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Self-Assembled α-Helical Polypeptide Films

Published online by Cambridge University Press:  21 February 2011

Erwin P. Enriquez  and
Edward T. Samulski
Erwin P. Enriquez
Affiliation:
Department of Chemistry, University of North Carolina, Chapel Hill, NC 27599-3290
Edward T. Samulski
Affiliation:
Department of Chemistry, University of North Carolina, Chapel Hill, NC 27599-3290
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Abstract

Poly(γ-benzyl-L-glutamate) (PBLG) derivatized at its N-terminus with lipoic acid, a disulfide-containing moiety, self-assembles on gold from helicogenic solvents to give a thin film with the polypeptide α-helices orientation distribution different from the planar orientation in the unlabeled, physisorbed PBLG films (control) and Langmuir-Blodgett monolayers. The SA films were studied by angle-dependent XPS, reflection-absorption FTIR spectroscopy, and ellipsometry. The IR dichroic properties of the amide I and amide II bands were used to infer the orientational distribution of the helices in the self-assembled film and lead to two extreme pictures of the helix axis distribution function: (a) random (hemispherical distribution) and (b) perfect order with a tilt of 53° from the surface normal. Additional characterization is necessary to differentiate between these two distributions.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 255: Symposium Z – Hierarchically Structured Materials , 1991 , 423
Copyright
Copyright © Materials Research Society 1992

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References

1. Ulman, A., An Introduction to Ultrathin Organic Films: From Langmuir- Blodgett to Self-assembly (Academic Press, New York, 1991); and references cited therein.Google Scholar
2. Swalen, J. D., Allara, D. L., Andrade, J. D., Chandross, E. A., Garoff, S., Israelachvili, J., McCarthy, T. J., Murray, R., Pease, R. F., Rabolt, J. F., Wynne, K. J., and Yu, H., Langmuir 3, 932 (1987); J. D. Swalen, Annu. Rev. Mater. Sci. 21, 373 (1991).Google Scholar
3. See for example, Thompson, N. L. and Palmer, A. G. III, Comments Mol. Cell. Biophys. 5, 39 (1988).Google Scholar
4. Bain, C. D., Troughton, E. B., Tao, Y., Evall, J., Whitesides, G. M., and Nuzzo, R. G., J. Am. Chem. Soc. 111, 321 (1989); C. D. Bain, H. A. Biebuyck, and G. M. Whitesides, Langmuir 5, 723 (1989).Google Scholar
5. Sagiv, J., J. Am. Chem. Soc. 102, 92 (1980).Google Scholar
6. Wasserman, S. R., Tao, Y., and Whitesides, G. M., Langmuir 5, 1074 (1989).Google Scholar
7. Allara, D. L. and Nuzzo, R. G., Langmuir 1, 45 (1985); Langmuir., 1, 52 (1985).CrossRefGoogle Scholar
8. Allara, D. L. and Swalen, J. D., J. Phys. Chem. 86, 2700 (1982).Google Scholar
9. Merrifield, B., Science 232, 341 (1986).Google Scholar
10. See for example, Inai, Y., Sisido, M., and Imanishi, Y., J. Phys. Chem. 95, 3847 (1991).CrossRefGoogle Scholar
11. Wada, A., Adv. Biophys. 9, 1 (1976).Google Scholar
12. Block, H., Poly(γ-Benzyl-L-Glutamate) and Other Glutamic Acid Containing Polymers (Gordon and Breach, New York, 1983); and references cited therein.Google Scholar
13. Tsuji, K., Ohe, H., and Watanabe, H., Polymer J. 4, 553 (1973).Google Scholar
14. McMaster, T. J., Carr, H. J., Miles, M. J., Cairns, P., and Morris, V. J., Macromolecules 24, 1428 (1991); J. Vac. Sci. Technol. A 8, 648 (1990).Google Scholar
15. Fabianowski, W., Coyle, L. C., Weber, B. A., Granata, R. D., Castner, D. G., Sadownik, A., and Regen, S. L., Langmuir 5, 35 (1989).Google Scholar
16. The average length of the polypeptide used was ∼ 120 Å (1.5 Å / repeating unit times the degree of polymerization = 80). The degree of polymerization data were from Sigma Chemical Co. provided with the PBLG sample purchased (20 kd, lot # 89F5536; Mvis = 20,100; Mw = 15,600).Google Scholar
17. Enriquez, E. P., Gray, K. H., Guarisco, V. F., Linton, R. W., Mar, K. D., and Samulski, E. T., presented at the American Vacuum Society 38th National Symposium, Seattle, WA, 1991 (J. Vac. Sci. Technol. A, in press).Google Scholar
18. Greenler, R. G., J. Chem. Phys. 44, 310 (1966).Google Scholar
19. Swalen, J. D. and Rabolt, J. F. in Fourier Transform Infrared Spectroscopy: Applications to Chemical Systems, vol.4, edited by Ferraro, J. R. and Basile, L. J. (Academic Press, New York, 1985), chap. 7.Google Scholar
20. Allara, D. L., Baca, A., and Pryde, C. A., Macromolecules 11, 1215 (1978).Google Scholar
21. Ishino, Y. and Ishida, H., Langmuir 4, 1341 (1988).Google Scholar
22. Hsu, S. L. in Comprehensive Polymer Science, vol 1., edited by Allen, G. and Bevington, J. C. (Pergamon Press, New York, 1989), pp. 459–461.Google Scholar
23. Tsuboi, M., J. Polymer Sci. 59, 139 (1962).CrossRefGoogle Scholar
24. Takenaka, T., Harada, K., and Matsumoto, M., J. Colloid & Interface Sci. 73, 569 (1980).Google Scholar
25. Michl, J. and Thulstrup, E. W., Spectroscopy with Polarized Light: Solute Alignment by Photoselection, in Liquid Crystals, Polymers, and Membranes (VCH Publishers, Deerfield Beach, FL, 1986), chap. 4.Google Scholar
26. Jones, R. and Tredgold, R. H., J. Phys. D: Appl. Phys. 21, 449 (1988).Google Scholar
27. The value that can be calculated from direct transmission spectrum (K > 2), say, of an isotropic PBLG film is different due to the optical effects inherent in the reflection technique (see text).+2),+say,+of+an+isotropic+PBLG+film+is+different+due+to+the+optical+effects+inherent+in+the+reflection+technique+(see+text).>Google Scholar
28. Hickel, W., Duda, G., Jurich, M., Kröhl, T., Rochford, K., Stegeman, G. I., Swalen, J. D., Wegner, G., and Knoll, W., Langmuir 6, 1403 (1990).CrossRefGoogle Scholar
29. Tredgold, R. H., Nature 354, 120 (1991).Google Scholar