Monodisperse liquid crystalline peptides

Abstract

Solid phase peptide synthesis (SPPS) has been used as a synthetic tool to prepare monodisperse mesogen–oligopeptide conjugates with novel molecular architectures. Building upon previous success in this area, we have extended our methodologies to include a mesogenically substituted l-glutamic acid residue, and incorporated this derivative, as well as the l-lysine derivative previously reported, into a variety of new structures. Some novel liquid crystalline materials have been discovered. Bothalpha;-helical and beta;-sheet secondary structures have been explored as alternative scaffolds for the pendant mesogenic groups. The helical systems show most promise in terms of their ease of synthesis and handling, but at the relatively lower levels of mesogenic substitution studied so far, compared to the previously reported homo-oligopeptide materials, mesophases are not observed. The beta;-sheet materials prepared are rather insoluble and too high melting to have any practical value as thermotropic materials without further manipulation of their structures.

References

1. V. Percec, M. Lee and C. Ackerman, Polymer, 1992, 33(4), 703.
2. H. Finkelmann, Angew. Chem., Int. Ed. Engl., 1987, 26, 816.
3. V. Percec and D. Tomazos, Adv. Mater., 1992, 4(9), 548.
4. N. Koide, T. Kumada and K. Iimura, Abstr., 14th Symp. Liquid Crystals, Sendai, Sept. 29th, 1988, 164.
5. R. Bohnert, H. Finkelmann and P. Lutz, Makromol. Chem. Rapid Commun., 1993, 14(2), 139.
6. W. Kreuder, O. W. Webster and H. Ringsdorf, Makromol. Chem. Rapid Commun., 1986, 7, 5.
7. M. Hefft and J. Springer, Makromol. Chem. Rapid Commun., 1990, 11(8), 397.
8. Z. Komiya, C. Pugh and R. R. Schrock, Macromolecules, 1986, 25, 6586.
9. C. Pugh, Macromol. Symp., 1994, 77, 325.
10. P. A. G. Cormack, D. C. Sherrington and B. D. Moore, Chem. Commun., 1996, 353.
11. M. A. Gallop, R. W. Barrett, D. J. Dower, S. P. A. Fodor and E. M. Gordon, J. Med. Chem., 1994, 37, 1233.
12. R. M. Baum, Chem. Eng. News, 1994, 20.
13. R. M. J. Liskamp, Angew. Chem., Int. Ed. Engl., 1994, 33, 633.
14. M. Bodanszky, Peptide Chemistry: A Practical Textbook, Springer Verlag, Berlin, 1988.
15. Side Chain Liquid Crystal Polymers, ed. C. B. McArdle, Blackie, Glasgow, New York, 1989.
16. J. L. West, US Patent 5,093,471.
17. H. Guéniffey, R. Garnier and C. Pinazzi, Makromol. Chem., 1977, 178, 1277.
18. V. Percec and M. Lee, Macromolecules, 1991, 24(5), 1017.
19. F. E. King and D. A. A. King, J. Chem. Soc., 1949, 3315.
20. J. Feijen, W. M. Sederel, K. de Groot, A. C. de Visser and A. Bantjes, Makromol. Chem., 1974, 175, 3193.
21. I. Schumann and R. A. Boissonnas, Helv. Chim. Acta, 1952, 35, 2235.
22. W. H. Daly, D. S. Poché and I. I. Negulescu, Prog. Polym. Sci., 1994, 19(1), 79.
23. P. Y. Chou and G. D. Fasman, Annu. Rev. Biochem., 1978, 47, 251.
24. M. Narita, Y. Tomotake, S. Isokawa, T. Matsuzawa and T. Miyauchi, Macromolecules, 1984, 17, 1903.
25. M. Mutter, Angew. Chem., Int. Ed. Engl., 1985, 24, 639.
26. C. Toniolo, G. M. Bonora, E. Benedetti, A. Bavoso, B. D. Blasio, V. Pavone and C. Pedone, Biopolymers, 1983, 22, 1335.
27. A. Bierzynski, P. S. Kim and R. L. Baldwin, Proc. Natl. Acad. Sci. USA, 1982, 79, 2470.
28. I. L. Karle and P. Balaram, Biochemistry, 1990, 29, 6747.
29. K. R. Shoemaker, P. S. Kim, O. N. Brems, S. Marqusee, E. J. York, I. M. Chaiken, J. M. Stewart and R. L. Baldwin, Proc. Natl. Acad. Sci. USA, 1985, 82, 2349.
30. S. Krimm and J. Bandekar, Adv. Protein Chem., 1986, 38, 181.