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RARE METALS · 2026 ·Vol. 45 ·期 5 ·e70300 · IF 12.1

Phosphotungstic Acid Modulated PNIPAM/P(AA-co-AM) Bilayer Hydrogels With Programmable Thermo-Responsive Kinetics and Enhanced Toughness

Hui Liu,Hongli Jia,Xiaojin Yan,Rouling Chen,Yingying Wang,Kun Chen

en This link goes to a English section zh This link goes to a Chinese section Thermo-responsive hydrogels based on poly(N-isopropylacrylamide) (PNIPAM) are promising candidates for soft actuation, yet their practical applications are often constrained by sluggish thermo-responsive kinetics and insufficient mechanical robustness. Herein, phosphotungstic acid (PTA), a tungsten-containing polyoxometalate, was incorporated to regulate the phase transition behavior and modulate a PNIPAM/P(AA- co -AM) bilayer hydrogel, in which the thermo-responsive PNIPAM layer serves as the actuator whereas the non-thermo-responsive P(AA- co -AM) layer provides mechanical support. By increasing the PTA content up to 4 wt%, the thermally induced deformation time of the PNIPAM layer was prolonged from 30 to 120 s, whereas the recovery time at low temperature was shortened from 120 to 60 min, thereby enabling programmable thermo-responsive kinetics. The thermal transition of the PTA-PNIPAM layer was effectively regulated by PTA, with the lower critical solution temperature (LCST) gradually increasing and tunable up to 42°C, accompanied by an improved thermal stability manifested by reduced mass loss at 150°C. Mechanical characterization demonstrated that the P(AA- co -AM) layer modulated the tensile properties of hydrogel networks, and the bilayer configuration significantly outperformed the pristine PNIPAM hydrogel. Benefiting from the synergistic effects of kinetic regulation and mechanical modulation, the bilayer hydrogel further exhibited multi-substrate adhesion and reversible deformation, enabling an underwater gripping demonstration. This work highlights a polyoxometalate-enabled strategy for simultaneously controlling thermo-responsive kinetics and toughening PNIPAM-based hydrogels, thereby advancing functional soft materials for actuation-related applications. 摘要 en This link goes to a English section zh This link goes to a Chinese section 聚(N-异丙基丙烯酰胺)(PNIPAM)的温敏水凝胶是软体动力领域的有力候选材料,但其迟缓的热响应动力学和有限的机械鲁棒性往往限制了其实际应用。在此,我们在PNIPAM/P(AA- co -AM)双层水凝胶中引入了磷钨酸(PTA),以调控其相变行为并增强材料性能。在该双层结构中,温敏性PNIPAM层作为动力层,而非温敏性P(AA- co -AM)层则提供机械支撑。通过将PTA的含量提高至4 wt%,PNIPAM层的热诱导变形时间从30秒延长至120秒,而在低温下的恢复时间则从120分钟缩短至60分钟,从而实现了可编程的热响应动力学。PTA有效调控了PTA-PNIPAM层的热转变行为,使其低临界溶解温度(LCST)逐渐升高且最高可调至42°C。同时,材料的热稳定性也得到提升,150°C时的质量损失明显减少。力学表征表明,P(AA- co -AM)层调节了水凝胶网络的拉伸性能,且该双层结构的性能显著优于原始PNIPAM水凝胶。得益于动力学调控与机械增韧的协同效应,该双层水凝胶进一步展现出多基底黏附性和可逆变形能力,并成功实现了水下抓取演示。本工作提出了一种基于多金属氧酸盐的水凝胶改性策略,可同时控制PNIPAM基水凝胶的热响应动力学并增强其韧性,从而推动了功能性软材料在相关应用中的发展。

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COLLOIDS AND SURFACES B-BIOINTERFACES · 2026 · IF 5.9

Engineered near-infrared-responsive PNIPAM/alginate hydrogels for active mechanical stimulation and infection control in diabetic wound healing

Hailiang Pei,Tao Xu,Yu Cao,Zhimei Wang,Sidi Zhao,Jiapu Wang,Xuan Wang,Longfei Wang,Ziwei Liang,Di Huang

Chitosan anchors the PNIPAM/Alg/GO/TH double-network hydrogel to wet wound tissue. • NIR-driven LCST transition contracts the hydrogel, pulling wound edges together mechanically. • Photothermal effect triggers on-demand tetracycline release, killing 98.5% S. aureus and 99.25% E. coli. • In infected diabetic mice, the hydrogel reduces inflammation, promotes angiogenesis, and achieves 94.75% closure by day 10. Diabetic wound healing is severely impaired by four core pathological barriers—persistent hyperglycemia, excessive inflammation, bacterial infection, and deficient wound contraction. Herein, we developed a near-infrared (NIR)-responsive antibacterial hydrogel composed of poly(N-isopropylacrylamide), sodium alginate, graphene oxide, and tetracycline hydrochloride (PNIPAM/Alg/GO/TH), in which chitosan serves as an interfacial bridging component that covalently and electrostatically anchors the hydrogel to tissue rather than acting as a bulk matrix constituent. As a natural polysaccharide, sodium alginate serves as the essential hydrogel matrix, endowing the system with high water retention, biocompatibility, and a porous network favorable for exudate absorption and tissue regeneration, while also forming a mechanically robust double-network structure with PNIPAM. Through chitosan-mediated interfacial bioadhesion, the hydrogel firmly adheres to wound tissues, enabling transfer of the contraction force to the wound edges. Under NIR irradiation, the hydrogel exhibited potent broad-spectrum antibacterial activity, with bactericidal rates of 98.5 ± 0.53% against Staphylococcus aureus and 99.25 ± 0.75% against Escherichia coli. Meanwhile, NIR stimulation induced a phase transition and active mechanical contraction, promoting centripetal wound closure, while the photothermal effect triggered sustained tetracycline release for prolonged antimicrobial protection. In vivo, in a Staphylococcus aureus-infected diabetic mouse wound model, the hydrogel significantly downregulated inflammatory markers and promoted neovascularization and collagen deposition, achieving a wound healing rate of 94.75 ± 2.09% on day 10. This study presents a sodium alginate-based interfacial hydrogel strategy that integrates interfacial adhesion, active mechanical contraction, and on-demand drug delivery for rapid diabetic wound healing.

✓ 已验证 DOI 高影响因子
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JOURNAL OF MEMBRANE SCIENCE · 2023 · IF 9.5

Preparation and properties of PEEK-g-PNIPAm separation membranes with thermo-responsiveness for emulsion and organic liquid separation

Fan Yang,Su Li,Hongyan Qi,Weibo Sun,Jinbao Li,Mei Zhang,Zheng Chen,Jinhui Pang,Zhenhua Jiang

Although poly (ether ether ketone) (PEEK) exhibits excellent solvent resistance , it could not be prepared directly by non-solvent induced phase separation (NIPS) method due to its poor solubility. Herein, PEEK porous membranes were successfully fabricated by combining NIPS and acid hydrolysis. The superhydrophilic thermo-responsive poly (N-isopropylacrylamide) (PNIPAm) polymer was in-situ grafted on the PEEK membrane surface via the UV grafting polymerization and improved the membrane interface hydrophilicity, making the membrane water contact angle changed from 89.5° to 0° at 25 °C. After heating the membrane surface to 40 °C, the membrane exhibited hydrophobicity (100°), realizing the thermo-responsiveness via switching the temperature. Furthermore, due to the transferred membrane wettability at different temperatures, PEEK-g-PNIPAm could separate different types of oil-bearing systems with high rejection above 99.0 %. What’s more, the PNIPAm layer also enhanced the membrane anti-fouling capacity. Benefiting from the extraordinary solvent resistance of the PEEK matrix, PEEK-g-PNIPAm maintains its intact morphology after 6 h immersion in various organic solvents , addressing the commonly reported problem of polymer membranes having certain solubility in solvents. The PEEK-based membranes with excellent solvent resistance could be useful in the oil-bearing separation.

✓ 已验证 产品关联 DOI 高影响因子
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AICHE JOURNAL · 2014 ·Vol. 61 ·期 1 ·35-45 · IF 2.581

Self-assembly micelles from novel tri-armed star C3-(PS-b-PNIPAM) block copolymers for anticancer drug release

Feng Xu,Jing-Wen Xu,Bi-Xia Zhang,Luo Yan-Ling

Novel tri-armed star polystyrene-block-poly(N-isopropylacrylamide) block copolymers with trimesic acid as central molecules were synthesized by successive two-step atom transfer radical polymerization, and confirmed by Fourier-transform infrared spectra, 1 H nuclear magnetic resonance, and laser light scattering gel chromatography system. The copolymers could self-assemble into spherical core-shell micelles in aqueous media independent on drug loading. Physicochemical properties of the blank and drug-loaded micelles were examined by surface tension, fluorescence spectroscopy, UV-vis, transmission electron microscope, and dynamic light scattering measurements. The copolymer micelles exhibited thermo-triggered phase transition, with low critical solution temperature of 33.7 and 34.6°C, varying with copolymer compositions. The critical aggregate concentrations were 11.62 and 47.61 mg L −1 , and hydrodynamic diameters from 200 to 220 nm. Water-insoluble 10-hydroxycamptothecine was encapsulated into the micelle aggregates to investigate the change in the resulting physicochemical parameters, thermo-triggered in vitro drug release, and the applicability as drug targeting release carriers. MTT assays were carried out to uncover cytotoxicity of the newly developed micelle-based drug formulations. © 2014 American Institute of Chemical Engineers AIChE J , 61: 35–45, 2015

研究领域: 材料科学 · 药学 · 肿瘤学
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GOLD BULLETIN · 2021 ·Vol. 54 ·期 1 ·59-67 · IF 1.61

Gold nanorods crosslinking PNIPAM hydrogels via dynamic Au-thiolate interaction with stretchable, adhesive, self-healing, and photothermal properties

Lin Shijun,Jiang Sirui,Zhang Yuchen,Dai Zhengwei,Dai Yu,Xia Fan,Zhang Xiaojin

Gold nanorod (AuNR) nanocomposite hydrogels have attracted increasing attention due to the photothermal effect of AuNRs. However, a facile strategy that avoids multi-step surface modification for synthesis of AuNR crosslinkers is still a critical challenge. Here, AuNRs crosslinking PNIPAM hydrogels were prepared by polymerization of NIPAM with N , N ′-bis(acryloyl)cystamine (BACA)-modified AuNRs as crosslinkers. BACA contains a disulfide bond in the structure. Dynamic and reversible Au-thiolate bonding was formed by directly mixing AuNRs and BACA to facilely prepare AuNR crosslinkers before hydrogel formation. The addition of AuNRs gives hydrogels their photothermal effect and remarkable mechanical behaviors. Hydrogels could repeatedly adhere to the surface of pigskin, metal, plastic, and glass with a relatively stable adhesion. The damaged hydrogels heal within 2 min with near-infrared (NIR) laser (808 nm, 300 mW∙cm −2 ) irradiation. This work provides a line of thinking for improvement of PNIPAM hydrogels, making them promising for further applications in biomedicine.

CAS / MDL: 868-77-9
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JOURNAL OF INORGANIC BIOCHEMISTRY · 2020 · IF 3.212

Fabrication of PNIPAM-chitosan/decatungstoeuropate/silica nanocomposite for thermo/pH dual-stimuli-responsive and luminescent drug delivery system

Na Huang,Jun Wang,Xiaoyan Cheng,Yafei Xu,Wuke Li

A luminescent and dual-stimuli-responsive nanocomposite based on mesoporous silica , poly (N-isopropylacrylamide)-chitosan and decatungstoeuropate was prepared. To fabricate the nanocomposite, the mesoporous silica nanoparticles were coated with thermo/pH dual-responsive poly (N-isopropylacrylamide)-chitosan and the luminescent decatungstoeuropate particles were grafted onto copolymers . The designed nanocarrier could show exhibit good red luminescence as well as obvious thermo/pH stimuli-responsive properties, which could be employed as a drug storage reservoir for the loading and release of anticancer drug doxorubicin (DOX). The research indicated that the releases of DOX were thermo/pH dependent and high temperatures/acidic conditions were favorable for the fast release of drug. In vitro cytotoxicity tests revealed that the drug delivery carrier displayed excellent biocompatible and the composites loaded with DOX showed significant suppression effect on HeLa cells. Luminescence spectra showed that the composite containing decatungstoeuropate displayed fine red luminescence at various temperatures and pH values, which could be utilized as a potential labeling material in field of medicine.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF APPLIED POLYMER SCIENCE · 2019 ·Vol. 137 ·期 12 ·48486 · IF 2.188

Enhanced mechanical properties and self-healing behavior of PNIPAM nanocomposite hydrogel by using POSS as a physical crosslinker

Xiaojing Zhang,Weiwei Shen,Jingcheng Dou,Yang Meng,Shaoming Fang,Ruixue Liu

In this study, water-soluble octa(3-chloroammoniumpropyl) silsesquioxane (OCAPS) was found to aggregate into nanoparticles with a positive charge in solution, which can attract persulfate anion radical to initiate N-isopropylacrylamide monomers. Due to the electrostatic and hydrogen bond interaction between OCAPS and poly(N-isopropylacrylamide) (PNIPAM) chain, OCAPS can act as an effective physical crosslinker to result in a nanocomposite hydrogel (OCAPS-PNIPAM) with very small loading N, N′-methylene-bisacrylamide (50–100 ppm). The incorporation of OCAPS increases the crosslinking degree of the PNIPAM hydrogel and decreases the swelling ratio in deionized water. The mechanical properties of OCAPS-PNIPAM hydrogel were enhanced greatly by the presence of OCAPS and can be adjusted by the feed ratio. The compression and elasticity moduli vary from 3.52 to 7.59 kPa and 7.67 to 33.91 kPa, respectively. The tensile strength ranges from 6.82 to 243.41 kPa with fracture energy between 503.5 and 4781.7 J·m −2 . Rheological measurements suggest that OCAPS-PNIPAM hydrogels have stable networks and the loss factor decreases as increasing OCAPS content. OCAPS-PNIPAM hydrogels also can self-heal under certain conditions with low crosslinker loading. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137 , 48486.

CAS / MDL: 919-30-2
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DYES AND PIGMENTS · 2015 · IF 3.966

Light and temperature responsive block copolymer assemblies with tunable fluorescence emissions

Dehua Li,Alexis Munyentwali,Guang Wang,Meiduo Zhang,Shuangxi Xing

A dual-responsive amphiphilic diblock copolymer , poly(styrene- co -1-(2-methacryloxyethoxy)-2-(2-pyridyl)benzimidazole)- block -Poly( N -isopropylacrylamide- co -3-biphenyl-3-phenyl-8-methacryloxy-3 H -naphtho[2,1- b ]pyran- co -4-methamino-9-allyl-1,8-naphthalimide), also denoted as P(St- co -PBI)- b -P(NIPAM- co -NP- co -MANI), was synthesized by reversible addition fragmentation chain transfer polymerization followed by assembling into micelles with hydrophobic P(St- co -PBI) block as core and thermoresponsive P(NIPAM- co -NP- co -MANI) block as the shell in aqueous solution. Dynamic light scattering , transmission electron microscopy and optical transmittance were used to characterize the particle morphology and thermosensitivity of the micelles solution. In addition, the fluorescence emission of the micelles could be reversibly modulated “on” and “off” by the photochromic naphthopyran upon UV and thermal back reaction, which promoted naphthopyran transformation between merocyanine forms and original closed form. Moreover, the spatial distance between the two fluorescence dyes could be regulated by temperature, resulting from the collapse or extension of PNIPAM in aqueous solution. This property enabled the polymeric assemblies to serve as sensitive ratiometric fluorescent thermometers.

研究领域: 高分子化学 · 材料科学 · 纳米技术
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Journal of Materials Chemistry A · 2026 · IF 9.5

A long-term stable thermochromic smart window of PNIPAM-based hydrogels with excellent water retention and visible light modulation

Xin Li,Xianglei Bu,Jie Huang,Ying Li,Likui Wang,Hongyan Miao,Gang Shi

Poly(N-isopropylacrylamide) (PNIPAM)-based hydrogel thermochromic smart windows exhibit advantages in near-room-temperature phase transition and strong solar modulation. However, their poor water retention performance limits the phase transition cycle stability. Here, PNIPAM microgels as thermochromic components, gelatin, poly(acrylamide-acrylic cacid) (PAM-AA) and AlCl3 were combined to form a PNIPAM/gelatin/PAM-AA/Al3+ hydrogel by copolymerization and cross-linking. This composite hydrogel was then sandwiched between two pieces of glass to form a smart window. The multiple interpenetrating polymer networks can improve the mechanical properties of the hydrogel, and the hydrophilic groups of PAM-AA and gelatin can enhance the water retention capacity of the hydrogel, ensuring the phase transition cycle stability of the smart window. The elongation at break, Young's modulus and toughness of the hydrogel reach up to 460%, 65 kPa and 0.52 MJ/m3, respectively. The smart window exhibits excellent visible light transmittance (Tlum=85.6%) and visible light modulation (ΔTlum=51.8%). During 150 phase transition cycles, the visible light modulation capability of the smart window remained highly stable. In comparison with an air sandwich window, the smart window equipped on a simulated chamber can achieve a maximum temperature reduction of ~ 7 °C in a 7-day outdoor experiment.

CAS / MDL: 110-18-9 2210-25-5
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ACS Applied Materials & Interfaces · 2011 · IF 2.925

Synthesis and Characterization of Silica Nanoparticles with Well-Defined Thermoresponsive PNIPAM via a Combination of RAFT and Click Chemistry

Jiucun Chen,Mingzhu Liu,Chen Chen,Honghong Gong,Chunmei Gao

Covalent functionalization of azide-modified SiO2 with well-defined, alkyne-terminated poly(N-isopropylacrylamide) was accomplished by the Cu(I)-catalyzed [3 + 2] Huisgen cycloaddition. The alkyne-terminated RAFT chain transfer agent was first synthesized, and then the alkyne-terminated thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) with different molecular weights were synthesized by the RAFT of NIPAM monomer. The polymerization kinetics and the evolution of number-average molecular weights (Mn), and polydispersities (Mw/Mn), with monomer conversions were investigated. A copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) “grafting to” method was used to attach thermoresponsive polymers onto the exterior surface of SiO2 nanoparticles which produced relatively high grafting density. The as-synthesized hybrid nanoparticles showed thermoresponsive behavior and were characterized by FTIR, XPS, TGA, DLS, and TEM, etc.

研究领域: 高分子化学 · 纳米材料 · 表面改性 · 智能材料 · 胶体与界面科学
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Polymers · 2022 ·Vol. 15 ·期 1 ·116 · IF 4.967

The Dual Modification of PNIPAM and β-Cyclodextrin Grafted on Hyaluronic Acid as Self-Assembled Nanogel for Curcumin Delivery

Tisana Kaewruethai,Yuan Lin,Qian Wang,Jittima Amie Luckanagul

Curcumin is an extract of turmeric (Curcuma longa) which possesses anti-inflammatory, anti-cancer and wound-healing effects and has been used as an active compound in biomedical research for many years. However, its poor solubility presents challenges for its use in drug delivery systems. A modified nanogel delivery system, with PNIPAM and β-cyclodextrin grafted onto hyaluronic acid (PNCDHA), was utilized to enhance the solubility. The polymer was characterized by NMR, and the inclusion complex between curcumin and β-cyclodextrin was confirmed by FTIR. The potential of this PNCDHA polymer complex as a drug delivery vehicle was supported by a curcumin encapsulation efficiency of 93.14 ± 5.6% and the release of encapsulated curcumin at 37 °C. At a concentration of 0.5%w/vin water, PNCDHA nanogels were biocompatible with fibroblast cell line (L929) up to a curcumin concentration of 50 µM. There was a direct concentration between curcumin loading and cellular internalization. A more detailed study of the cellular internalization of PNCDHA nanogel should be considered in order to clarify cellular delivery mechanisms and to assess how its viability as a carrier may be optimized.Keywords:hyaluronic acid;β-cyclodextrin;PNIPAM;thermoresponsive;nanogel;self-assembly;curcumin

CAS / MDL: 25952-53-8 6066-82-6
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PHARMACEUTICAL RESEARCH · 2013 ·Vol. 31 ·期 2 ·291-304 · IF 4.742

Thermosensitive mPEG-b-PA-g-PNIPAM Comb Block Copolymer Micelles: Effect of Hydrophilic Chain Length and Camptothecin Release Behavior

Yang Xiao-Li,Luo Yan-Ling,Xu Feng,Chen Ya-Shao

Purpose Block copolymer micelles are extensively used as drug controlled release carriers, showing promising application prospects. The comb or brush copolymers are especially of great interest, whose densely-grafted side chains may be important for tuning the physicochemical properties and conformation in selective solvents, even in vitro drug release. The purpose of this work was to synthesize novel block copolymer combs via atom transfer radical polymerization, to evaluate its physicochemical features in solution, to improve drug release behavior and to enhance the bioavailablity, and to decrease cytotoxicity. Methods The physicochemical properties of the copolymer micelles were examined by modulating the composition and the molecular weights of the building blocks. A dialysis method was used to load hydrophobic camptothecin (CPT), and the CPT release and stability were detected by UV–vis spectroscopy and high-performance liquid chromatography, and the cytotoxicity was evaluated by MTT assays. Results The copolymers could self-assemble into well-defined spherical core-shell micelle aggregates in aqueous solution, and showed thermo-induced micellization behavior, and the critical micelle concentration was 2.96–27.64 mg L −1 . The micelles were narrow-size-distribution, with hydrodynamic diameters about 128–193 nm, depending on the chain length of methoxy polyethylene glycol (mPEG) blocks and poly(N-isopropylacrylamide) (PNIPAM) graft chains or/and compositional ratios of mPEG to PNIPAM. The copolymer micelles could stably and effectively load CPT but avoid toxicity and side-effects, and exhibited thermo-dependent controlled and targeted drug release behavior. Conclusions The copolymer micelles were safe, stable and effective, and could potentially be employed as CPT controlled release carriers.

CAS / MDL: 2210-25-5 920-46-7
研究领域: 材料科学 · 药学
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