全亲水无规共聚物P(NIPAM-co-AA)的pH和温度双重刺激响应性水相自组装

doi:10.3866/PKU.WHXB201405092

物理化学学报 >> 2014, Vol. 30 >> Issue (7): 1290-1296.doi: 10.3866/PKU.WHXB201405092

全亲水无规共聚物P(NIPAM-co-AA)的pH和温度双重刺激响应性水相自组装

陈韩婷, 樊晔, 方云

江南大学化学与材料工程学院, 食品胶体与生物技术教育部重点实验室, 江苏无锡 214122

收稿日期:2014-02-14 修回日期:2014-05-09 发布日期:2014-06-30
通讯作者: 方云 E-mail:yunfang@126.com
基金资助:
国家自然科学基金（21276113）资助项目

Dual pH-and Thermo-Responsive Self-Assembly of the P(NIPAM-co-AA) Hydrophilic Random Copolymer in Pure Aqueous Solution

CHEN Han-Ting, FAN Ye, FANG Yun

Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu Province, P. R. China

Received:2014-02-14 Revised:2014-05-09 Published:2014-06-30
Contact: FANG Yun E-mail:yunfang@126.com
Supported by:
The project was supported by the National Natural Science Foundation of China (21276113).

摘要/Abstract

摘要：

从N-异丙基丙烯酰胺（NIPAM）和丙烯酸（AA）单体合成了一种全亲水无规共聚物P（NIPAM-co-AA），实验发现该聚合物在水相中可以产生pH或温度双重刺激响应性自组装. 采用透射电子显微镜（TEM）观察了自组装体的形貌，采用动态光散射（DLS）和静态光散射（SLS）观察了其粒径及粒径分布. 测定了该聚合物水溶液的最低临界溶解温度（LCST）及其zeta 电位随pH的变化，通过分析NIPAM和AA两种链节的质子化状态随温度和pH变化的趋势，阐释了其在水相中产生双重响应性自组装的推动力；并结合傅里叶红外（FT-IR）光谱测定自组装体表面富集基团的结果，进一步阐释了不同环境下自组装体的微结构. 这类全亲水无规共聚物的合成方法简单，具有pH和温度双重响应性，其全水相中的刺激响应性自组装行为在药物释放等方面具有潜在的应用价值.

关键词: 全亲水无规共聚物, N-异丙基丙烯酰胺, 丙烯酸, 刺激响应性, 自组装

Abstract:

The random poly(N-isopropylacrylamide-co-acrylic acid) copolymer (P(NIPAM-co-AA)) was synthesized and its stimuli-responsive self-assembly in pure aqueous solution was investigated. P(NIPAMco-AA) is a dual pH-and thermo-responsive hydrophilic random copolymer because it can self-assemble in pure aqueous solution in response to the stimuli of pH and temperature. The morphologies of P(NIPAM-co-AA) assemblies were imaged by transmission electron microscopy, and the radius (R_h) and radius distribution were determined by dynamic and static light scattering. The lower critical solution temperature (LCST) of P(NIPAM-co-AA) and the zeta potential change of the aqueous solution of P(NIPAM-co-AA) with respect to pH were measured. The driving force for pH-and thermo-responsive self-assembly of P(NIPAMco-AA) was deduced from the protonation degrees of two different chain units based on LCST and zeta potential data. The response of the special microstructure of the assemblies to environmental stimulation was confirmed by combining the above results with Fourier-transform infrared spectroscopy, which can provide information about the enriched chain units on the surface of assemblies. The experimental results showed that the P(NIAPM-co-AA) random copolymer can be easily synthesized and is both pH-and thermoresponsive. The stimuli-responsive self-assembly behavior of P(NIAPM-co-AA) in pure aqueous solution can potentially be applied to drug delivery.

Key words: Hydrophilic random copolymer, N-isopropylacrylamide, Acrylic acid, Stimuli-responsive, Self-assembly

陈韩婷, 樊晔, 方云. 全亲水无规共聚物P(NIPAM-co-AA)的pH和温度双重刺激响应性水相自组装[J]. 物理化学学报, 2014, 30(7): 1290-1296.

CHEN Han-Ting, FAN Ye, FANG Yun. Dual pH-and Thermo-Responsive Self-Assembly of the P(NIPAM-co-AA) Hydrophilic Random Copolymer in Pure Aqueous Solution[J]. Acta Phys. -Chim. Sin., 2014, 30(7): 1290-1296.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201405092

https://www.whxb.pku.edu.cn/CN/Y2014/V30/I7/1290

参考文献

(1) Jiang, M.; Eisenberg, A.; Liu, G. J.; Zhang, X. Macromolecular Self-Assembly; Science Press: Beijing, 2006; pp 137-181. [江明, 艾森伯格, A., 刘国军, 张希. 大分子自组装. 北京: 科学出版社, 2006: 137-181.]
(2) Liu, S. Y.; Billingham, N. C.; Armes, S. P. Angew. Chem. Inter. Edit. 2001, 40 (12), 2328. doi: 10.1002/1521-3773(20010618) 40:12<2328::AID-ANIE2328>3.0.CO; 2-M
(3) Colfen, H. Macromol. Rapid Commun. 2001, 22, 219.
(4) Gil, E. S.; Hudson, S. A. Prog. Polym. Sci. 2004, 29, 1173. doi: 10.1016/j.progpolymsci.2004.08.003
(5) Bütün, V.; Billingham, N. C.; Armes, S. P. J. Am. Chem. Soc. 1998, 120 (45), 11818. doi: 10.1021/ja982295a
(6) Rodríguez-Hernández, J.; Lecommandoux, S. J. Am. Chem. Soc. 2005, 127 (7), 2026. doi: 10.1021/ja043920g
(7) Chang, C.;Wie, H.; Feng, J.;Wang, Z. C.;Wu, X. J.;Wu, D. Q.; Cheng, S. X.; Zhang, X. Z.; Zhuo, R. X. Macromolecules 2009, 42 (13), 4838. doi: 10.1021/ma900492v
(8) Smith, A. E.; Xu, X.; Kirkland-York, S. E.; Aavin, D. A.; McCormik, C. L. Macromolecules 2010, 43 (3), 1210. doi: 10.1021/ma902378k
(9) Shih, Y. J.; Chang, Y.; Deratani, A.; Quemener, D. Biomacromolecules 2012, 13 (9), 2849. doi: 10.1021/bm3008764
(10) Wang, A.; Gao, H.; Sun, Y. F.; Sun, Y. L.; Yang, Y.W.;Wu, G. L.;Wang, Y. N.; Fan, Y.; Ma, J. B. Int. J. Pharmaceut. 2013, 441, 30. doi: 10.1016/j.ijpharm.2012.12.021
(11) Bian, J.; Zhang, M. Z.; He, J. L.; Ni, P. H. React. Funct. Polym. 2013, 73, 579. doi: 10.1016/j.reactfunctpolym.2012.12.010
(12) Joshi, R. V.; Nelson, C. E.; Poole, K. M.; Skala, M. C.; Duvall, C. L. Acta Biomater. 2013, 9, 6526. doi: 10.1016/j.actbio.2013.01.041
(13) Ganta, S.; Devalapally, H.; Shahiwala, A.; Amiji, M. J. Control. Release. 2008, 126, 187. doi: 10.1016/j.jconrel.2007.12.017
(14) Calejo, M. T.; Cardoso, A. M. S.; Kjøniksen, A. L.; Zhu, K. Z.; Morais, C. M.; Sande, S. A.; Caedoso, A. L.; Lima, P. D.; Jurado, A.; Nyström, B. Int. J. Pharmaceut. 2013, 448, 105. doi: 10.1016/j.ijpharm.2013.03.028
(15) Bronstein, L. M.; Sidorov, S. N.; Gourkova, A. Y.; Valetsky, P. M.; Hartmann, J.; Breulmann, M.; Cölfen, H.; Antonietti, M. Inorg. Chim. Acta 1998, 280, 348. doi: 10.1016/S0020-1693(98) 00208-4
(16) Li, L. Y.; He,W. D.; Li,W. T.; Zhang, K. R.; Pan, T. T.; Ding, Z. L.; Zhang, B. Y. J. Polym. Sci. Pol. Chem. 2010, 48, 5018. doi: 10.1002/pola.v48:22
(17) Mitsukami, Y.; Donovan, M. S.; Lowe, A. B.; McCormik, C. L. Macromolecules 2001, 34 (7), 2248. doi: 10.1021/ma0018087
(18) Patrickios, C. S.; Lowe, A. B.; Armes, S. P.; Billinghan, N. C. J. Polym. Sci. Pol. Chem. 1998, 36 (4), 617.
(19) Quek, J. Y.; Zhu, Y.; Roth, P. J.; Davis, T. P.; Lowe, A. B. Macromolecules 2013, 46 (18), 7290. doi: 10.1021/ma4013187
(20) Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; San, H. T. Macromolecules 1998, 31 (16), 5559.
(21) Lowe, A. B.; McCormick, C. L. Prog. Polym. Sci. 2007, 32 (3), 283. doi: 10.1016/j.progpolymsci.2006.11.003
(22) Yang, P.; Ratcliffe, L. P. D.; Armes, S. P. Macromolecules 2013, 46, 8545. doi: 10.1021/ma401797a
(23) Tao, Y. H.; Yang, Y. Q.; Shi, D. J.; Chen, M. Q.; Yang, C.; Liu, X. Y. Polymer 2012, 53, 1551. doi: 10.1016/j. polymer.2012.02.001
(24) Tian, F.; Yu, Y. Y.;Wang, C. C.; Yang, S. Macromolecules 2008, 41 (10), 3385. doi: 10.1021/ma800142j
(25) Liu, X. Y.; Kim, J.;Wu, J.; Eisenberg, A. Macromolecules 2005, 38 (16), 6749. doi: 10.1021/ma050665r
(26) Liu, X. Y.;Wu, J.; Kim, J.; Eisenberg, A. Langmuir 2006, 22 (1), 419. doi: 10.1021/la0519610
(27) Li, N.; Li, Y. B.;Wang, X. G. Polymer 2012, 53, 3975. doi: 10.1016/j.polymer.2012.07.001
(28) Li, N.;Wang, X. Acta Polym. Sin. 2013, No. 4, 549.
(29) Wang, Y.;Wang, Y.;Wu, G. L.; Fan, Y. G.; Ma, J. B. Colloids and Surfaces B 2009, 68 (1), 13. doi: 10.1016/j.colsurfb.2008.08.026
(30) Fang, Y.; Pang, P. P.; Lai, Z. Y. Chem. Lett. 2011, 40 (10), 1074. doi: 10.1246/cl.2011.1074
(31) Fang, Y.; Lai, Z. Y.; Pang, P. P.; Jiang, M. Acta Physico-Chimica Sinica 2011, 27 (7), 1712. [方云, 赖中宇, 庞萍萍, 江明. 物理化学学报, 2011, 27 (7), 1712.]
(32) Qian, J.;Wu, F. J. Mater. Chem. B 2013, 1 (28), 3464. doi: 10.1039/c3tb20527d
(33) Zhang, X.; Yang, P.; Dai, Y. Adv. Funct. Mater. 2013, 23 (33), 4067. doi: 10.1002/adfm.v23.33
(34) Li, C.; Alam, M. M.; Bolisetty, S. Chem. Commun. 2011, 47 (10), 2913. doi: 10.1039/c0cc05126h
(35) Zhang, Q.; Ye, J.; Liu, Y.; Nie, T.; Xue, D.; Song, Q.; Chen, H.; Zhang, G.; Tang, Y.;Wu, C.; Xie, Z. Macromolecules 2008, 41, 2228. doi: 10.1021/ma702139b
(36) Liu, T.; Zhao, Z.;Wu, C.; Chu, B.; Schneider, D. K.; Nace, V. M. J. Phys. Chem. B 1997, 101, 8808. doi: 10.1021/jp963810zh

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全亲水无规共聚物P(NIPAM-co-AA)的pH和温度双重刺激响应性水相自组装

Dual pH-and Thermo-Responsive Self-Assembly of the P(NIPAM-co-AA) Hydrophilic Random Copolymer in Pure Aqueous Solution

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