition. P(AM/AN) copolymer was grafted onto the starch backbone and endowed the grafted copolymer thermosensitivity. The molecular structure and composition of P(AM/AN) copolymers were characterized by gel permeation chromatography (GPC), FTIR, and NMR, indicating a structurally controllable side chain of the grafted copolymer. Results of X-ray diffraction (XRD) demonstrate that the crystallinity of grafted copolymer decreases compared with starch due to side chains destruct the structural regularity of starch. Scanning electron microscopy (SEM) images show that grafted copolymer displays a rough, multilayer, and irregular morphology. Dynamic light scattering (DLS) and UV tests indicate that the grafted copolymer forms aggregates in aqueous solution and the UCST of the grafted copolymer is dependent on percent grafting (PG) and molecular interactions of side chains.
研究领域:
高分子化学
·
材料科学
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DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2023
·
IF 6
Xinyu Ma,Pan Du,Ben Niu,Jiaxuan Zhang,Huaisong Yong,Xianru He
Though the mechanism of temperature-induced lower critical solution temperature (LCST) in water is clear for the classic homopolymer poly( N -isopropylacrylamide) (PNIPAM), the LCST of other homopolymer or copolymer remains to be understood. In this work, a novel random copolymer poly(2-hydroxyethyl- co -methyl acrylate) (P(HEA- co -MA)) was prepared. The LCST of the copolymer P(HEA- co -MA) can vary from 11 °C to 65 °C by adjusting flexibly the ratio of the two monomers, showing a broad tunable range. The experimental results showed that the balance of hydrogen bond bridge formed by P(HEA- co -MA) in water and the hydrophobic interaction between polymers can cause the LCST transition of P(HEA- co -MA). An interesting observation is that the sharp phase transition (cosolvency) of P(HEA- co -MA) exists when a rather small amount of alcohol or water is added in polymer solutions at constant temperatures. Moreover, it was found that the increase of LCST is correlated with the increase of alcohol concentration in the water-rich regime, but the decrease of upper critical solution temperature (UCST) is related to the increase of water concentration in the alcohol-rich regime. This work shed light on the understanding of cosolvency by studying the solution behavior of copolymer P(HEA- co -MA) in mixed solvents, which can be of interest for the design of stimuli-responsive polymer materials by variation in solvent composition.
研究领域:
高分子化学
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材料科学
·
物理化学
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产品关联
DOI
高影响因子
MOLECULES
·
2015
·Vol. 20
·期 9
·17378-17392
·
IF 2.416
Jing Zhang,Jingjiang Liu,Yong Zuo,Rongmin Wang,Yubing Xiong
In this study, thermo-responsive polymeric nanogels were facilely prepared via one-step cross-linking copolymerization of ethylene glycol dimethacrylate/divinylbenzene and ionic liquid (IL)-based monomers, 1,n-dialkyl-3,3′-bis-1-vinyl imidazolium bromides ([CnVIm]Br;n= 6, 8, 12) in selective solvents. The results revealed that stable and blue opalescent biimidazolium (BIm)-based nanogel solutions could be obtained without any precipitation when the copolymerizations were conducted in methanol. Most importantly, these novel nanogels were thermo-response, and could reversibly transform to precipitation in methanol with temperature changes. Turbidity analysis and dynamic light scatting (DLS) measurement illustrated that PIL-based nanogel solutions presented the phase transform with upper critical solution temperature (UCST) in the range of 5–25 °C. The nanogels were characterized using Fourier transform infrared (FTIR), thermogravimetric analyses (TGA), and scanning electron microscopy (SEM). In addition, BIm-based nanogels could also be used as highly active catalysts in the cycloaddition reaction of CO2and epoxides. As a result, our attributes build a robust platform suitable for the preparation of polymeric nanomaterials, as well as CO2conversion.Keywords:ionic liquids;thermo-response;nanogels;cross-linking polymerization;UCST;CO2conversion
研究领域:
材料科学
·
催化化学
·
高分子化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）