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Synthesis of pH-Sensitive Amphiphilic Copolymer Brush by the Combination of ARGET ATRP with ROP and Its Self-Assembly Behavior

  • Yang Youqiang ,
  • Sun Qingqing ,
  • Zhang Canyang ,
  • Guo Xindong ,
  • Zhang Lijuan ,
  • Wen Xiufang
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  • School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640

Received date: 2011-08-30

  Revised date: 2011-10-30

  Online published: 2011-11-09

Supported by

Project supported by the National Natural Science Foundation of China (No. 21176090), Team Project of Natural Science Foundation of Guangdong Province (No. S2011030001366), Guangdong Province Science Foundation (No. 9251064101000009), Guangzhou Municipal Bureau of Science and Technology (No. 2009J1-C511-2) and the Fundamental Research Funds for the Central Universities (No. 2011ZM0041).

Abstract

A random hydrophobic/pH-sensitive copolymer brush poly(polylactide methacrylate-comethacrylic acid)-b-poly(poly(ethylene glycol) methyl ether methacrylate) [P(PLAMA-co-MAA)-b-PPEGMA] was synthesized by the combination of activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) with ring opening polymerization (ROP). The chemical structure, molecular weight and polydispersity index were characterized by nuclear magnetic resonance hydrogen spectrum (1H NMR) and gel permeation chromatography (GPC). The reaction conditions of polymerization were optimized and polymer products with controllable molecular weight and narrow distribution were obtained. The self-assembly behavior (micelle size, morphology and pH-sensitive properties) of the polymer brush was investigated by dynamic light scattering (DLS) and scanning electron microscopy (SEM). The P(PLAMA-co-MAA)-b-PPEGMA self-assembled micelles were sphere in morphology and with an uniform particle size. As the solution pH decreased from 7 to 3, the deionization of carboxyl groups of PMAA contributed to the shrinking of micelle structure, which made the micelle size decreased from 200~300 nm to about 150 nm. When the solution pH decreased to below 2, the surface charge of micelle became very small which resulting in the aggregation of micelles and the increase of micelle size.

Cite this article

Yang Youqiang , Sun Qingqing , Zhang Canyang , Guo Xindong , Zhang Lijuan , Wen Xiufang . Synthesis of pH-Sensitive Amphiphilic Copolymer Brush by the Combination of ARGET ATRP with ROP and Its Self-Assembly Behavior[J]. Acta Chimica Sinica, 2012 , 70(04) : 505 -511 . DOI: 10.6023/A1108302

References

1 Torchilin, V. P. Cell. Mol. Life Sci. 2004, 61, 2549.  

2 Bromberg, L. J. Controlled Release 2008, 128, 99.  

3 Gaucher, G.; Dufresne, M. H.; Sant, V. P.; Kang, N.; Maysinger, D.; Leroux, J. C. J. Controlled Release 2005, 109, 169.  

4 Zhou, Z. Y.; D'Emanuele, A.; Lennon, K.; Attwood, D. Macromolecules 2009, 42, 7936.  

5 Tyrrell, Z. L.; Shen, Y. Q.; Radosz, M. Prog. Polym. Sci. 2010, 35, 1128.  

6 Xu, J. X.; Tang, J. B.; Zhao, L. H.; Shen, Y. Q. Acta Pharmacol. Sin. 2009, 44, 1328 (in Chinese). (许金霞, 唐建斌, 赵鲁杭, 申有青, 药学学报, 2009, 44, 1328.)

7 Kim, S.; Kim, J. Y.; Huh, K. M.; Acharya, G.; Park, K. J. Controlled Release 2008, 132, 222.  

8 Lee, E. S.; Gao, Z. G.; Kim, D.; Park, K.; Kwon, I. C.; Bae, Y. H. J. Controlled Release 2008, 129, 228.  

9 Zhang, L.; Li, W.; Zhang, A. F. Prog. Chem. 2006, 18, 939 (in Chinese). (张磊, 李文, 张阿方, 化学进展, 2006, 18, 939.)

10 Lee, H. I.; Pietrasik, J.; Sheiko, S. S.; Matyjaszewski, K. Prog. Polym. Sci. 2010, 35, 24.  

11 Shen, Y. Q.; Zhan, Y. H.; Tang, J. B.; Xu, P. S.; Johnson, P. A.; Radosz, M.; Van Kirk, E. A.; Murdoch, W. J. AIChE J. 2008, 54, 2979.

12 Xie, M. R.; Dang, J. Y.; Shi, J. X.; Han, H. J.; Song, C. M.; Huang, W.; Zhang, Y. Q. Acta Chim. Sinica 2009, 67, 869 (in Chinese). (谢美然, 党靖雅, 史佳鑫, 韩会景, 宋春梅, 黄炜, 张以 群, 化学学报, 2009, 67, 869.)

13 Yang, Y. Q.; Zheng, L. S.; Guo, X. D.; Qian, Y.; Zhang, L. J. Biomacromolecules 2010, 12, 116.

14 Xu, F. J.; Neoh, K. G.; Kang, E. T. Prog. Polym. Sci. 2009, 34, 719.  

15 Matyjaszewski, K.; Tsarevsky, N. V. Nat. Chem. 2009, 1, 276.  

16 Mori, H.; Muller, A. H. E. Prog. Polym. Sci. 2003, 28, 1403.  

17 Mori, H.; Seng, D. C.; Lechner, H.; Zhang, M. F.; Muller, A. H. E. Macromolecules 2002, 35, 9270.  

18 Jakubowski, W.; Kirci-Denizli, B.; Gil, R. R.; Matyjaszewski, K. Macromol. Chem. Phys. 2008, 209, 32.  

19 Jakubowski, W.; Min, K.; Matyjaszewski, K. Macromolecules 2006, 39, 39.  

20 Jakubowski, W.; Matyjaszewski, K. Angew. Chem., Int. Ed. 2006, 45, 4482.  

21 Ring, J. O.; Thomann, R.; Mulhaupt, R.; Raquez, J. M.; Degee, P.; Dubois, P. Macromol. Chem. Phys. 2007, 208, 896.  

22 Nouvel, C.; Dubois, P.; Dellacherie, E.; Six, J. L. J. Polym. Sci. Part A: Polym. Chem. 2004, 42, 2577.  

23 Li, Z.; Day, M.; Ding, J. F.; Faid, K. Macromolecules 2005, 38, 2620.  

24 Sun, G. X.; Zhang, M. Z.; Xu, Y.; Lu, Y. M.; Ni, P. H. Acta Chim. Sinica 2009, 67, 1685 (in Chinese). (孙桂香, 张明祖, 许杨, 陆一鸣, 倪沛红, 化学学报, 2009, 67, 1685.)

25 Zhong, L.; He, X. H.; Zhou, Y. F.; Yan, D. Y.; Pan, C. Y. Acta Polym. Sin. 2007, (10), 986 (in Chinese). (钟玲, 贺小华, 周永丰, 颜德岳, 潘才元, 高分子学报, 2007, (10), 986.)
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