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CHEMISTRY-A EUROPEAN JOURNAL · 2017 ·Vol. 23 ·期 32 ·7737-7747 · IF 5.317

Robust Stimuli-Responsive Membranes Prepared from a Blend of Polysulfone and a Graft Copolymer Bearing Binary Side Chains with Thermo- and pH-Responsive Switching Behavior

Lei Miao,Yuanyuan Tu,Yang Yang,Shudong Lin,Jiwen Hu,Min Zhang,Yue Li,Fei Li,Yangmiao Mo

Graphical Doubly responsive : A thermo- and pH-sensitive binary graft copolymer bearing anchoring side chains was synthesized and blended with commercial polysulfone to prepare thermo- and pH-responsive blended membranes, which exhibited robust, reversible, independent temperature- and pH-responsive water wettability and water permeability (see figure). A stimuli-responsive membrane exhibiting independent pH- and temperature-responsive behavior was fabricated from a blend of commercial polysulfone with a functional amphiphilic binary graft copolymer, namely, polysulfone- graft -(poly(isopropylacrylamide- co -acrylic acid)- random -poly(methyl acrylate)), denoted PSf- g -(P(NIPAAm- co -AA)- r -PMMA). Two graft copolymers with different lengths of P(NIPAAm- co -AA) side chains were designed and enriched on the membrane surface to serve as thermo- and pH-responsive on/off switches. The differences between the dual-responsive behaviors of the two kinds of polymer-blend membranes were studied by water-flux and contact-angle measurements. The PMMA side chains served to securely anchor the graft copolymers to the membrane substrate, and the blended membrane prepared from binary graft copolymer was more stable and exhibited more robust stimuli-responsive behavior than that prepared from mono-graft copolymer PSf- g -P(NIPAAm- co -AA).

研究领域: 材料科学 · 高分子化学
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JOURNAL OF MEMBRANE SCIENCE · 2017 · IF 6.035

Development of smart poly(vinylidene fluoride)-graft-poly(acrylic acid) tree-like nanofiber membrane for pH-responsive oil/water separation

Bowen Cheng,Zongjie Li,Quanxiang Li,Jingge Ju,Weimin Kang,Minoo Naebe

A smart tree-like nanofiber membrane with pH-responsivity was successfully fabricated by electrospinning poly(vinylidene fluoride)-graft-poly(acrylic acid) (PVDF-g-PAA). X-ray photoelectron spectroscopy, field emission scanning electron microscopy , Fourier transform infrared spectroscopy , and Brunauer-Emmett-Teller surface area measurement were employed to study the molecular structure and morphology of membranes. Through realizing protonation and deprotonation in response to the pH of the aqueous media, the as-prepared membrane is able to alter its wettability and conformation, resulting in the switchable surface oil/water wettability in the aqueous media. More importantly, the as-prepared membrane realized on-demand oil/water separation using gravity alone by switching the pH of the medium. Both separations exhibited excellent efficiency and flux which were attributed to the tree-like structure of the membrane. We believed that this smart membrane with such excellent controllable permeation has potential to be used for several applications, such as water purification , oil recovery and some separation systems.

CAS / MDL: 1112-67-0
研究领域: 材料科学 · 环境工程
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ANALYTICAL CHEMISTRY · 2017 · IF 6.32

pH-Responsive Graphene Oxide–DNA Nanosystem for Live Cell Imaging and Detection

Chen Shao,Jia Liang,Sihui He,Tianqi Luan,Jiantao Yu,Haoran Zhao,Jingyuan Xu,Leilei Tian

The interaction between graphene oxide (GO) and DNA is very sensitive to the environment. For example, under acidic conditions, the affinity of GO for DNA is enhanced, weakening the capability of GO to distinguish DNAs with different conformations. This effect has impeded the development of sensitive pH biosensors based on GO–DNA nanosystems. In this work, we systematically studied the affinity between GO and i-motif forming oligonucleotides (IFOs) at different pH values and developed a herring sperm DNA (HSD) treatment method. Using this method, HSD occupies the surface of GO, compromising the attractive force of GO that is significantly enhanced under acidic conditions. As a result, the ability of GO to distinguish between “open” and “closed” IFOs is successfully generalized to a wider pH range. Finally, a pH-sensitive GO–IFO nanosystem was fabricated that showed excellent sensing ability both in vitro and for intracellular pH detection. Because the interaction between GO and DNA is the basis for constructing GO–DNA biosensors, the strategy developed in this work shows great potential to be applied in a variety of other GO–DNA sensing systems.

研究领域: 生物化学 · 纳米生物学 · 分析化学
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ACS Applied Materials & Interfaces · 2016 · IF 7.145

A Simple Dual-pH Responsive Prodrug-Based Polymeric Micelles for Drug Delivery

Jie Mao,Yang Li,Tong Wu,Conghui Yuan,Birong Zeng,Yiting Xu,Lizong Dai

To precisely deliver drug molecules at a targeted site and in a controllable manner, there has been great interest in designing a synergistical drug delivery system that can achieve both surface charge-conversion and controlled release of a drug in response to different stimuli. Here we outline a simple method to construct an intelligent drug carrier, which can respond to two different pH values, therefore achieving charge conversion and chemical-bond-cleavage-induced drug release in a stepwise fashion. This drug carrier comes from the self-assembly of a block copolymer-DOX conjugate synthesized through a Schiff base reaction between poly(2-(diisopropylamino)ethyl methacrylate-b-poly(4-formylphenyl methacrylate-co-polyethylene glycol monomethyl ether methacrylate) (PDPA-b-P(FPMA-co-OEGMA)) and DOX. The surface charge of the BCP-DOX micelles reversed from negative to positive when encountering a weakly acidic environment due to the protonation of PDPA segments. In vitro cellular uptake measurement shows that the cellular uptake and internalization of the BCP-DOX micelles can be significantly enhanced at pH ∼ 6.5. Moreover, this drug carrier exhibits a pH-dependent drug release owing to the cleavage of the imine bond at pH < 5.5. With this dual-pH responsive feature, these micelles may have the ability to precisely deliver DOX to the cancer cells.

研究领域: 生物材料 · 药剂学 · 肿瘤学
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AUSTRALIAN JOURNAL OF CHEMISTRY · 2013 ·Vol. 67 ·期 1 ·134-141 · IF 1.869

Responsive P(NIPAM-co-AA) Particle-Functionalized Magnetic Microspheres

Yiheng Wang,Mengge Xia,Yongtao Wu,Meifang Zhu

Functionalized magnetic microspheres were prepared by anchoring cross-linked core–shell poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPAM-co-AA)) nanoparticles onto silica-coated magnetic microspheres (Fe3O4@SiO2). First, the smaller polystyrene/P(NIPAM-co-AA) core–shell nanoparticles were synthesized through seed emulsion polymerization and adhered to the surface of amino-modified Fe3O4@SiO2 micorspheres, which were made using the modified Stöber method through electrostatic interaction under appropriate preparation conditions. An amidation reaction between the carboxylic and amino groups on the respective surfaces was then catalyzed. Finally, the novel architecture magnetic microspheres with multiresponsive functionalities were obtained, and their polymerization conditions, environmental sensitivity, and magnetic properties were discussed and optimized. The superparamagnetism and temperature/pH dual responsivity and excellent dispersibility of the P(NIPAM-co-AA) functionalized magnetic microspheres provide them with high potential to be used in the fields of controlled drug delivery, bioseparation, and catalysis.

CAS / MDL: 7758-94-3
研究领域: 材料科学 · 生物医学工程
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2013 ·Vol. 52 ·期 2 ·188-199 · IF 3.543

Synthesis and pH-responsive assembly of methoxy poly(ethylene glycol)-b-poly(ε-caprolactone) with pendant carboxyl groups

Yan Zhang,Jinhong Li,Zhengzhen Du,Meidong Lang

pH-responsive methoxy poly(ethylene glycol)- b -poly(ε-caprolactone) bearing pendant carboxyl groups mPEG- b -P(2-CCL- co -6-CCL) was synthesized based on our newly monomer benzyloxycarbonylmethly functionalized ε-caprolactone. Their structure was confirmed by 1 H NMR, 13 C NMR, and Fourier transform infrared spectrum spectra. In addition, SEC results indicated that the copolymers had a relatively narrow polydispersity. WXRD and DSC demonstrated that the introduction of carboxymethyl groups had significant effect on the crystallinity of the copolymers. Furthermore, the solution behavior of mPEG- b -P(2-CCL- co -6-CCL) has been studied by various methods. The results indicated that mPEG- b -P(2-CCL- co -6-CCL) had a rich pH-responsive behavior and the micelles could be formed by pH induction, and the mPEG- b -P(2-CCL- co -6-CCL) could existed as unimers, micelles or large aggregates in different pH range accordingly. The mechanism of which was supposed to depend on the counteraction between the hydrophobic interaction from PCL and the ionization of the carboxyl groups along the polymer chain. Moreover, the mPEG- b -P(2-CCL- co -6-CCL) copolymers displayed good biocompatibility according to the preliminary cytotoxicity study. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52 , 188–199

CAS / MDL: 5437-45-6 937-14-4
研究领域: 高分子化学 · 生物材料 · 药物递送
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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 9 ·4472-4477 · IF 3.3

Multiple switchable circularly polarized luminescence from nucleotide/terbium(III) complexes

Chujing Yang,Zhiwei Zhang,Jingqi Chen,Xinying Zhang,Yankai Dai,Xuyi Li,Yingying Chen,Jiaqiang Xu,Lingyan Feng

We found that the complexes of nucleotides and terbium(III) exhibit circularly polarized luminescence (CPL). The CPL of GMP/Tb/Ag coordination polymer nanoparticles (CPNs) was converted by a magnetic field and pH. The CPL of the purine nucleobase of nucleotides was opposite to that of the pyrimidine nucleobase. GMP/Tb/Ag CPNs could be used as advanced safety coatings and acid–base switches, and Tb/Ag could be used as CPL probes for rapid differentiation of nucleotides, which provided ideas for multiple transformations and applications of CPL.

研究领域: 生物化学 · 材料科学 · 光学
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

pH-Responsive foams triggered by particles from amino acids with metal ions

Yanan Xing,Liya Zhang,Li Yu,Aixin Song,Junqing Hu

Stimuli-responsive Pickering foams have attracted wide attention due to their good stability and controllable foamability. In this work, pH-switchable Pickering foams were constructed using particles from amino acids with metal ions as stabilizers. Some hydrophobic amino acids, phenylalanine, leucine and tryptophan, can induce the production of particles with suitable wettability in the case of combination with some metal ions at their deprotonated forms, and further form Pickering foams. The foams exhibit good stability and can be cycled between foaming and defoaming forms by modulating pH of solutions. When pH was increased, the amino acids were in anionic forms and could easily coordinate with metal ions, forming insoluble particles to stabilize the foams. As pH was decreased, the protonation of amino acids led to the disappearance of particles, resulting in the defoaming state. This work proposes a simple method to prepare Pickering foams with environmentally friendly amino acids as the raw materials, providing a new idea for the construction of stimuli-responsive disperse systems.

研究领域: 材料科学 · 化学工程 · 胶体与界面科学
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2023 ·Vol. 25 ·期 37 ·25780-25788 · IF 3.3

pH/magnetic dual responsive Pickering emulsion stabilized by Fe3O4@SiO2@chitosan nanoparticles

Runna He,Shuangqing Sun,Jianpeng Cui,Mingshuo Chi,Zhikun Wang,Songqing Hu

In recent years, Pickering emulsifiers have been widely used in various production fields due to their excellent structural stability, biocompatibility and environmental friendliness. For some applications, it is required that the emulsifier can quickly respond to environmental stimuli and control the transition between stable and unstable emulsions. In this paper, we report a novel composite Pickering emulsifier with Fe3O4 as the core and magnetic response recognition body, silica as the intermediate protective layer, and chitosan (CS) of different molecular weights to endow solid particles with surface activity and pH-responsive properties. This emulsifier can stabilize the emulsion in the emulsion system with deionized water as the aqueous phase and liquid paraffin as the oil phase and can control the demulsification of the formed emulsion under the dual pH/magnetic stimulation. The experimental results show that Fe3O4@SiO2@CS has good paramagnetism and pH responsiveness. The particle size of the composite emulsifier nanoparticles is between 90 nm and 120 nm, and the best stabilizing effect of the emulsion is achieved when the dosage is 0.5 wt%. In the pH range of 3–11, the emulsifier can rapidly demulsify a stable paraffin oil–water emulsion system under the action of a magnetic field of strength 0.4 T. The pH response of the emulsifier is as follows: when pH ≤ 2, the system can form a stable emulsion, which is composed of fully protonated chitosan as a free chain segment and Fe3O4@SiO2. Emulsion stabilization was achieved with monolithic Fe3O4@SiO2@CS as an emulsifier at pH > 2, and demulsification was achieved at pH ≈ pKb (CS) at 298 K. The research in this paper can provide a feasible idea and synthesis method for the preparation of organic–inorganic composite structure emulsifier.

研究领域: 材料科学 · 化学工程 · 纳米技术
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Multifunctional Organohydrogels for pH-Responsive Fluorescent and Electrostimulus Writing

Siyu Yang,Qiuyan Luo,Chuanluan Guo,Jia Jiang,Xiaohong Wang,Juguo Dai,Dongxu Li,Kaibin He,Yiting Xu,Conghui Yuan,Weiang Luo,Lizong Dai

Hydrogels have attracted widespread attention in anticounterfeiting due to their unique physical/chemical properties and designability. However, hydrogels’ poor mechanical properties and sluggish response to chemical stimuli pose challenges for their wide application. A fluorescent tough organohydrogel capable of freeform writing of information is reported in this work. By incorporation of the fluorescent monomer 7-methylacryloxy-4-methylcoumarin into the polyacrylamide network in a covalently cross-linked manner while intertwining with the carboxymethyl cellulose sodium network, a fluorescent tough organohydrogel with a dual-network structure is prepared. The organohydrogel shows acid–base-mediated adjustable fluorescence through the transformation of fluorescent monomers. Ion printing and electrical stimulation design achieved free information storage and encryption. In addition, the prepared organohydrogel has good antifreezing properties and can be encrypted and decrypted at subzero temperatures. The encrypted information in the organohydrogel can be read only after UV-light irradiation. These patterned fluorescent organohydrogels should find applications in protected message displays for improved information security.

研究领域: 材料科学 · 化学
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MATERIALS SCIENCE FORUM · 2020 · IF 0

Synthesis of pH-Responsive Glycopolymer with End Group Zinc(II) Phthalocyanines as Potential Photosensitizer

Shu Guo Dong,Gui Hua Cui,Qian Duan

A novel end-functionalized glycopolymer poly (3-O-methacryloyl-D-glucofuranose) -b-poly (2-Diethylaminoethyl Methacrylate) (PMAGlc-b-PDEA-ZnTAPc) with zinc (II) teraamaninophthalocyanine was synthesized. First, a pH-responsive copolymer PMAIpG-b-PDEA was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Then PMAIpG-b-PDEA reacted with ZnTAPc and deprotected to form a water-soluble and pH-responsive photosensitizer. The structure of the PMAGlc-b-PDEA-ZnTAPc was characterized by 1H NMR and GPC. The photophysical properties were evaluated by UV-Vis and fluorescence spectra. The PMAGlc-b-PDEA-ZnTAPc can generate singlet oxygen species with good singlet oxygen quantum yields (Φ△=0.38), which is believed to be the major cytotoxic reactive oxygen species (ROS) for photodynamic therapy. The ZnPc functionalized glycopolymer will be used as a potential photosensitizer in the fields of photodynamic therapy.

研究领域: 材料科学 · 生物医学工程 · 药物化学
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JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY · 2019 ·Vol. 31 ·期 6 ·739-746 · IF 0.934

Synthesis of Water-Soluble Spiropyran-Modified Poly(acrylic acid) Micelles and Their Optical Behaviors

Rui Xue,Xinghua Zhang,Jintao Tian

In this study, a spiropyran derivative (SPOH) is firstly grafted onto a polymer backbone of a poly(acrylic acid) (PAA) via an esterification process. The synthesized spiropyran-modified poly(acrylic acid) (PAA-SP) polymer is characterized by FTIR and 1H NMR. The synthesized PAA-SP is then dissolved into water to achieve water-soluble micelles. The optical behaviors of PAA-SP micelles are investigated by ultraviolet-visible (UV-Vis) absorption spectra and fluorescence emission spectra under acid/base and light stimuli in aqueous solution. Our experimental results reveal that the as-prepared PAA-SP micelles are water-soluble and show good photochromic and emissive behaviors. Meanwhile, the optical behaviors of the micelles are light-responsive and acid/base-responsive and hence can be tailored via the adjustments of both light and pH value of the solution sample. And our results may be meaningful for practical application of hydrophobic spiropyran derivatives in aquatic environments.

研究领域: 材料科学 · 化学
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