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Iron-mediated AGET atrp of Styrene and Methyl Methacrylate Using Ascorbic Acid Sodium Salt as Reducing Agent

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Chinese Journal of Polymer Science 2014年第8期32卷 1010-1018页

作者： Jin-long Pan Zhen Li Li-fen Zhang 程振平朱秀林 Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Department of Polymer Science and Engineering College of Chemistry Chemical Engineering and Materials Science Soochow University

atom transfer radical polymerization of styrene （St） and methyl methacrylate （MMA） in bulk and in different solvents using activators generated by electron transfer （AGET atrp） were investigated in the presence of a limited amount of air using FeC13-6H2O as the catalyst, ascorbic acid sodium salt （AsAc-Na） as the reducing agent, and a cheap and commercially available tetrabutylammonium bromide （TBABr） as the ligand. It was found that polymerization in THF resulted in shorter induction period than that in bulk and in toluene for AGET atrp of St, while referring to AGET atrp of MMA, polymerization in THF showed three advantages compared with that in bulk and toluene：1） shortening the induction period, 2） enhancing the polymerization rate and 3） having better controllability. The living features of the obtained polymers were verified by chain end analysis and chain-extension experiments.

关键词： atom transfer radical polymerization （atrp） AGET atrp Iron catalyst Kinetics （polym.）.

Oriented Antibody Immobilization and Immunoassay Based on Boronic Acid-containing Polymer Brush

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Chinese Journal of Polymer Science 2018年第4期36卷 472-478页

作者： Jie Zhao Ru Mo Li-Mei Tian Ling-Jie Song Shi-Fang Luan Jing-Hua Yin Lu-Quan Ren Key Laboratory of Bionic Engineering Ministry ofEdueationJilin UniversityChangchun 130022China State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China Jilin Province People's Hospital Changchun 130021China

High sensitive immunoassay platforms have gained intense attention due to their vital roles in early-stage disease diagnosis and therapeutic information feedback. Although random covalent-binding of antibody has been widely adopted in immunoassays due to its simplicity and effectiveness, it readily loses its activity and fails to exhibit high antigen-binding capacity. In this work, copolymer of zwitterionic sulfobetaine methacrylate（SBMA） and glycidyl methacrylate（GMA） brushes were immobilized onto inert polypropylene（PP） via surface-initiated atom transfer radical polymerization（atrp） based on biomimetic dopamine pretreatment. Subsequently, boronic acid（BA） groups were covalently bonded via active GMA units, followed by the introduction of oriented immobilization of antibody. Owing to the oriented immobilization of antibody facilitated by BA groups in polymer brush, the bioactivity of antibody is well preserved, which endows the surface with significantly enhanced antigen-binding capacity. Moreover, the existence of SBMA segments in polymer brushes renders the surface high resistance to nonspecific protein adsorption, significantly alleviating the signal interference of antigen recognition. This strategy could find potential applications in developing high sensitive immunoassay platforms based on the different substrates.

关键词： Biomimetic dopamine atom transfer radical polymerization （atrp） Boronic acid （BA） Immunoassay Biomimetic

One-step synthesis and self-assembly behavior of thermo-responsive star-shaped β-cyclodextrin-（P（M EO2MA-co-PEGMA））21 copolymers

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Frontiers of Materials Science 2017年第3期11卷 223-232页

作者： Lulu WEI Beibei LU Lei LI Jianning WU Zhiyong LIU Xuhong GUO School of Chemistry and Chemical Engineering Shihezi University/Key Laboratory of Materials-Oriented Chemical Engineering of Xinjiang Uygur Autonomous Region/Engineering Research Center of Materials-Oriented Chemical Engineering of Xinjiang Bingtuan Shihezi 832003 China State Key Laboratory of Chemical Engineering East China University of Science and Technology Shanghai 200237 China

A novel β-cyclodextrin-poly（2-（2-methoxyethoxy）ethyl methacrylate）-co- poly（ethylene glycol） methacrylate （abbreviated as： β-CD-（P（MEO2MA-co-PEGMA））21） was prepared by using the one-step strategy, and then the star-shaped copolymers were used in the atom transfer radical polymerization （atrp）. The structure of star-shaped β- CD-（P（MEO2MA-co-PEGMA））21 copolymers were studied by FTIR, 1H NMR and gel permeation chromatography （GPC）. The star-shaped copolymers could self-assembled into micelles in aqueous solution owing to the outer amphiphilic β-CD as a core and the hydrophilic P（MEO2MA-co-PEGMA） segments as a shell. These thermo-responsive starshaped copolymers micelles exhibited lower critical solution temperature （LCST） in water, which could be finely tuned by changing the feed ratio of MEO2MA to PEGMA. The LCST of star-shaped β-CD-（P（MEO2MA-co-PEGMA））21 copolymer micelles were increased from 35℃ to 58℃ with the increasing content of PEGMA. The results were investigated by DLS and TEM. When the temperature was higher than corresponding LCSTs, the micelles started to associate and form spherical nanoparticles. Therefore, β- CD-（P（MEO2MA-co-PEGMA））21 star-shaped copolymer micelles could be potentially applied in nano-carrier, nano-reactor, smart materials and biomedical fields.

关键词： star-shaped copolymers thermo-responsive β-cyclodextrin （β-CD） self- assembly atom transfer radical polymerization （atrp）

Cellulose Functionalization via atrp Grafting of Glycidyl Methacrylate for Cr（VI） Adsorption

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Chinese Journal of Chemistry 2013年第12期31卷 1551-1556页

作者： Chunxiang Lin Sha Qiao Danhui Liu Minghua Liu College of Environment & Resources Fuzhou University Fuzhou Fuj ian 350108 China

Cellulose was first grafted with glycidyl methacrylate （GMA） in an ionic liquid via atom transfer radical polymerization （atrp） and then the introduced epoxy groups were reacted with ethanediamine （EDA） to obtain an amino adsorbent. The grafting copolymer and the obtained adsorbent were characterized by FTIR, aH NMR, TEM and SEM. The results showed that the grafted copolymers had grafted polymer chains with well-controlled molecu- lar weight and polydispersity, the polymerization was a controlled system. The cellulose adsorbent had numerous micropores on the surface and showed high performance for Cr（VI） adsorption. The adsorption behavior was pH dependent and the sorption equilibrium was achieved within 2 h on the adsorbent.

关键词： cellulose functionalization atom transfer radical polymerization （atrp） ionic liquid sorption Cr（VI）

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by atrp

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Chinese Chemical Letters 2009年第11期20卷 1353-1356页

作者： Xin De Tang Xiao Chao Liang Nian Feng Han Institute of New Materials Shandong Jiaotong University Ji'nan 250023 China College of Chemistry & Molecular Engineering Peking University Beijing 100871 China

Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （atrp）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the atrp ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.

关键词： Y-shaped Block copolymer Poly（ethylene glycol） Poly（N-isopropylacrylamide） atom transfer radical polymerization （atrp）

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）

元素碘存在下合成醋酸乙烯酯-甲基丙烯酸甲酯嵌段共聚物

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元素碘存在下合成醋酸乙烯酯-甲基丙烯酸甲酯嵌段共聚物