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Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles

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Frontiers of Materials Science 2016年第2期10卷 178-186页

作者： Junbo LI Jianlong ZHAO Wenlan WU Ju LIANG Jinwu GUO Huiyun ZHOU Lijuan LIANG College of Chemical Engineering & Pharmaceutics Henan University of Science & Technology Luoyang 471023 China Medical School Henan University of Science & Technology Luoyang 471003 China

In this paper, double hydrophilic ionic liquid block copolymers （ILBCs）, poly poly[1-methyl-3-（2-methacryloyloxy propylimidazolium bromine）]-block-（***. pylacrylamide）（PMMPImB-b-PNIPAAm） was first synthesized by reversible addition- fragmentation chain transfer （RAFT） and then attached on the surface of gold nanoparticles （Au NPs） via a strong gold-sulfur bonding for preparing hybrid nanoparticles （PMMPImB-b-PNIPAAm-@-Au NPs）. The hybrid NPs had a three layers micelle-like structure, including a gold core, thermo-responsive inner shell and anion responsive outer corona. The self-assembling behavior of thermal- and anion-response from shell and corona were respectively investigated by change of temperature and addition of （CF3SO2）2N-. The results showed the hybrid NPs retained a stable dispersion beyond the lower critical solution temperature （LCST） because of the space or electrostatic protecting by outer PMMPImBo However, with increasing concentration of （CF3SO2）2N-, the micellization of self-assembling PMMPImB-b-PNIPAAm-@-Au NPs was induced to form micellar structure containing the core with hydrophobic PMMPImB- （CF3SO2）2N- surrounded by composite shell of Au NPs-PNIPAAm via the anion- responsive properties of ILBCs. These results indicated that the block copolymers protected plasmonic nanoparticles remain self-assembling properties of block copoly- mers when phase transition from outer corona polymer.

关键词： block copolymer dual stimuli-responsive gold nanoparticles (Au NPs) self-assembly

Synthesis of poly(ethylene glycol)-SS-poly(ε-caprolactone)-SS-poly(ethylene glycol)triblock copolymers via end-group conjugation and self-assembly for reductively responsive drug delivery

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Frontiers of Materials Science 2019年第4期13卷 410-419页

作者： Junbo LI Junting JIANG Biyu ZHOU Chaohuang NIU Wendi WANG Wenlan WU School of Chemical Engineering and Pharmaceutics Henan University of Science and TechnologyLuoyang 471023China School of Medicine Henan University of Science and TechnologyLuoyang 471023China

In this study,we describe a simple synthesis route to prepare triblock copolymers with disulfide-linkers,poly(ethylene glycol)-SS-poly(ε-caprolactone)-SS-poly(ethylene glycol)(PEG-SS-PCL-SS-PEG)for application in the reductively responsive release of doxorubicin(DOX).To synthesize PEG-SS-PCL-SS-PEG,two end-groups of PCL-diol were first modified with cystamine to introduce disulfide bonds and subsequently conjugated with PEG-NHS via carbodiimide ***-SS-PCL-SSPEG fabricated into polymeric micelles with stable structure and different nanoscale sizes via adjusting the PCL chain length,showing obvious reductive responsiveness and fast drug release of encapsulated DOX in the presence of glutathione(GSH).Moreover,DOX-loaded PEG-SS-PCL-SS-PEG micelles exhibited higher therapeutic efficacy than reduction-insensitive PEG-b-PCL micelles in ***,end-groups conjugation is a simple and straightforward strategy to introduce intelligent responsiveness in biocompatible block copolymers and improve their therapeutic efficacy.

关键词： poly-ε-caprolactone poly(ethylene glycol) block copolymer reductive responsiveness drug release

Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP

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Chinese Chemical Letters 2008年第2期19卷 237-240页

作者： Xin De Tang Long Cheng Gao Xing He Fan Qi Feng Zhou Institute of New Materials Shandong Jiaotong University Ji＇nan 250023 China Department of Polymer Science and Engineering College of Chemistry and Molecular Engineering Peking University Beijing 100871 China

H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide）（PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.

关键词： H-type Amphiphilic block copolymer Liquid crystalline property Atom transfer radical polymerization (ATRP)

Synthesis of Dendritic-Linear block copolymers by Atom Transfer Radical Polymerization

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Chinese Chemical Letters 2001年第7期12卷 595-596页

作者： You Liang ZHAO Ai Jun GONG Jing JIANG Hong Wei LIU Chuan Fu CHEN Fu XI State Key Laboratory of Polymer Physics and Chemistry Center of Molecular ScienceInstitute of ChemistryChinese Academy of SciencesBeijing 100080

The dendritic polyarylether 2-bromoisobutyrate as the macromolecular initiator for the controlled free radical polymerization of styrene was investigated. The polymerization was carried out with CuBr/2,2 ' -bipyridine catalyst at 110 degreesC. It is found that the hybrid dendritic-linear block copolymers possess well-defined molecular weights and low polydispersities.

关键词： Atom transfer radical polymerization dendrimer polystyrene block copolymer

Recent Advances in Helical Polyisocyanide-based block copolymers:Preparation,Self-assembly and Circularly Polarized Luminescence

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Chemical Research in Chinese Universities 2023年第5期39卷 719-725页

作者： ZHOU Li CHEN Kun ZHOU Xing-Yu WU Zong-Quan Department of Polymer Science and Engineering School of Chemistry and Chemical EngineeringAnhui Key Laboratory of Advanced Functional Materials and DevicesHefei University of TechnologyHefei 230009P.R.China State Key Laboratory of Supramolecular Structure and Materials College of ChemistryJilin UniversityChangchun 130012P.R.China

Polyisocyanides and their block copolymers have widespread applications in many fields due to their unique helix and self-assembly *** first,the latest progress in the preparation of helical polyisocyanide-based block copolymers via the method of one-pot sequential controlled synthesis and stepwise polymerization was highlighted in this *** categories of helical polyisocyanide-based copolymers including amphiphilic block copolymers,UV-response block copolymers,π-conjugated block copolymers,etc.,have been prepared ***,recent advances in the self-assembly and circularly polarized luminescence performance of amphiphilic andπ-conjugated helical polyisocyanide-based copolymers have been introduced,*** hope this minireview will not only inspire more interest in developing helical polyisocyanide-based copolymers,but also encourage further progress in the field of building artificial functional materials.

关键词： Helical polyisocyanide block copolymer Self-assemble Circularly polarized luminescence

Amphiphilic block copolymers directed synthesis of mesoporous nickel-based oxides with bimodal mesopores and nanocrystal-assembled walls

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Chinese Chemical Letters 2019年第12期30卷 2003-2008页

作者： Yuan Ren Xuanyu Yang Xinran Zhou Wei Luo Yi Zhang Xiaowei Cheng Yonghui Deng Department of Chemistry State Key Laboratory of Molecular Engineering of PolymersShanghai Key Laboratory of Molecular Catalysis and Innovative MaterialsiChEMFudan UniversityShanghai 200433China State Key Laboratory for Modification of Chemical Fibers and Polymer Materials College of Materials Science and EngineeringDonghua UniversityShanghai 201620China School of Materials Science and Energy Engineering Foshan UniversityFoshan 528000China

Mesoporous late-transition metal oxides have great potential in applications of energy,catalysis and chemical sensing due to their unique physical and chemical ***,their synthesis via the flexible and scalable soft-template method remain a great challenge,due to the weak organic-inorganic interaction between the frequently used surfactants(e.g.,Pluronic-type block copolymers) and metal oxide precursors,and the low crystallization temperature of metal *** this study,ordered mesoporous NiO with dual mesopores,high surface area and well-interconnected crystalline porous frameworks have been successfully synthesized via the facile solvent evaporation-induced co-assembly(EICA) method,by using lab-made amphiphilic diblock copolymer polystyrene-b-poly(4-vinylpyridine)(PS-b-P4 VP) as both the structure-directing agent(the soft template) and macromolecular chelating agents for nickel species,THF as the solvent,and nickel acetylacetonate(Ni(acac)2) as inorganic ***,by using Ni(acac)2 and Fe(acac)3 as the binary precursors,ordered mesoporous Fedoped NiO materials can be obtained,which have bimodal mesopores of large mesopores(32.5 nm) and secondary mesopores(4.0-11.5 nm) in the nanocrystal-assembled walls,high specific surface areas(~74.8 m^2/g) and large pore value(~0.167 cm^3/g).The obtained mesoporous Fe-doped NiO based gas sensor showed superior ethanol sensing performances with good sensitivity,high selectivity and fast response-recovery dynamics.

关键词： block copolymer Co-assembly Metal oxides Mesoporous Gas sensing

Effect of bovine serum albumin on the micellization of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers in aqueous solutions by fluorescence spectroscopy

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Science China Chemistry 2006年第6期49卷 541-549页

作者： GUO Chen WANG Jing LIANG Xiangfeng ZHENG Lili LIU Huizhou Laboratory of Separation Science and Engineering State Key Laboratory of Biochemical EngineeringInstitute of Process EngineeringGraduate University of Chinese Academy of SciencesBeijing 100080China

Effect of bovine serum albumin(BSA)on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)(PEO-PPO-PEO)block copolymers was investigated using pyrene fluorescence *** critical micellization temperature(CMT)of pluronics in aqueous solution was increased by the addition of BSA.A closed association model was used to obtain the standard free energies(△DG^(0)),enthalpies(△DH^(0)),and entropies(△DS^(0))of *** standard enthalpy and entropy of micellization for pluronic polymers in water were decreased with an increase of the BSA *** more PPO component in the pluronic polymer,the higher the changed values of micellization enthalpy and *** hydrophobic part of the pluronics,PPO,was responsible for the interaction between pluronics and *** interaction between PPO and BSA was correlated to the alternation of the PPO-PPO interaction by the addition of BSA,which would shift the CMT toward higher temperature and alter the thermodynamic parameters of micellization for pluronics in aqueous solutions.

关键词： block copolymer bovine serum albumin micelle fluorescence spectroscopy.

STUDIES ON POLY(ETHYLENE TEREPHTHALATE)-POLY(TETRAMETHYLENE ETHER) MULTIblock copolymer.Ⅱ.THE MOLAR SEGMENT MASS AND MOLAR MASS

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Chinese Journal of Polymer Science 1991年第2期9卷 137-144页

作者：詹永坚应琦琮吴美琰钱人元 Institute of Chemistry Academia Sinica Beijng 100080

The molar segment mass, weight-average molar mass, and molar mass distribution of a poly-(ethylene terephthalate)-poly (tetramethylene ether) multiblock copolymer sample were determined by the methods of proton nuclea... 详细信息

关键词： Segmented copolymer Polyester Elastorner Polyester-Polyether block copolymer

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Construction of triblock copolymer-gold nanorod composites for fluorescence resonance energy transfer via pH-sensitive allosteric

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Chinese Chemical Letters 2020年第12期31卷 3131-3134页

作者： Li Zeng Zhipeng Su Xingyi Li Shuai Shi Institute of Biomedical Engineering School of Ophthalmology&Optometry and Eye HospitalWenzhou Medical UniversityWenzhou 325027China Department of Neurosurgery First Affiliated Hospital of Wenzhou Medical UniversityWenzhou 325000China

To explore the effects of microenvironmental adjustments on fluorescence,a pH-sensitive nanocomposite system based on fluorescence resonance energy transfer(FRET)was *** model system included a modified triblock copolymer(polyhistidine-b-polyethylene glycol-b-polycaprolactone)and gold nanoparticles.A near-infrared dye was used as the donor,and spectrally matched gold nanorods,attached after C-terminus modification with α-lipoic acid,were used as the receptor to realize control of the FRET effect over the fluorescence intensity for two polymer configurational changes(i.e.,"folded"and"stretched"states)in response to *** synthesis and characterization,we investigated the self-assembly behavior of the *** by quartz crystal microbalance revealed the pH sensitivity of the polymer,which exhibited"folding"and"stretching"states with changes in pH,providing a structural basis for the FRET *** spectrophotometry investigations also revealed the regulatory impact of the assembled system on fluorescence.

关键词： Fluorescence resonance energy transfer pH response Self-assembled nanoparticle Au nanorod block copolymer