新型两亲性含糖嵌段聚合物的合成与自组装

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (8): 1676.

新型两亲性含糖嵌段聚合物的合成与自组装

陈丽琼^1,2, 张黎明¹, 陈建军², 杨建², 李荣先²

1. 中山大学化学与化学工程学院, 新型聚合物材料设计合成与应用广东省高校重点实验室, 广州 510275;
2. 深圳清华大学研究院, 深圳 518057

收稿日期:2010-10-14 出版日期:2010-08-10 发布日期:2010-08-10
通讯作者: 张黎明, 男, 博士, 教授, 博士生导师, 主要从事天然大分子改性及其功能化、医用高分子与纳米生物技术等方面的研究. E-mail: ceszhlm@mail.sysu.edu.cn
基金资助:
国家自然科学基金(批准号: 20676155, 20874116) 和广东省自然科学基金(批准号: 8151027501000004)资助.

Synthesis and Self-assembly Behavior of a Novel Amphiphilic Block Glycopolymer

CHEN Li-Qiong^1,2, ZHANG Li-Ming^1*, CHEN Jian-Jun², YANG Jian², LI Rong-Xian²

1. Key Laboratory for Designed Synthesis and Application of Polymer Materials, School of Chemistry and Chemical Engineering, Sun Yat-Sen(Zhongshan) University, Guangzhou 510275, China;
2. Research Institute of Tsinghua University in Shenzhen, Shenzhen 518057, China

Received:2010-10-14 Online:2010-08-10 Published:2010-08-10
Contact: ZHANG Li-Ming. E-mail: ceszhlm@mail.sysu.edu.cn
Supported by:
国家自然科学基金(批准号: 20676155, 20874116) 和广东省自然科学基金(批准号: 8151027501000004)资助.

摘要/Abstract

摘要： 以β-环糊精(β-CD)和2-乙基-2-噁唑啉(EtOz)为原料, 通过活性端基化学偶联法制备了乙酰麦芽七糖/聚(2-乙基-2-噁唑啉)两嵌段聚合物(AcMH-b-PEtOz), 借助核磁共振氢谱、红外光谱和凝胶渗透色谱等手段证实了产物的化学结构. 采用核磁共振氢谱、荧光光谱、透射电子显微镜、动态光散射及紫外-可见分光光度等方法探讨了产物在水溶液中的自组装行为. 结果表明, 所得嵌段聚合物直接溶于水后可通过自组装形成纳米球形“核-壳”结构胶束, 同时具有温度响应性. 所得聚合物的临界胶束浓度(cmc)为4~7 mg/L, 平均粒径(d)为83~115 nm, 临界相转变温度(LCST)为49~64 ℃, 并且均可通过PEtOz的链长进行调控.

关键词: 两亲性嵌段聚合物, 含糖聚合物, 聚(2-乙基-2-噁唑啉), 自组装, 温度敏感

Abstract: A novel amphiphilic block polymers based on peracetylated maltoheptaose and poly(2-ethyl-2-oxazoline)(AcMH-b-PEtOz) was synthesized by endcapping reaction. Their structures were confirmed by the combined analyses from hydrogen nuclear magnetic resonance(¹H NMR), gel permeation chromatograph(GPC) and Fourier transform infrared spectrometry(FTIR). Their micellar formation and characteristics in an aqueous phase were investigated by means of ¹H NMR, fluorescence spectrum, transmission electron microscopy(TEM), dynamic light scattering(DLS) and UV-Visible spectrum. It was found that the obtained block polymers could self-assemble into nanosize spherical micelles with a core-shell structure in aqueous solution triggered by its amphiphilic character without any organic solvent and exhibited thermal sensitivity. The critical micelle concentration(cmc) of the micelles ranged from 4 to 7 mg/L with mean diameters in the range of 83—115 nm and lower critical solution temperatures(LCST) in the range of 49—64 ℃. The cmc, size and thermal sensitivity of the self-assembled micelles could be tailored by changing the PEtOz content of the resultant block polymer.

Key words: Amphiphilic block copolymer, Glycopolymer, Poly(2-ethyl-2-oxazoline), Self-assembly, Thermo-sensitive

TrendMD:

陈丽琼, 张黎明, 陈建军, 杨建, 李荣先. 新型两亲性含糖嵌段聚合物的合成与自组装. 高等学校化学学报, 2010, 31(8): 1676.

CHEN Li-Qiong, ZHANG Li-Ming*, CHEN Jian-Jun, YANG Jian, LI Rong-Xian. Synthesis and Self-assembly Behavior of a Novel Amphiphilic Block Glycopolymer. Chem. J. Chinese Universities, 2010, 31(8): 1676.

参考文献

[1]Yasugi K., Nakamura T., Nagasaki Y., Kato M., Kataoka K.. Macromolecules[J], 1999, 32: 8024—8032 [2]LIANG Yu-Zeng(梁玉增), LI Zi-Chen(李子臣), LI Fu-Mian(李福绵). Chem. J. Chinese Universities(高等学校化学学报)[J], 1999, 20(11): 1820—1822 [3]Li Z. C., Liang Y. Z., Chen G. Q., Li F. M.. Macromol. Rapid Commun.[J], 2000, 21: 375—380 [4]Ohno K., Izu Y., Yamamoto S., Miyamoto T., Fukuda T.. Macromol. Chem. Phys.[J], 1999, 200: 1619—1625 [5]Nagasaki Y., Yasugi K., Yamamoto Y., Harada A., Kataoka K.. Biomacromolecules[J], 2001, 2: 1067—1070 [6]WANG Yun-Yun(王芸芸), FAN Qu-Li(范曲立), WANG Pei(王培), MA Zhun(马谆), WANG Lian-Hui(汪联辉), HUANG Wei(黄维). Chem. J. Chinese Universities(高等学校化学学报)[J], 2007, 28(7): 1377—1382 [7]Rieger J., Stoffelbach F., Cui D., Imberty A., Lameignere E., Putaux J. L., Jerome R., Auzely-Velty R.. Biomacromolecules[J], 2007, 8: 2717—2725 [8]Rieger J., Freichels H., Imberty A., Putaux J. L., Delair T., Jerome C., Auzely-Velty R.. Biomacromolecules[J], 2009, 10: 651—657 [9]Jule E., Nagasaki Y., Kataoka K.. Bioconjugate Chem.[J], 2003, 14: 177—186 [10]XIONG Xiang-Yuan(熊向源), LI Zi-Chen(李子臣), DU Fu-Sheng(杜福胜), LI Fu-Mian(李福绵). Acta Polymerica Sinica(高分子学报)[J], 2001, 6: 787—792 [11]Haddleton D. M., Ohno K.. Biomacromolecules[J], 2000, 1: 152—156 [12]Li B. G., Zhang L. M.. Carbohydr. Polym.[J], 2008, 74: 390—395 [13]Kamitakahara H., Nakatsubo F.. Cellulose[J], 2005, 12: 209—219 [14]Kamitakahara H., Nakatsubo F.. Cellulose[J], 2005, 12: 527—541 [15]Bosker W. T. E., Agoston K., Cohen Stuart M. A., Norde W., Timmermans J. W., Slaghek T. M.. Macromolecules[J], 2003, 36: 1982—1987 [16]Zhu J., Gosen C., Marchant R. E.. J. Polym. Sci., Part A: Polym. Chem.[J], 2006, 44: 192—199 [17]Hernandez O. S., Soliman G. M., Winnik F. M.. Polymer[J], 2007, 48: 921—930 [18]Liu J. Y., Zhang L. M.. Carbohydr. Polym.[J], 2007, 69: 196—201 [19]Bernard J., Save M., Arathoon B., Charleux B.. J. Polym. Sci., Part A: Polym. Chem.[J], 2008, 46: 2845—2857 [20]Loos K., Stadler R.. Macromolecules[J], 1997, 30: 7641—7643 [21]Loos K., Muller A. H. E.. Biomacromolecules[J], 2002, 3: 368—373 [22]Akiyoshi K., Kohara1 M., Ito K., Kitamura S., Sunamota J.. Macromol. Rapid Commun.[J], 1999, 20: 112—115 [23]Yang Y., Kataoka K., Winnik F. M.. Macromolecules[J], 2005, 38: 2043—2046 [24]Wang C. H., Fan K. R., Hsiue G. H.. Biomaterials[J], 2005, 26: 2803—2811 [25]Hsiue G. H., Wang C. H., Lo C. L., Hsiue G. H., Wang C. H., Lo C. L., Wang C. H., Li J. P., Yang J. L.. Int. J. Pharm.[J], 2006, 317: 69—75 [26]Kim C., Lee S. C., Kang S. W., Kwon I. C., Jeong S. Y.. J. Polym. Sci., Part B: Polym. Phys.[J], 2000, 38: 2400—2408 [27]Lee S. C., Kang S. W., Kim C., Kwon I. C., Jeong S. Y.. Polymer[J], 2000, 41: 7091—7097 [28]Wang C. H., Hsiue G. H.. Biomacromolecules[J], 2003, 4: 1487—1490 [29]Becer C. R., Paulus R. M., Hppener S., Hoogenboom R., Fustin C. A., Gohy J. F. O., Schubert U. S.. Macromolecules[J], 2008, 41: 5210—5215 [30]Heald C. R., Stolnik S., Kujawinski K. S., Matteis C. De, Garnett M. C., Illum L., Davis S. S., Purkiss S. C., Barlow R. J., Gellert P. R.. Langmuir[J], 2002, 18: 3669—3675 [31]Lee S. C., Kim C., Kwon I. C., Chung H., Jeong S. Y.. J. Controlled Release[J], 2003, 89: 437—446 [32]Lee S. C., Chang Y., Yoon J. S., Kim C. H., Kwon I. C., Kim Y. H., Jeong S. Y.. Macromolecules[J], 1999, 32: 1847—1852 [33]Weberm C., Becer C. R., Hoogenboom R., Weber C., Becer C. R., Hoogenboom R., Schubertt U. S.. Macromolecules[J], 2009, 42: 2965—2971