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Helical, Disordered, and What that Means: Structural Characterization of a New Series of Methyl 1-Thiaoligo(ethylene Oxide) Self-Assembled Monolayers

  • David J. Vanderah (a1), Jennifer Arsenault (a1), Hongly La (a1), Vitalii Silin (a1), Curtis W. Meuse (a1) and Richard S. Gates (a1)...

Abstract

Self-assembled monolayers (SAMs) of a series of linear thiols containing a 1-thiaoligo(ethylene oxide) [TOEO] moiety, i.e., HS(CH2CH2O)xCH3, where x = 3 - 6, were prepared on polycrystalline gold (Au) and characterized by reflection absorption infrared spectroscopy (RAIRS) and spectroscopic ellipsometry (SE). For x = 5 and 6, the RAIRS data show that the TOEO segment, oriented normal to the substrate, adopts the highly ordered 7/2 helical structure of the folded-chain crystal polymorph of poly(ethylene oxide). For x = 3 and 4, the RAIRS and SE data indicate disordered, “amorphous” SAMs with essentially no evidence of the helical conformation in the TOEO segment. These data suggest that, for SAMs with TOEO segments, a minimum of five ethylene oxide units is required to adopt a helical conformation.

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References

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1. Ratner, B.D.; Hoffman, F.J.; Schoen, J.E.; Lemons, F. Biomaterials Science. An Introduction to Materials in Medicine, Academic Press: New York, 1996.
2. Hench, L.L. Biomaterials: An Interfacial Approach; Academic Press, New York, 1982.
3. Stelzle, M.; Wagner, R.; Nisch, W.; Jägermann, W.; Fröhlich, R.; Schaldach, M. Biosensors & Bioelectronics 1997, 12, 853.
4. Wedler, F.C.; Riedhammer, T.M., Biocompatability in Clinical Practice 1982, 11, 1.
5. Vadgama, P. Chemistry in Britain 1992, 249.
6. Benesch, J.; Svedhem, S.; Svensson, S.C.T.; Valiokas, R.; Liedberg, B.; Tengvall, P. J. Biomat. Sci. - Polym. E. 2001, 12, 581597.
7. Harder, P.; Grunze, M.; Dahint, R.; Whitesides, G.M.; Laibinis, P.E., J. Phys. Chem. B 1998, 102, 426.
8. Silin, V.; Weetall, H.; Vanderah, D.J., J. of Coll. and Interface Sci. 1997, 185, 94.
9. Prime, K.L.; Whitesides, G.M., J. Am. Chem. Soc. 1993, 115, 10714.
10. Prime, K.L.; Whitesides, G.M., Science 1991, 252, 1164.
11. Pale-Grosdemange, C.; Simon, E.S.; Prime, K.L.; Whitesides, G.M., J. Am. Chem. Soc 1991, 113, 12.
12. Papra, A.; Gadegaard, N.; Larsen, N.B., Langmuir 2001, 17, 1457.
13. Yang, Z.; Galloway, J.A.; Yu, H. Langmuir 1999, 15, 8405.
14. Vanderah, D.J.; Valincius, G.; Meuse, C.W., Langmuir, submitted.
15. Vanderah, D.J.; Meuse, C.W.; Silin, V.; Plant, A.L., Langmuir 1998, 14, 69166923.
16. Kobayashi, M.; Sakashita, M. J. Chem. Phys. 1992, 96, 748760.
17. Dissanayake, M.A.K.L.; Frech, R. Macromolecules 1995, 28, 53125319.
18. Laibinis, P.; Bain, C.D.; Nuzzo, R.G.; Whitesides, G.M., J. Phys. Chem. 1995, 99, 7663.
19. Vanderah, D.J.; Gates, R.S.; Silin, V.; Meuse, C.W.; Zeiger, D.N.; Valincius, G. Langmuir, submitted.
20. Vanderah, D.J.; Pham, C.P.; Springer, S.K.; Silin, V.; Meuse, C.W., Langmuir 2000, 16, 6527.
21. The specification of commercial products is for clarity only and does not constitute endorsement by NIST.
22. HRMS: (EO)6CH3 characterized by HRMS as reported earlier.14 (EO)5CH3:HR FAB [M + 1]+calcd for C11H25O5S 269.14227; found 269.14309. (EO)4CH3: HR FAB [M + 1]+ calcd for C9H21O4S 225.11606; found 225.11533. (EO)3CH3: HR FAB no mass found for C7H16O3S; [M + 1]+ found for disulfide, calcd for C14H31O6S2 359.15622; found 359.15418. 270 MHz 1H NMR for x = 3 - 5; δ 2.70 (relative to tetramethylsilane), 2H, dt, J ≈ 6.5 Hz and 6.2 Hz; HSCH2CH2O)xCH3; 3.38, 3H, s, HSCH2CH2O)xCH3.
23. Miyazawa, T.; Fukushima, K.; Ideguchi, Y. J. Chem. Phys. 1962, 37, 2764.
24. Bailey, F.E. Jr; Koleske, J.Y., Poly(ethylene oxide), Academic Press: New York, 1976, p 115.
25. Takahashi, Y.; Tadokoro, H. Macromolecules 1973, 23, 672675.

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