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CHINESE JOURNAL OF POLYMER SCIENCE · 2021 ·Vol. 39 ·期 9 ·1169-1176 · IF 3.603

Hyperbranched Azopolymer with Quadruple Responsibility

Tian Chen,Zhou Ke-Cong,Lu Yu-Fei,Li Jin-Jie,Yao Yuan,Tao Xin-Feng,Zhuang Qi-Xin,Xie Yu-Feng,Lin Shao-Liang

Simply constructing multiple responsive polymers with obvious shape and dimension variations on their assemblies upon different stimuli is still rarely reported. In this study, we report a hyperbranched polymer named HPAzoBAHB- star -PEG 9 with quadruple-response to light, temperature, pH and oxidation stimuli. The polymer contains azobenzene chromophore, sulfide, amide and amine groups in its hydrophobic hyperbranched core, and the core is capped with hydrophilic polyethylene glycol (PEG 9 ) arms. HPAzoBAHB- star -PEG 9 could assemble into unusual leaf-like lamellar micelles at 25 °C under the guidance of orderly arranged H -aggregate of azobenzene moieties. These leaf-like lamellar micelles can transform into vesicles upon UV irradiation and lower temperature, or convert to smaller spherical micelles in acidic or oxidative environments, respectively, with the destroy of ordered azobenzene arrangements. This quadruple-responsive hyperbranched polymer is suitable to construct multiple stimuli-responsive micro/nanostructures, or accurate delivery and release following subtle stimuli sequences.

研究领域: 材料科学 · 化学
✓ 已验证 DOI 高影响因子
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LANGMUIR · 2017 · IF 3.833

Investigation of Novel Triple-Responsive Wormlike Micelles

Mingwei Zhao,Mingwei Gao,Caili Dai,Chenwei Zou,Zhe Yang,Xuepeng Wu,Yifei Liu,Yining Wu,Sisi Fang,Wenjiao Lv

Smart wormlike micelles with stimuli-tunable rheological properties may be useful in a variety of applications, such as in molecular devices and sensors. The formation of triplestimuli-responsive systems so far has been a challenging and important issue. In this work, a novel triplestimuli (photo-, pH-, and thermoresponsive) wormlike micelle is constructed with N-cetyl-N-methylmorpholinium bromide and trans-cinnamic acid (CA). The corresponding multiresponsive behaviors of wormlike micellar system were revealed using cryogenic transmission electron microscopy, a rheometer, and 1H NMR. The rheological properties of wormlike micellar system under different temperatures, pH conditions, and UV irradiation times are measured. As confirmed by 1H NMR, chemical structure of a CA molecule can be altered by the multiple stimulation from an exotic environment. We expect it to be a good model for triple-responsive wormlike micelles, which is helpful to understand the mechanism of triple-responsiveness and widen their applications.

研究领域: 化学 · 材料科学 · 生物医学工程
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2020 ·Vol. 222 ·期 2 ·2000339 · IF 2.335

Facile Fabrication of Multiresponsive Self-Healing Hydrogels with Logic-Gate Responses

Xiaoyue Pei,Liping Fang,Weiping Chen,Xin Wen,Libin Bai,Xinwu Ba

Smart hydrogels have received great attention for application in various fields. In this work, the monomers dopamine methacrylamide (DMA) and methacrylamidophenylboronic acid (MAPBA), and the crosslinker bis(methacrylamide) cysteine (BMAC) are first synthesized. The multiresponsive self-healing hydrogels are subsequently prepared by photoinitiation polymerization of the DMA, the MAPBA, the BMAC, and the monomer dimethylaminoethyl methacrylate (DMAEMA) using one-pot method. The dynamic covalent bonds are formed by the reaction of the catechol groups in DMA and phenylboronic acid groups in MAPBA, which contribute as the second crosslinking of the hydrogels besides the BMAC. The hydrogels show pH, temperature, glucose, and redox tetra-responsiveness derived from the reversible dynamic covalent bonds (borate ester and disulfide bonds) and responsive polymer chain PDMAEMA. The hydrogels display gel–sol transition in the presence of HCl and dithiothreitol (DTT) together, which exhibits AND logic gate response. In addition, the hydrogels show excellent self-healing ability due to the well-known dynamic covalent bond of borate esters. This multifunctional and smart hydrogels have potential applications in the fields of sensors, actuators, controlled drug delivery etc.

CAS / MDL: 62-31-7 2867-47-2
研究领域: 材料科学 · 化学 · 生物医学工程
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2014 ·Vol. 52 ·期 15 ·2131-2138 · IF 3.245

Triple stimuli-responsive amphiphilic glycopolymer

Wenjuan Guo,Tieshi Wang,Xinde Tang,Qun Zhang,Faqi Yu,Meishan Pei

Triple stimuli (temperature/pH/photo)-responsive amphiphilic glycopolymer, poly(2-(dimethylamino)ethyl methacrylate- co -6- O -methacryloyl-1,2,3,4-di- O -isopropylidene-D-galactopyranose)- b -poly(4-(4-methoxyphenylazo)phenoxy methacrylate) [P(DMAEMA- co -MAIpGP)- b -PMAZO] was synthesized by atom transfer radical polymerization, followed by the hydrolysis of MAIpGP groups, resulting in the target product poly(2-(dimethylamino)ethyl methacrylate- co -6- O -methacryloyl-D-galactopyranose)- b -poly(4-(4-methoxyphenylazo)phenoxy methacrylate) [P(DMAEMA- co -MAGP)- b -PMAZO]. The composition, moleculer weight, and moleculer weight distribution of the resultant polymers were characterized by 1 H NMR and gel permeation chromatography. The micelles formed in aqueous solutions were simulated by various chemical and physical stimuli and characterized by dynamic light scattering, transmission electron microscopy, and UV-vis spectroscopy. It was found that the glycopolymer is responsive to three different types of stimulus (light, temperature, and pH). The poly(2-(dimethylamino) ethyl methacrylate) segments give thermo- and pH-responsiveness. The presence of the azobenzene moiety endows the block copolymer to exhibit light-responsiveness due to its reversible trans-cis isomerization conversion. The triple stimuli-responsive glycopolymer micelles can simulate biomacromolecues in vivo / in vitro environment and can be expected to open up new applications in various fields. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 , 2131–2138

研究领域: 高分子化学 · 材料科学 · 生物医学工程
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Polymer Chemistry · 2018 ·Vol. 10 ·期 5 ·656-662 · IF 4.927

Multi-stimuli responsive poly(amidoamine) dendrimers with peripheral N-dialkylaminoethyl carbamate moieties

Qi-Song Tong,Wei Xu,Qiu-Yue Huang,Ya-Ru Zhang,Xiao-Xiao Shi,Hua Huang,Hong-Jun Li,Jin-Zhi Du,Jun Wang

A novel type of multi-stimuli responsive dendrimer with thermo-, pH-, and CO2-responsiveness was developed through facile modification of polyamidoamine dendrimers (PAMAM) with various N-dialkylaminoethyl carbamate moieties. A series of modified PAMAM dendrimers with a well controlled structure were obtained and characterized by 1H NMR. The aqueous solutions of these dendrimers showed a lower critical solution temperature (LCST)-type thermoresponse, and their cloud point temperature (Tcp) was determined by turbidity measurements. Tcp was tunable from 8 to 70 °C, depending on the hydrophobicity and substitution number of the terminal N-dialkylaminoethyl groups, PAMAM generation, pH values, and salt concentrations. Additionally, the solubility of the resultant dendrimers could be reversibly modulated by alternately bubbling CO2 and argon. Our study offers a simple but effective approach to making new multi-stimuli responsive dendrimers for potential smart material applications.

CAS / MDL: 100-37-8 108-01-0
研究领域: 材料科学 · 化学
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JOURNAL OF APPLIED POLYMER SCIENCE · 2021 ·Vol. 138 ·期 24 ·50580 · IF 3.125

Polyion complex micelles formed by azobenzene-based polymer with multi-responsive properties

Dandan Zhang,Jilu Li,Hongmei Xie,Aoqi Zhu,Yiting Xu,Birong Zeng,Weiang Luo,Lizong Dai

Compared with the single polymer micelle system, the polyion complex micellar system is consisted of two or more polymers with different composition, which has more flexible structural adjustment and better performance, making them widely used in drug control release. In this work, two azobenzene-based amphiphilic copolymers P (MMA- co -PEGMA- co -NIPAM- co -HAZOMA) with ionized carboxyl and P (MMA- co -PEGMA- co -NIPAM- co -NNAZOMA) with protonated tertiary amine group were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. We studied self-assembled behavior of polymers and multi-component polymers, including their multiple responsiveness and the encapsulation, controlled release properties of polyion complex micelle. Light, pH, temperature, and reduction responsiveness of three micelles were investigated by UV–vis spectroscopy, transmission electron microscope (TEM), and dynamic light scattering. Compared to RCP 1, and RCP 2, RCP 1/RCP 2 micelle can release Nile red in both acidic and alkaline environment. When temperature reached critical solution temperature, RCP 1/RCP 2 micelle would release Nile red faster. Polyion complex micelle had better release performance compared to single micelles at the same environment, and could release in a wider range pH, making it had more potential applications in biological science field.

研究领域: 高分子化学 · 药物传递系统 · 生物材料
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LANGMUIR · 2024 · IF 3.7

Multiresponsive Behavior of the Pickering Emulsifier and Its Application for Collecting Small Oil Droplets in Water

Jing Li,Keran Li,Qin Zhang,Lifei Peng,Xiaoping Zhu

Responsive Pickering emulsions, with unique nanoparticle interfaces and sensitivity to external stimuli, significantly enhanced the stability and applicability of Pickering emulsions. Multifunctional composite material poly((2-(dimethylaminoethyl methacrylate)-b-(acrylate cyclodextrin))/Fe3O4 nanoparticles, namely P(DMAEMA-b-A-CD)/Fe3O4, with both multiresponsive characteristics and emulsifying capabilities had been designed to remove small oil droplets from water. Using the reversible addition–fragmentation chain transfer (RAFT) method, diblock polymers P(DMAEMA-b-A-CD) were grown in a controlled manner on the surface of Fe3O4. The Fe3O4 core showed responsiveness to a magnetic field, and the block copolymers prepared via the RAFT method demonstrated reactivity to both pH and CO2. The P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles exhibited the capability to form Pickering/Oxford emulsions with exceptional stabilization properties. It could be observed that the introduction of CO2, acid, and a magnetic field led to the breakage of the emulsion, while the emulsion could be restabilized by removing the CO2 and the magnetic field or by adding alkali. Measurements of interfacial tension, ζ-potential, and contact angle demonstrated that the emulsification/breakdown mechanisms associated with pH and CO2/N2 were related to the surface wettability of the nanoparticles. In addition, the emulsifier had an excellent cycling capacity with at least 10 cycles by CO2/N2. Additionally, P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles exhibited excellent stability in oil phases with large polarity differences and various real oil phases with different viscosities. Importantly, the P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles could serve as functional materials for efficiently separating small oil droplets from water through the application of a magnetic field. Therefore, P(DMAEMA-b-A-CD)/Fe3O4 nanoparticles held promising potential as materials with economic and commercial value for oil–water separation applications.

CAS / MDL: 2867-47-2
研究领域: 材料科学 · 环境工程 · 界面化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2018 · IF 5.091

Dual stimuli-responsive polysulfone membranes with interconnected networks by a vapor-liquid induced phase separation strategy

Li-Jing Zhu,Hai-Ming Song,Gang Wang,Zhi-Xiang Zeng,Qun-Ji Xue

Dual pH- and thermo-responsive polysulfone (PSf) membranes with three-dimensionally interconnected networks are fabricated by introducing poly(acrylic acid- co - N -isopropylacrylamide) (P(AA-NIPAm)) into the membrane surfaces and pore walls during membrane formation via a vapor-liquid induced phase separation (V-LIPS) process. After introducing the copolymers of P(AA-NIPAm), the fabricated membranes exhibit impressive open network pores on the surfaces, meanwhile their cross-sectional structure turns from classical asymmetric finger-like structure into bi-continuous nanopores throughout the whole thickness of membrane, due to high solution viscosity and low mass transfer rate of VIPS process. Furthermore, pure water permeation tests show that the pure water permeation ( L p ) and the molecular weight cutoff (MWCO) of the fabricated PSf/P(AA-NIPAm) membranes increases sharply as the solution pH decreases from 12.5 to 1.5 and the feed temperature increases from 25 to 50 °C, attributing to the increasing pore size. With the decreasing mass ratio of AA to NIPAm, the pH-responsive coefficient decreases, while the temperature- responsive coefficient increases. In particular, for the fabricated membrane with the mass ratio of AA to NIPAm of 3 to 2, L p changes from ∼16.0 to ∼821.4 L m −2  h −1  bar −1 and MWCO increases from ∼223.1 to ∼1493.2 kDa, as the filtration experiments are operated with feed pH and temperature of 12.5/25 °C and 1.5/50 °C respectively. The results proposed in this study provide a novel mode for design and development dual responsive porous membranes in situ, which will enable good separation of various materials and expand the scope of membrane applications.

研究领域: 材料科学 · 分离技术
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JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS · 2013 ·Vol. 51 ·期 20 ·1494-1504 · IF 2.221

Synthesis and characterization of polyhedral oligomeric silsesquioxane hybrid co-crosslinked poly(N-isopropylacrylamide-co-dimethylaminoethyl methacrylate) hydrogels

Yi Chen,Yuanqin Xiong,Chang Peng,Wenyong Liu,Yue Peng,Weijian Xu

Polyhedral oligomeric silsesquioxane hybrid temperature and pH double-responsive hydrogels with organic–inorganic co-crosslinked networks are synthesized by in situ , free-radical polymerization of N -isopropylacrylamide and dimethylaminoethyl methacrylate in the presence of both organic crosslinker N , N ′-methylenebis(acrylamide) (BIS) and inorganic crosslinker octavinyl polyhedral oligomeric silsesquioxane (OvPOSS) in tetrahydrofuran media. The resulting hydrogels (OR-OvP gels) display obvious temperature and pH double responsiveness, OvPOSS particles dispersed in polymer make a dominant effect on the properties of gels. With the increase of OvPOSS, the aggregation of particles on nano- or microscale happens and causes a considerable change on the properties of gels, such as the lower critical solution temperature and better compression strength. Specially, the interconnected microporous structure of gels ascribed to the microphase separation results in faster deswelling rate, which makes the gel become attractive. Besides, the crosslink by BIS intensifies the heterogeneity of gels significantly, which could also be used to adjust the properties of gels. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51 , 1494–1504

研究领域: 材料科学 · 高分子化学
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JOURNAL OF POLYMER SCIENCE · 2021 ·Vol. 59 ·期 17 ·1958-1971 · IF 0

pH/enzyme/light triple-responsive vesicles from lysine-based amphiphilic diblock copolymers

Guoyang Qin,Cong Hu,Yanfen Jiang,Shuqi Dong,Li Liu,Hanying Zhao

We report the synthesis of pH- and enzyme-responsive amphiphilic diblock copolymers through reversible addition-fragmentation chain transfer polymerization of a lysine-derived methacrylate monomer comprising p -nitrobenzyl carbamate ( p NBC) functionality using a poly(ethylene glycol)-modified macro-chain transfer agent. Depending on the hydrophobic block length, the diblock copolymers self-assemble to form spherical micelles, wormlike micelles, and bilayered vesicles in the aqueous solution. The responsive behaviors of the polymeric vesicles to pH, enzyme, and light are investigated in detail. As the pH lowers to pH 5.0, the polymeric vesicles undergo a morphological transition from vesicles to spherical micelles. In the presence of nitroreductase and a cofactor NADH, the decomposition of p NBC releases the ε-NH 2 of the lysine moiety and hence induces the generation of the vesicles with crosslinked membranes at pH 7.4. Moreover, owing to the degradation of p NBC moiety under UV irradiation, the polymeric vesicles also demonstrate a photo-responsive feature. As the irradiation time prolongs, it is observed a light-triggered morphological transition from vesicles to wormlike micelles with network-like structures. Graphical

CAS / MDL: 13734-28-6
研究领域: 材料科学 · 生物化学 · 纳米医学
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CHEMISTRY OF MATERIALS · 2021 · IF 9.811

Biomimetic Self-Deformation of Polymer Interpenetrating Network with Stretch-Induced Anisotropicity

Ying Liu,Yi Lei,Luqin Hua,Jianlei Lu,Kaojin Wang,Chuanzhuang Zhao

The introduction of anisotropicity is the key step of developing stimuli-responsive polymer hydrogels into intelligent devices. Among these anisotropic materials, hydrogels with oriented structures have attracted tremendous attention. However, most of oriented hydrogels are fabricated through aligning nanofillers or microchannels with external fields. In this work, instead of adding inert materials, we report a facile method to fabricate temperature and pH dual-responsive hydrogels with orientated polymer chains. The hydrogels are based on the interpenetrating network (IPN) of poly(acrylic acid) (PAAc) and poly(acrylamide) (PAAm), which can form temperature- and pH-switchable hydrogen bonds (H-bonds). The two polymerized networks are synthesized sequentially, which allows the application of a stretching force on the primary PAAm network and to “memorize” the orientation through the photopolymerization of the secondary PAAc network. Thanks to the aligned polymer chains and the oriented H-bonds, the obtained gels (i.e., PINSIA) exhibit anisotropic volume phase transition in response to temperature and pH. Due to the bilayer structure generated by the photopolymerization, the directions of the internal stresses of these two layers, that is, the bottom and top layer of the PINSIA gels, are perpendicular, driving the gels to form helices when tailored into narrow strips. Furthermore, the helical structure can be programmed by changing the cutting angle and the width of the gel strip and regulated by switching pH and temperature. This work provides a facile method to construct anisotropic hydrogels that can deform into programmable shapes, which could inspire the design and fabrication of smart hydrogels with potential applications as actuators, information carriers, etc.

研究领域: 材料科学 · 高分子化学
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Journal of the Taiwan Institute of Chemical Engineers · 2016 · IF 2.848

pH, temperature and reduction multi-responsive polymeric microspheres as drug delivery system for anti-tumor drug: Effect of middle hollow layer between pH and reduction dual-responsive cores and temperature sensitive shells

Jiagen Li,Jin Zeng,Xu Jia,Lei Liu,Tingting Zhou,Peng Liu

Multi-responsive polymeric microspheres have attracted more and more interest as drug delivery system (DDS) for anti-tumor drugs because they could achieve “on-demand” drug release, triggered by the tumor micro-environment. Here the pH, temperature and reduction multi-stimuli responsive polymeric microspheres were fabricated via distillation–precipitation polymerization technique, with or without the middle hollow layer between their pH and reduction responsive poly(methacrylic acid) (PMAA) cores and temperature sensitive poly( N -isopropylacrylamide) (PNIPAM) shells. The effect of the hollow layer on their drug loading and drug release performance was investigated in detail. It was found that the PMAA/PNIPAM yolk/shell microspheres with hollow layer possessed a higher drug loading capacity, while the PMAA/PNIPAM core/shell microspheres without hollow layer exhibited a better controlled release behavior. This understanding must be helpful on designing intelligent anti-tumor DDS.

CAS / MDL: 70-18-8 2530-85-0
研究领域: 药学 · 生物材料学 · 肿瘤学
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