CHINESE JOURNAL OF POLYMER SCIENCE
·
2023
·
IF 4.3
Zou Zhi,Xu Xiang,Zhao Hai-Tao,Cheng Jian-Nan,He Wei-Wei,Zhang Li-Fen,Cheng Zhen-Ping
Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli. In this work, dual temperature-responsive block copolymers are synthesized via reversible addition-fragmentation chain transfer polymerization (RAFT) polymerization utilizing zwitterionic monomer methacryloyl ethyl sulfobetaine (SBMA) and N -isopropyl acrylamide (NIPAAm) as monomers. The thermal responsive behaviors can be easily modulated by incorporating additional hydrophobic monomer benzyl acrylate (BN) or hydrophilic monomer acrylic acid (AA), adjusting concentration or pH, or varying the degree of polymerization of the block chain segments. The cloud points of the copolymers are determined by UV-Vis spectrophotometry, and these copolymers exhibit both controlled upper and lower critical solubility temperatures (LCST and UCST) in aqueous solution. This study analyzes and summarizes the influencing factors of dual temperature responsive block copolymers by exploring the effects of various conditions on the phase transition temperature of temperature-sensitive polymers to explore the relationship between their properties and environment and structure to make them more selective in terms of temperature application range and regulation laws. It is very interesting that the introduction of poly-acrylic acid (PAA) segments in the middle of di-block copolymer PSBMA 55 - b -PNIPAAm 80 to form PSBMA 55 - b -PAA x - b -PNIPAAm 80 results in a reversal of temperature-responsive behaviors from ‘U’ (LCST < UCST) to ‘n’ (LCST > UCST) type, while the copolymer PSBMA 55 - b -P(NIPAAm 80 - co -AA x ) not. This work provides a clue for tuning the phase transition behavior of polymers for manufacture of extreme smart materials.
研究领域:
材料科学
·
高分子化学
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DOI
高影响因子
EUROPEAN POLYMER JOURNAL
·
2020
·
IF 3.862
Wenhao Du,Pengwei Wu,Zhixin Zhao,Xi Zhang
Aqueous dispersion polymerization is an environmentally friendly and low-energy method for the preparation of micron polymer microspheres. Crosslinked polymer microspheres could be obtained by aqueous dispersion polymerization via methods such as controlled radical polymerization. However, most of these commonly used cross-linking methods are complicated and the product is toxic. Herein, we provided a facile approach for the preparation of temperature-responsive crosslinked polymer microspheres (c-PMAD) by aqueous dispersion polymerization. Chain transfer reaction of 2-(dimethylamino) ethyl methacrylate (DMAEMA) instead of traditional crosslinkers was used to achieve the crosslinking. It is found that the microsphere is a spherical material with uniform surface, which has an average particle size of 5.21 μm in deionized water at 25 °C. It has a relatively high thermal stability. The microsphere has the upper critical solution temperature transition (UCST) behavior at 66.5 °C. The particle size of c-PMAD could increase with increasing temperature and decrease with increasing dosage of NaCl. Moreover, diameter of c-PMAD could decrease to original size with decreasing temperature, which endows it the feature of reusing. The UCST behavior of c-PMAD could be kept in 8 wt% NaCl solution. In addition, the effect of process conditions of preparation on the particle size of microspheres were studied in this paper. Micron-sized microspheres could be obtained at 45–65 °C. Microspheres size decreased with increasing initiator dosage, decreasing monomers concentration, increasing of acrylamide dosage and increasing of crosslinker dosage.
研究领域:
材料科学
·
高分子化学
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Luqin Hua,Manqing Xie,Yukun Jian,Baoyi Wu,Chongyi Chen,Chuanzhuang Zhao
Thermoresponsive hydrogel actuators have attracted tremendous interest due to their promising applications in artificial muscles, soft robotics, and flexible electronics. However, most of these materials are based on polymers with lower critical solution temperature (LCST), while those from upper critical solution temperature (UCST) are rare. Herein, we report a multiple-responsive UCST hydrogel actuator based on the complex of poly(acrylic acid) (PAAc) and poly(acrylamide) (PAAm). By applying a heterogeneous photopolymerization, a bilayer hydrogel was obtained, including a layer of the interpenetrating network (IPN) of PAAm/PAAc and a layer of a single network of PAAm. When cooled down below the UCST, the PAAm/PAAc layer contracted due to the hydrogen bonding of the two polymers while the PAAm layer stays in swelling state, driving the hydrogel to curl. By adjusting the composition of the two layers, the amplitude of actuation behavior could be regulated. By creating patterned IPN domains with photomasks, the hydrogel could deform into complex two-dimensional (2D) and three-dimensional (3D) shapes. An active motion was realized in both water and oil bath, thanks to the internal water exchange between the two layers. Interestingly, the hydrogel actuator is also responsive to urea and salts (Na2SO4, NaCl, NaSCN), due to that the strength of the hydrogen bonds in the IPN changes with the additives. Overall, the current study realized an anisotropic UCST transition by introducing asymmetrically distributed polymer–polymer hydrogen bonds, which would inspire new inventions of intelligent materials.
研究领域:
材料科学
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软体机器人
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高分子化学
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智能材料
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功能水凝胶
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DOI
高影响因子
Advanced Science
·
2024
·Vol. 11
·期 31
·2400938
·
IF 14.3
Huiyao Xu,Haocheng Li,Yan Zhang,Ying Guan,Yongjun Zhang
It remains a great challenge to achieve strong and reversible hydrogel adhesion. Hydrogel adhesives also suffer from poor environmental stability due to dehydration. To overcome these problems, here reversible adhesive gels are designed using a new switching mechanism and new solvent. For the first time, the study observes UCST (upper critical solution temperature)-type thermosensitive behaviors of poly(benzyl acrylate) (PBnA) polymer and gel in menthol:thymol deep eutectic solvents (DESs). The temperature-induced phase transition allows adjusting cohesive force, and hence adhesion strength of PBnA gels by temperature. To further improve the mechanical and adhesion properties, a peptide crosslinker is used to allow energy dissipation when deforming. The resulting eutectogel exhibits thermal reversible adhesion with a high switching ratio of 14.0. The adhesion strength at attachment state reaches 0.627 MPa, which is much higher than most reversible adhesive hydrogels reported before. The low vapor pressure of DES endows the gel excellent environmental stability. More importantly, the gel can be repeatedly switched between attachment and detachment states. The strong and reversible gel adhesive is successfully used to design soft gripper for the transport of heavy cargos and climbing robot capable of moving on vertical and inverted surface in a manner similar to gecko.
研究领域:
材料科学
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生物医学工程
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产品关联
DOI
PubMed
高影响因子
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
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高分子化学
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DOI
高影响因子
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
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2015
·Vol. 54
·期 10
·1348-1356
·
IF 3.113
Mengxiang Zhu,Yanzhi Xu,Chenglong Ge,Ying Ling,Haoyu Tang
A series of OEGylated poly(γ-benzyl- l -glutamate) with different oligo-ethylene-glycol side-chain length, molecular weight (MW = 8.4 × 10 3 to 13.5 × 10 4 ) and narrow molecular weight distribution (PDI = 1.12–1.19) can be readily prepared from triethylamine initiated ring-opening polymerization of OEGylated γ-benzyl- l -glutamic acid based N -carboxyanhydride. FTIR analysis revealed that the polymers adopted α-helical conformation in the solid-state. While they showed poor solubility in water, they exhibited a reversible upper critical solution temperature (UCST)-type phase behavior in various alcoholic organic solvents (i.e., methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, and isopropanol). Variable-temperature UV–vis analysis revealed that the UCST-type transition temperatures ( T pt s) of the resulting polymers were highly dependent on the type of solvent, polymer concentration, side- and main-chain length. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54 , 1348-1356
研究领域:
高分子化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Cleaner Production
·
2023
·
IF 11.1
Zhaohui Chen,Jiacong Wu,Wenrui Huang,Yuanyuan Li,Yanli Mao,Juan Han,Yun Wang,Liang Ni
Phenolic compounds are toxic substances that exert harmful effects on all living organisms. Irrigation farmland with phenolic wastewater can result in reduced crop yields or even crop failure, while consuming phenolic wastewater has a strong carcinogenic effect. Horseradish peroxidase (HRP), a heme-containing peroxidase, is capable of catalyzing the oxidative conversion and coupling reaction of phenols in sewage to form polymerization products in the presence of hydrogen peroxide (H 2 O 2 ). However, free HRP can only function within a relatively narrow range of temperature and pH conditions , and its excellent water solubility makes it difficult to recover, thereby significantly increasing the cost of enzyme utilization. The immobilized enzyme was prepared by incorporating HRP and self-synthesized UCST (Upper Critical Solution Temperature) and pH dual responsive polymer P(NAGA-b-AA-b-VBA). The loading capacity of HRP reached 295 mg/g while maintaining the UCST performance. Compared to the free enzyme , the immobilized enzyme exhibited enhanced pH stability, thermal stability and storage stability. In laboratory experiments as well as actual water samples, the immobilized enzyme achieved phenol degradation rates of 90.4% and 88.4% respectively, within 1 h. After five cycles, the immobilized enzyme retained 80.1% catalytic activity with a recovery rate of 84.5%. Furthermore, it was demonstrated that the biological toxicity of the reaction product was significantly lower than that of simulated pollutant phenol.
研究领域:
环境生物学
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酶工程
·
污染治理
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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
·
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
LANGMUIR
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2011
·
IF 4.269
Zhixin Dong,Jun Mao,Muquan Yang,Dapeng Wang,Shuqin Bo,Xiangling Ji
Biocompatible and zwitterionic poly(sulfobetaine methacrylate) (PSBMA) was grafted onto the surface of initiator-modified silica nanoparticles via surface-initiated atom transfer radical polymerization. The resultant samples were characterized via nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, and thermogravimetric analysis. Their molecular weights and molecular weight distributions were determined via gel permeation chromatography after the removal of silica by etching. Moreover, the phase behavior of these polyzwitterionic-grafted silica nanoparticles in aqueous solutions and stability in protein/PBS solutions were systematically investigated. Dynamic light scattering and UV–visible spectroscopy results indicate that the silica-g-PSBMA nanoparticles exhibit an upper critical solution temperature (UCST) in aqueous solutions, which can be controlled by varying the PSBMA molecular weight, ionic strength, silica-g-PSBMA nanoparticle concentration, and solvent polarity. The UCSTs shift toward high temperatures with increasing PSBMA molecular weight and silica-g-PSBMA nanoparticle concentration. However, increasing the ionic strength and solvent polarity leads to a lowering of the UCSTs. The silica-g-PSBMA nanoparticles are stable for at least 72 h in both negative and positive protein/PBS solutions at 37 °C. The current study is crucial for the translation of polyzwitterionic solution behavior to surfaces to exploit their diverse properties in the development of new, smart, and responsive coatings.
研究领域:
材料科学
·
生物医学工程
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Dazhen Xiong,Qian Zhang,Wenjie Ma,Yang Wang,Wenrui Wan,Yunlei Shi,Jianji Wang
Amino acids are vital compounds in animal and human nutrition. However, it is still a great challenge to develop a cost-effective process for selective separation of amino acids. In the present study, a class of deep eutectic solvents (DESs) with short-chain alkanolamines as hydrogen bond acceptors (HBAs) and phenolic compounds as hydrogen bond donors (HBDs) have been explored for selective separation of aromatic amino acids for the first time. It is found that these DESs exhibit upper critical solution temperature (UCST)-type phase behavior in water, and their phase transition temperature is related with the pK a values of HBAs and HBDs as well as the hydrophobicity of HBDs. The UCST-type phase separation process is investigated by dynamic light scattering (DLS), FT-IR spectroscopy and temperature-variable 1 H NMR in details, and the stability of the DESs in water is also examined. Interestingly, these UCST-type DESs/water systems are applicable to selective separation of aromatic amino acids. The separation factor between L-tryptophan and L-tyrosine as well as between L-tryptophan and L-phenylalanine can reach up to 476.1 and 87.9, respectively, which is about 20 and 19 times that reported in ionic liquids-based extraction solvents.
研究领域:
化学工程
·
分析化学
·
生物技术
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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
·
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
EUROPEAN POLYMER JOURNAL
·
2025
·
IF 6.3
Ruizhen Zhang,Chengwen Jin,Pengjie Xie,Tao Chen
The coordinated release of multiple substances presents a significant technical challenge, primarily due to their distinct release kinetics and potential intermolecular interactions. To address this, we developed a composite nanoreactor and strategically selected two hydrophobic fluorescent dyes, Coumarin 102 and Nile Red, as model payloads. Firstly, a photoresponsive block copolymer, P(DMA 50 - b -SPMA 60 ) ( P1 ), containing carbamate spiropyran methacrylate units, and a thermoresponsive block copolymer with an Upper Critical Solution Temperature (UCST), P(DMA 50 - b -SBMA 48 ) ( P2 ), were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. These copolymers self-assembled into micelles, which encapsulated Coumarin 102 and Nile Red within the hydrophobic cores of P1 and P2 , respectively. The individual stimulus-responsive release profiles were monitored via fluorescence spectroscopy. Composite nanoreactors were then prepared by physical blending the two loaded micelle types. The stability of the composite system was verified by fluorescence spectroscopy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). Upon exposure to specific stimuli (light or temperature), selective release of the respective hydrophobic molecules was achieved: UV irradiation triggered a 80% release of Coumarin 102 from M3 micelles, while heating above the UCST induced a 75% release of Nile Red from M4 micelles. The composite micelles thus integrate multiple orthogonal stimulation responses with precise selective release control, offering a promising platform for advanced controlled-release applications in nanotechnology and biotechnology.
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DOI
高影响因子
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