Fluorinated functional materials possessing biological activities: gel formation of novel fluoroalkylated end-capped 2-acrylamido-2-methylpropanesulfonic acid polymers under non-crosslinked conditions

Abstract

New fluoroalkylated end-capped 2-acrylamido-2-methylpropanesulfonic acid homopolymers were prepared by reaction of fluoroalkanoyl peroxides with 2-acrylamido-2-methylpropanesulfonic acid (AMPS). Similarly, fluoroalkylated end-capped copolymers were prepared by reaction of fluoroalkanoyl peroxides with AMPS and the comonomers such as trimethylvinylsilane and methyl methacrylate. These thus-obtained fluoroalkylated end-capped AMPS polymers were found to form gels not only in water but also in organic polar solvents such as methanol, ethanol,N,N-dimethylformamide and dimethyl sulfoxide under non-crosslinked conditions. On the other hand, AMPS polymer containing fluoroalkylene units {[-R_F-(AMPS)_q]_p-} could cause no gelation under similar conditions. This suggests that fluoroalkylated end-capped AMPS polymers can cause gelation where strong aggregation of the end-capped fluoroalkyl segments is involved sterically in establishing the physical gel network in these media. Interestingly, these fluoroalkylated end-capped AMPS polymer hydrogels had a strong metal ion binding power. Moreover, it was demonstrated that these fluoroalkylated gelling polymers are potent and selective inhibitors of HIV-1 replication in cell culture. In addition, one of these gelling polymers was found to possess antibacterial activity againstStaphylococcus aureus. Therefore, these fluorinated gelling polymers are suggested to have high potential for new functional materials through their gelling ability and biological activity.

References

1. (a) L. A. Wall, Fluoropolymer, Wiley, New York, 1972, Vol. XXV; (b) P. R. Resnick, Polym. Prepr. (Am. Chem. Soc. Div. Polym. Chem.), 1990, 31, 312; (c) N. Nakamura, T. Kawasaki, M. Unoki, K. Oharu, N. Sugiyama, I. Kaneko and G. Kojima, Preprints of the First Pacific Polymer Conference, Am. Chem. Soc. Div. Polym. Chem., Maui, HI, Dec. 1989; American Chemical Society, Washington, DC, 1989, p. 369; (d) Z.-Y. Yang, A. E. Feiring and B. E. Smart, J. Am. Chem. Soc., 1994, 116, 4135.
2. (a) H. Sawada, N. Itoh, T. Kawase, M. Mitani, H. Nakajima, M. Nishida and Y. Moriya, Langmuir, 1994, 10, 994; (b) H. Sawada, K. Tanba, N. Itoh, C. Hosoi, M. Oue, M. Baba, T. Kawase, M. Mitani and H. Nakajima, J. Fluorine Chem., 1996, 77, 51.
3. H. Sawada, S. Katayama, M. Oue, T. Kawase, Y. Hayakawa, M. Baba, T. Tomita and M. Mitani, J. Jpn. Oil Chem. Soc., 1996, 45, 161.
4. H. Sawada, H. A. Ohashi, A. M. Baba, T. Kawase and Y. Hayakawa, J. Fluorine Chem., 1996, 79, 149.
5. J. F. Elman, B. D. Johs, T. E. Long and J. T. Koberstein, Macromolecules, 1994, 27, 5341.
6. S. Affrossman, M. Hartshorne, T. Kiff, R. A. Pethrick and R. W. Richards, Macromolecules, 1994, 27, 1588.
7. M. O. Hunt, Jr., A. M. Belu, R. W. Linton and J. M. DeSimone, Macromolecules, 1993, 26, 4854.
8. S. Affrossman, P. Bertrand, M. Hartshorne, T. Kiff, D. Leonard, R. A. Pethrick and R. W. Richards, Macromolecules, 1996, 29, 5432.
9. B. Xu, L. Li, A. Yekta, Z. Masoumi, S. Kanagalingam, M. A. Winnik, K. Zhang, P. M. Macdonald and S. Menchen, Langmuir, 1997, 13, 2447.
10. J. Wang, G. Mao, C. K. Ober and E. J. Kramer, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1997, 38, 953.
11. Z. Su, D. Wu, S. L. Hsu and T. J. McCarthy, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 1997, 38, 951.
12. A. Laschewsky and I. Zerbe, Polymer, 1991, 32, 2070.
13. H. Sawada, S. Katayama, Y. Nakamura, T. Kawase and Y. Hayakawa, Polymer, 1998, 39, 743.
14. (a) H. Sawada, Y.-F. Gong, Y. Minoshima, T. Matsumoto, M. Nakayama, M. Kosugi and T. Migita, J. Chem. Soc., Chem. Commun., 1992, 537; (b) H. Sawada, Y. Minoshima and Y. Nakajima, J. Fluorine Chem., 1992, 65, 169.
15. (a) K. Hanabusa, R. Tanaka, M. Suzuki, M. Kimura and H. Shirai, Adv. Mater., 1997, 9, 1095; (b) K. Hanabusa, K. Okui, K. Karaki, M. Kimura and H. Shirai, J. Colloid Interface Sci., 1997, 195, 86.
16. K. Hanabusa, Y. Naka, T. Koyama and H. Shirai, J. Chem. Soc., Chem. Commun., 1994, 2683.
17. Y. Osada and M. Takase, Nippon Kagaku Kaishi, 1983, 439.
18. T. Kunitake, Y. Okahata and S. Yasunami, J. Am. Chem. Soc., 1987, 104, 5547.
19. T. Kunitake and N. Higashi, J. Am. Chem. Soc., 1985, 107, 692.
20. T. Kunitake and N. Higashi, Macromol. Chem. Phys. Suppl., 1985, No. 14, 81.
21. Y. Ishikawa, K. Kuwahara and T. Kunitake, Chem. Lett., 1989, 1737.
22. Y. Ishikawa, H. Kuwahara and T. Kunitake, J. Am. Chem. Soc., 1989, 111, 8530.
23. R. J. Twieg, T. P. Russell, R. Siemens and J. F. Rabolt, Macromolecules, 1985, 18, 1361.
24. H. Sawada, E. Sumino, M. Oue, M. Mitani, H. Nakajima, M. Nishida and Y. Moriya, J. Chem. Soc., Chem. Commun., 1994, 143.
25. H. Sawada, E. Sumino, M. Oue, M. Baba, T. Kira, S. Shigeta, M. Mitani, H. Nakajima, M. Nishida and Y. Moriya, J. Fluorine Chem., 1995, 74, 21.
26. M. Baba, R. Pauwels, J. Balzarini, J. Arnout, J. Desmyter and E. De Clercq, Proc. Natl. Acad. Sci. USA, 1988, 85, 6132.
27. M. Baba, T. Kira, S. Shigeta, T. Matsumoto and H. Sawada, J. Acquir. Immun. Defic. Syndr., 1994, 7, 24.
28. H. Sawada, A. Ohashi, M. Oue, M. Baba, M. Abe, M. Mitani and H. Nakajima, J. Fluorine Chem., 1995, 75, 121.
29. H. Sawada, K. Yamamoto, M. Oue, T. Kawase, Y. Hayakawa, M. Baba and M. Mitani, J. Jpn. Oil Chem. Soc., 1996, 45, 37.
30. H. Sawada, A. Wake, T. Maekawa, T. Kawase, Y. Hayakawa, T. Tomita and M. Baba, J. Fluorine Chem., 1997, 83, 125.
31. H. Sawada, K. Tanba, T. Tomita, T. Kawase, M. Baba and T. Ide, J. Fluorine Chem., 1997, 84, 141.
32. (a) H. Sawada and M. Nakayama, J. Fluorine Chem., 1990, 51, 117; (b) H. Sawada, M. Yoshida, H. Hagii, K. Aoshima and M. Kobayashi, Bull. Chem. Soc. Jpn., 1986, 59, 215.