\r姚芳莲¹，郭 旗¹，罗巧悦¹，田 苗¹，王进美¹，胡 剑²，杨志伟²，李俊杰\r¹\r
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AuthorsHTML:\r姚芳莲¹，郭 旗¹，罗巧悦¹，田 苗¹，王进美¹，胡 剑²，杨志伟²，李俊杰\r¹\r
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AuthorsListE:\rYao Fanglian¹，Guo Qi¹，Luo Qiaoyue¹，Tian Miao¹，Wang Jinmei¹，Hu Jian ²，Yang Zhiwei ²，Li Junjie\r¹\r
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AuthorsHTMLE:\rYao Fanglian¹，Guo Qi¹，Luo Qiaoyue¹，Tian Miao¹，Wang Jinmei¹，Hu Jian ²，Yang Zhiwei ²，Li Junjie\r¹\r
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Unit:\r\r1. 天津大学化工学院，天津 300350；\r
\r\r2. 华东交通大学材料学院，南昌 330013\r
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Unit_EngLish:\r1. School of Chemical Engineering and Technology，Tianjin University，Tianjin 300350，China；
2. School of Materials Science and Engineering，East China Jiaotong University，Nanchang 330013，China\r
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Abstract_Chinese:\r\r分子结构中含有甜菜碱基团的两性离子聚合物，由于独特的反聚电解质性质使其在药物释放、抗蛋白吸附、抗血栓材料等领域具有潜在的应用前景\r. \r但传统两性离子聚合物的可降解性较差，致使其在生物医学领域中的应用受到一定限制\r. \r本文以具有良好生物相容性及生物可降解性的琼脂糖为基本原料，开发了一种琼脂糖和\r3\r-\r[N\r，\rN\r-\r二甲基\r-\r[2\r-\r(\r2\r-\r甲基丙\r-\r2\r-\r烯酰氧基\r)\r乙基\r]\r铵\r]\r丙烷\r-\r1\r-\r磺酸内盐\r(\rSBMA\r)\r的接枝共聚物\r(\ragarose\r-\rg\r-\rPSBMA\r)\r. \r首先，通过琼脂糖与溴\r-\r异丁酰溴\r(\rBIBB\r)\r之间的酰胺化反应合成引发剂\ragarose\r-\rBr\r，探索了\rBIBB\r用量、反应时间等参数对\ragarose\r-\rBr\r取代度的调控作用，结果发现随反应物中\rBIBB\r过量倍数的增加，\ragarose\r-\rBr\r的取代度\r(\rDS\r)\r逐渐增大\r. \r在此基础上，以\ragarose\r-\rBr\r为引发剂，通过\rATRP\r反应，实现了\rSBMA\r在琼脂糖主链上的接枝聚合\r. \r通过调节\rSBMA\r与\ragarose\r-\rBr\r的投料比例，合成了一系列具有不同取代度及支链长度的\ragarose\r-\rg\r-\rPSBMA\r，且实验结果表明支链的聚合度与投料理论值基本保持一致，相对分子质量分布较窄\r(\r1.03\r＜\rPDI\r＜\r1.30\r)\r，接枝聚合的可控性强\r. \r以\r[η]\r为目标参数，详细并系统地研究了\ragarose\r-\rg\r-\rPSBMA\r在不同\rNaCl\r浓度溶液中的反聚电解质行为，发现随\rNaCl\r溶液浓度的增加其\r[\r\rh\r\r]\r也增大，且\ragarose\r-\rg\r-\rPSBMA\r的\r[η]\r符合\rHuggins\r-\rHouwink\r方程的规律，具有明显的反聚电解质行为\r. \r研究结果将为拓宽多糖及两性离子类聚合物结构设计及应用提供新的思路\r.\r\r
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Abstract_English:\r\rBetaine-based polymer is one of the typical zwitterionic polymers\r，\rand its unique anti-polyelectrolyte properties are shown to be potentially applicable in the areas of drug release\r，\ranti-protein adsorption, antithrombotic materials\r，\rand others. However\r，\rthe traditional zwitterionic polymer has poor degradability\r，\rwhich limits its application in the biomedical field. In this study\r，\ran agarose-graft-poly\r(\r3-dimethyl \r(\rmethacryloyloxyethyl\r)\r ammonium propanesulfonate\r) (agarose-g-PDMAPS) (agarose-g-PSBMA) copolymer was synthesized based on agarose with good biocompatibility and biodegradability. First, the macroinitiator of agaorose-Br was synthesized through the reaction of agarose and bromoisobutyryl bromide (BIBB). Substitution degree (DS) of the agarose-Br was adjusted by the feeding ratio of agarose and BIBB. Results suggested that the DS gradually increases with enhanced BIBB excess multiples. A series of copolymers were then synthesized by ATRP using agarose-Br as an initiator and SBMA as a monomer，varying graft degrees and graft lengths. Results suggested that the molecular weight of agarose-g-PSBMA is consistent with the theoretical values of the feed and the molecular weight distribution is narrow (1.03<PDI<1.30)，indicating that the controllability of this graft polymerization is very high. Using intrinsic viscosity [η] as the target parameter，the [η] of agarose-g-PSBMA in NaCl solutions with different concentrations was investigated to evaluate its “anti-polyelectrolyte effect”. Results found that [η] increases along with the concentration of NaCl solution，and [η] of agarose-g-PSBMA conforms to the law of the Huggins-Houwink equation，suggesting that the agarose-g-PSBMA has obvious anti-polyelectrolyte behavior. These results should provide new ideas for broadening the structural design of polysaccharides and zwitterionic polymers and their applications.\r
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Keyword_Chinese:两性离子聚合物；原子转移自由基聚合；琼脂糖；反聚电解质\r

Keywords_English:zwitterionic polymer；atom transfer radical polymerization；agarose；anti-polyelectrolyte\r


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