ADVANCED FUNCTIONAL MATERIALS
·
2024
·
IF 18.5
Jiaqing He,Qiang Zhou,Zhiqing Ge,Shunfeng Jiang,Jiahe Li,Wei Feng,Haiyang Yang
Temperature-responsive hydrogels including lower critical solution temperature (LCST)- and upper critical solution temperature (UCST)-type hydrogels are attractive in various fields. However, the swift switch between LCST and UCST stimuli-responsive behaviors remains intriguing and challenging. Here is reported a kind of hydrogel with pH-gated LCST and UCST response behaviors. This is achieved using the hydrogen bonding between carboxylic acid groups of poly(acrylic acid- co -acrylamide) and hydroxyl groups of hydroxypropyl cellulose (HPC). The poly(acrylic acid- co -acrylamide)-HPC (PACA-HPC) hydrogels exhibit pH-gated reversible LCST-UCST phase transition behavior. When the transparent PACA-HPC hydrogel is placed in an acid bath, the COO − groups get protonated, rapidly forming hydrogen bonds with HPC to render a light-scattering state making the hydrogel opaque. Furthermore, the opaque hydrogel exhibits UCST phase transition behavior at 20–45 °C. When the opaque PCAC-HPC hydrogel is placed in an alkaline environment, hydrogen-bonded complexes gradually dissociate as the COOH groups are deprotonated to form a homogeneous transparent state. The transparent hydrogel exhibits LCST phase transition behavior at 20–45° C. Therefore, is shown the hydrogen bonding strategy to fabricate hydrogels with tunable LCST and UCST responses. With this pH-gated hydrogel with switchable LCST/UCST responsive behaviors, are demonstrated its applications in smart windows and information encryption.
研究领域:
材料科学
·
化学工程
·
生物医学工程
✓ 已验证
产品关联
DOI
高影响因子
BIOMACROMOLECULES
·
2018
·
IF 5.738
Chao Xing,Zhekun Shi,Jiliang Tian,Jing Sun,Zhibo Li
Stimuli-responsive polymers have received increasing interest for a variety of applications. Here, we report a series of unique charge-determined thermoresponsive polypeptoids synthesized by a combination of ring-opening polymerization and click chemistry. The LCST-type and UCST-type behavior is mainly dominated by the charge state on the side chain. Further, the phase transition temperature highly depends on the degree of polymerization, the side-chain architecture, the pH value, and so on. The obtained polypeptoid solutions exhibit good stability against temperature and salt concentration. To our knowledge, this report presents the first charge-determined LCST/UCST-type polymer from identical homopolymer backbone that displays a wide range of tunable cloudy points in aqueous media. We propose the hydrogen-bonding interaction plays a critical part on the solution behavior. These features make polypeptoids ideal candidates for highly designable stimuli-responsive polymeric materials.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
POLYMER
·
2016
·
IF 3.586
Yong Zuo,Zhenqian Jiao,Li Ma,Pengfei Song,Rongmin Wang,Yubing Xiong
In this study, novel thermo-responsive nanogels were facilely fabricated via ternary cross-linking copolymerization of ionic liquid (IL)-based monomers and cross-linker in methanol. To achieve the thermo-responsive performance of nanogels, monomers with hydroxyl or carboxyl group which can contribute to hydrogen (H)-bonding interaction is the key point of this strategy. The thermo-responsive behavior of poly(ionic liquid)s (PIL)-based nanogels were testified using dynamic light scattering (DLS), turbidimetric method, and differential scanning calorimetry (DSC) measurements. The results demonstrated that these novel nanogels presented reversible upper critical solution temperature (UCST) phase transition with the temperature changing. And their UCSTs could be tuned via the feed ratio of IL-based monomers and cross-linker. The nanogels were also measured using scanning electronic microscopy (SEM), thermo-gravimetric analyses (TGA) and Fourier transform infrared spectroscopy (FT-IR) techniques. In addition, a possible mechanism of thermo-responsive performance was suggested based on the above results. As a result, our findings provide an efficient and applicable platform for the fabrication of thermo-responsive polymeric nanomaterials .
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2016
·Vol. 34
·期 6
·777-784
·
IF 1.811
Shi Mei,Duan Xin-rui,Liu Zhao-tie,Liu Zhong-wen,Jiang Jin-qiang
A betaine-type styrene monomer with the quaternary ammonium-borate anion inner-salt pair was synthesized through the quaternization reaction and polymerized to afford the target polybetaine of poly(4-vinylbenzyl methyl-diethanol ammonium borate) (PVMAB). The chemical structures of the monomer and polymer were well demonstrated with 1 H-NMR and 11 B-NMR spectra analysis. The thermal-sensitive experiment showed that PVMAB in water afforded gradually welldefined sigmoidal transmittance-temperature ( T - t ) curves along with the increasing polymer concentration. However, the phase transition temperatures at the bottom of the S-shaped curves were always below 10 °C due to the very weak zwitterionic association of the ammonium-borate inner-salt pairs. The UCST phase transition could also be tuned by changing the ethanol content in the ethanol/water mixture. And the cytotoxicity experiment demonstrated the good biomimetic property of PVMAB. This study enriches the toolbox of polybetaines by introducing the quaternary ammonium-borate anion zwitterionic pair in the repeat units, therefore broadens the scope of synthetic polybetaines.
研究领域:
材料科学
·
生物学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2023
·
IF 8.2
Tingting Ding,Ruixia Liu,Xiaofan Yan,Zuoyu Zhang,Fuquan Xiong,Xingong Li,Zhiping Wu
It is a promising idea to graft zwitterionic polymers onto lignin and prepare lignin-grafted-poly [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (Lignin-g-PDMAPS) thermosensitive polymer with the upper critical solution temperature (UCST). In this paper, an electrochemically mediated atom transfer radical polymerization (eATRP) method was used to prepare Lignin-g-PDMAPS. The structure and property of the Lignin-g-PDMAPS polymer were characterized by the fourier transform infrared spectrum (FT-IR), nuclear magnetic resonance (NMR), X-ray electron spectroscopy (XPS), dynamic light scattering (DLS), differential scanning calorimeter (DSC). Furthermore, the effect of catalyst structure, applied potential, amount of Lignin-Br, Lignin-g-PDMAPS concentration, NaCl concentration on UCST of Lignin-g-PDMAPS were investigated. It was worth noting that polymerization was well controlled when the ligand was tris (2-aminoethyl) amine (Me 6 TREN), applied potential was −0.38 V and the amount of Lignin-Br was 100 mg. And the UCST of the Lignin-g-PDMAPS aqueous solution (1 mg/ml) was 51.47 °C, the molecular weight was 8987 g/mol, and the particle size was 318 nm. It was also found that the UCST increased and the particle size decreased with the Lignin-g-PDMAPS polymer concentration increased, and the UCST decreased and the particle size increased with the NaCl concentration increases. This work investigated UCST-thermoresponsive polymer which possessed lignin main chain combining the zwitterionic side chain, and provided a new way for development of lignin based UCST-thermoresponsive materials and medical carrier materials, in addition to expand the scope of eATRP.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
MACROMOLECULAR CHEMISTRY AND PHYSICS
·
2019
·Vol. 220
·期 12
·1900061
·
IF 2.622
Liang Zhao,Lin Zhang,Zelai Zheng,Ying Ling,Haoyu Tang
Homopolypeptide bearing azobenzene and triethylene glycol spacers, and 1-butylimidazolium pendants, namely P(Azo-OEG 3 -ImX) (X = Cl, I, BF 4 ) are prepared by 1,3-dipolar cycloaddition and subsequent ion-exchange reaction. Both 1 H NMR and FTIR confirm the polymer structures and reveal a high grafting efficiency (97%). P(Azo-OEG 3 -ImI) shows reversible upper critical solution temperature (UCST)-type thermoresponsive property in ethanol while P(Azo-OEG 3 -ImI/BF 4 ) shows a UCST in ethanol/water solvent mixtures. P(Azo-OEG 3 -ImI) shows UCST-type phase transitions in ethanol or ethanol/water solvent mixtures. After UV irradiation, the UCST-type cloud point temperature ( T cp ) remains constant in ethanol. However, it decreases after UV irradiation and increases after visible light irradiation in ethanol/water solvent mixtures due to the trans – cis isomerization of azobenzene moieties. P(Azo-OEG 3 -ImCl/I) shows NaI-induced UCST in water. The T cp of the P(Azo-OEG 3 -ImCl/I) aqueous solution is highly related to the polymer/salt concentration and nature of counteranions. P(Azo-OEG 3 -ImCl) also shows reversible light-responsive properties in NaI aqueous solutions. Higher NaI concentration is needed to induce a UCST for P(Azo-OEG 3 -ImCl) after UV irradiation. Moreover, ciprofloxacin-loaded hydrogel containing P(Azo-OEG 3 -ImCl) shows more efficient drug release while the UV irradiation leads to slightly low drug release.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
ACS Applied Polymer Materials
·
2020
·
IF 0
Yongliang Ding,Youxian Yan,Qiang Peng,Baoxia Wang,Yuxian Xing,Zan Hua,Zhongkai Wang
It has been a significant challenge to prepare multiple-response hydrogels with both lower critical solution temperature (LCST) and upper critical solution temperature (UCST). This work reports the synthesis of methyl cellulose-graft-polyacrylamide (MC-g-PAM) hydrogels by ceric ion initiated graft polymerization. Mechanically strong MC-g-PAM hydrogels combine LCST and UCST in one system (LCST > UCST), which provides a transparent “temperature window”. The range of this temperature window can be tuned by changing cellulose contents or adding sodium chloride. In addition, the transmittance of MC-g-PAM hydrogels can be precisely controlled via application of varied DC voltage. These desirable properties make the MC-g-PAM hydrogels as smart materials.
研究领域:
材料科学
·
高分子化学
✓ 已验证
DOI
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
·
2022
·
IF 5.895
Xinnan Ma,Wenrui Huang,Yongqing Song,Juan Han,Jiacong Wu,Lei Wang,Yun Wang
The development of a suitable immobilization strategy to improve the performance of immobilized glucose isomerase for the isomerization of glucose to fructose is crucial to promoting the industrial production of high-fructose syrup. In this work, a novel recyclable upper critical solution temperature (UCST)-type mVBA-b-P(AAm-co-AN)@glucose isomerase biocatalyst (PVAA@GI) was prepared, and the immobilized glucose isomerase could capture the glucose substrate through the affinity of 4-vinylbenzeneboronic acid (4-VBA) and the glucose substrate, which led to the enhanced substrate affinity and catalytic efficiency of the PVAA@GI. The biocatalyst exhibited excellent stability in pH, thermal, storage, and recycling compared to the free enzyme. The mVBA-b-P(AAm-co-AN)@glucose isomerase biocatalyst displayed reversibly soluble–insoluble characteristics with temperature change, which was in the soluble state during the enzyme reaction process but could be recovered in an insoluble form by lowering the temperature after the reaction. The highest fructose production rate reached 62.79%, which would have potential application in the industrial production of high-fructose syrup.
研究领域:
生物化学
·
酶工程
·
工业生物技术
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产品关联
DOI
PubMed
高影响因子
POLYMER JOURNAL
·
2021
·Vol. 53
·期 8
·943-949
·
IF 3.08
Zhu Hongyu,Gu Dongxu,Rao Zikun,Li Yang,Liu Yu,Hao Jianyuan
Creating stimulus-responsive materials solely by controlling polypeptide secondary nanostructures is challenging. We synthesized a methyl poly(ethylene glycol)- b -poly(O-benzyl-L-threonine) (mPEG-PBnLT) diblock copolymer that exhibited gel-to-sol UCST (Upper Critical Solution Temperature) transition behavior in an aqueous solution. The transition temperature window was easily adjusted by changing the copolymer concentration or length of the PBnLT block. Disassembly of the initial β-sheet nanoassemblies caused nanofibril transformation to spherical aggregates with increasing temperature, resulting in a gel-to-sol UCST transition. This result inspires a brand-new strategy for the structural design and functional control of materials.
研究领域:
生物化学
·
材料科学
·
纳米技术
✓ 已验证
DOI
高影响因子
Polymer Chemistry
·
2017
·Vol. 8
·期 37
·5749-5760
·
IF 5.375
Hongcan Zhang,Jian Zhang,Wenxue Dai,Youliang Zhao
The simple and straightforward construction of multi-responsive systems with tunable LCST and UCST dual phase transitions is a great challenge. This study affords an efficient route to tune cloud points via control over the chemical composition of hydroxyl and diethylamino bearing poly(amido thioether)s which were prepared by one-pot thiol–amine–acrylate polyaddition. Owing to the balance of inter/intrachain interactions, various copolymers could exhibit LCST (fOH < 0.84), LCST–UCST (fOH = 0.84–0.89) and UCST (fOH > 0.89) behaviors relying on the hydroxyl fraction in comonomer units. Meanwhile, the thermoresponsive behaviors of copolymer solutions could be efficiently tuned via switching the solvent and solution pH, applying CO2/N2 bubbling, and oxidation. The success of this study further paves the way for the robust synthesis and practical applications of smart polymers with double thermoresponsivity.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Soft Matter
·
2016
·Vol. 12
·期 8
·2473-2480
·
IF 3.798
Lei Hou,Qijing Chen,Zesheng An,Peiyi Wu
The lower critical solution temperature (LCST) transition in water and the upper critical solution temperature (UCST) transition in ethanol of poly(oligo(ethylene glycol) acrylate) (POEGA)-based core cross-linked star (CCS) polymers have been investigated and compared by employing turbidity, dynamic light scattering (DLS), 1H NMR and FTIR measurements. Macroscopic phase transitions in water and in ethanol were observed to occur when passing through the transition temperature, as revealed by DLS and turbidity measurements. Analysis by IR indicated that the interactions between the polymer chains and solvent molecules in water are stronger than those in ethanol such that the CCS polymer arm chains in water adopt more extended conformations. Moreover, hydrophobic interaction among the aliphatic groups plays a predominant role in the LCST-type transition in water whereas weak solvation of the polymer chains results in the UCST-type transition in ethanol. Additionally, the LCST-type transition in water was observed to be much more abrupt and complete than the UCST-type transition in ethanol, as suggested by 1H NMR and IR at the molecular level. Finally, an abnormal “forced hydration” phenomenon was observed during the LCST transition upon heating. This study provides a detailed understanding of the subtle distinctions between the thermal transitions of CCS polymers in two commonly used solvents, which may be useful to guide future materials design for a wide range of applications.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
·
2016
·Vol. 54
·期 21
·3425-3435
·
IF 3.114
Wenjun Liu,Mengxiang Zhu,Jiang Xiao,Ying Ling,Haoyu Tang
A series of thermoresponsive polypeptides bearing 1-butyl, 1-hexyl, or 1-dodecyl side-chains (i.e., 6a - 6c ) were synthesized by copper-mediated 1,3-dipolar cycloaddition with high grafting efficiency (>95%) between side-chain “clickable” polypeptide, namely poly( γ -4-(propargoxycarbonyl)benzyl- L -glutamate) ( 5 ) and 1-azidoalkanes. 5 with different degree of polymerization (DP = 48–86) were prepared from triethylamine initiated ring-opening polymerization of γ -4-(propargoxycarbonyl)benzyl- L -glutamic acid based N -carboxyanhydride ( 4 ). 1 H NMR, FTIR, and GPC results revealed the successful preparation of the resulting polypeptides. 6a - 6c showed reversible UCST-type phase behaviors in methanol, ethanol, and ethanol/water solvent mixtures depending on the polymer main-chain length, alkyl side-chain length, weight percentage of ethanol ( f w ) in the binary solvent, and so forth. FTIR analysis revealed the presence of the van der Waals interaction between the alkyl pendants of polypeptides and alkyl groups of alcoholic solvents. Variable-temperature UV-vis spectroscopy revealed that the UCST-type phase transition temperature ( T pt ) increased as polymer main-chain length or concentration increased. In ethanol/water solvent mixtures, polypeptide with short alkyl pendant (i.e., 1-butyl group) and short main-chain length (DP = 41) showed the widest f w range and T pt s in the range of 61.0–71.1 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54 , 3425–3435
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子