Abstract
Novel 310-helical peptides having a disulfide group at the N-terminal and carrying naphthyl groups at the side chains in a linear arrangement were synthesized, those are 9mer, 18mer, and 27mer peptides with three, six, and nine naphthyl groups, respectively. Spectroscopic measurements of the peptide solutions showed that there was no interaction between the neighboring naphthyl groups. 310-Helical conformation was confirmed by circular dichroism spectroscopy and computational molecular modeling. The peptides were self-assembled on gold by an Au-S linkage, and the defect sites in the self-assembled monolayers (SAMs) were filled up with dodecanethiol. Cyclic voltammetry, ellipsometry, and infrared reflection-absorption spectroscopy studies on the SAMs showed that the peptides formed the densely-packed monolayers with vertical orientation. Upon photoexcitation of the naphthyl groups in an aqueous solution containing electron donors, the monolayer generated an anodic photocurrent by photoinduced electron transfer from the electron donor via the naphthyl groups to gold. The longest 27mer peptide generated the largest photocurrent among the peptides. Theoretical simulations successfully demonstrated that the helix scaffold with many naphthyl groups in a linear arrangement was effective to suppress quenching of the excited naphthyl group by gold due to the elongation of the helix length, and to promote electron hopping among the naphthyl groups enabling long-range electron transfer from the distant naphthyl group to gold, eventually realizing an efficient photocurrent generation molecular system.
Similar content being viewed by others
Article PDF
References
J. Deisenhofer and H. Michel, Angew. Chem., Int. Ed., 28, 829 (1989).
M. R. Wasielewski, Chem. Rev., 92, 435 (1992).
W. G. J. Hol, P. T. Vanduijnen, and H. J. C. Berendsen, Nature, 273, 443 (1978).
W. G. J. Hol, Prog. Biophys. Mol. Biol., 45, 149 (1985).
M. Sisido, S. Hoshino, H. Kusano, M. Kuragaki, M. Makino, H. Sasaki, T. A. Smith, and K. P. Ghiggino, J. Phys. Chem. B, 105, 10407 (2001).
S. Sek, A. Misicka, K. Swiatek, and E. Maicka, J. Phys. Chem. B, 110, 19671 (2006).
K. Kitagawa, T. Morita, and S. Kimura, J. Phys. Chem. B, 109, 13906 (2005).
J. F. Smalley, H. O. Finklea, C. E. D. Chidsey, M. R. Linford, S. E. Creager, J. P. Ferraris, K. Chalfant, T. Zawodzinsk, S. W. Feldberg, and M. D. Newton, J. Am. Chem. Soc., 125, 2004 (2003).
B. Q. Xu and N. J. J. Tao, Science, 301, 1221 (2003).
K. Kitagawa, T. Morita, and S. Kimura, Thin Solid Films, 509, 18 (2006).
T. Morita and S. Lindsay, J. Am. Chem. Soc., 129, 7262 (2007).
E. Galoppini and M. A. Fox, J. Am. Chem. Soc., 118, 2299 (1996).
M. A. Fox and E. Galoppini, J. Am. Chem. Soc., 119, 5277 (1997).
T. Morita, S. Kimura, S. Kobayashi, and Y. Imanishi, J. Am. Chem. Soc., 122, 2850 (2000).
S. Yasutomi, T. Morita, Y. Imanishi, and S. Kimura, Science, 304, 1944 (2004).
S. Yasutomi, T. Morita, and S. Kimura, J. Am. Chem. Soc., 127, 14564 (2005).
S. Yamada, H. Kohrogi, and T. Matsuo, Chem. Lett., 639 (1995).
S. Yamada, Y. Koide, and T. Matsuo, J. Electroanal. Chem., 426, 23 (1997).
K. Uosaki, T. Kondo, X. Q. Zhang, and M. Yanagida, J. Am. Chem. Soc., 119, 8367 (1997).
T. Kondo, M. Yanagida, S. Nomura, T. Ito, and K. Uosaki, J. Electroanal. Chem., 438, 121 (1997).
H. Imahori, H. Norieda, S. Ozawa, K. Ushida, H. Yamada, T. Azuma, K. Tamaki, and Y. Sakata, Langmuir, 14, 5335 (1998).
H. Imahori, T. Azuma, S. Ozawa, H. Yamada, K. Ushida, A. Ajavakom, H. Norieda, and Y. Sakata, Chem. Commun., 557 (1999).
H. Imahori, T. Azuma, A. Ajavakom, H. Norieda, H. Yamada, and Y. Sakata, J. Phys. Chem. B, 103, 7233 (1999).
T. Morita, S. Kimura, S. Kobayashi, and Y. Imanishi, Chem. Lett., 676 (2000).
H. Imahori, H. Yamada, Y. Nishimura, I. Yamazaki, and Y. Sakata, J. Phys. Chem. B, 104, 2099 (2000).
T. Kondo, M. Yanagida, X. Q. Zhang, and K. Uosaki, Chem. Lett., 964 (2000).
H. Imahori, H. Norieda, H. Yamada, Y. Nishimura, I. Yamazaki, Y. Sakata, and S. Fukuzumi, J. Am. Chem. Soc., 123, 100 (2001).
P. K. Sudeep, B. I. Ipe, K. G. Thomas, M. V. George, S. Barazzouk, S. Hotchandani, and P. V. Kamat, Nano Lett., 2, 29 (2002).
A. Nomoto and Y. Kobuke, Chem. Commun., 1104 (2002).
F. B. Abdelrazzaq, R. C. Kwong, and M. E. Thompson, J. Am. Chem. Soc., 124, 4796 (2002).
K. G. Thomas and P. V. Kamat, Acc. Chem. Res., 36, 888 (2003).
E. Soto, J. C. MacDonald, C. G. F. Cooper, and G. McGimpsey, J. Am. Chem. Soc., 125, 2838 (2003).
K. Yanagisawa, T. Morita, and S. Kimura, J. Am. Chem. Soc., 126, 12780 (2004).
E. Benedetti, A. Bavoso, B. Diblasio, V. Pavone, C. Pedone, M. Crisma, G. M. Bonora, and C. Toniolo, J. Am. Chem. Soc., 104, 2437 (1982).
C. Toniolo, G. M. Bonora, V. Barone, A. Bavoso, E. Benedetti, B. Diblasio, P. Grimaldi, F. Lelj, V. Pavone, and C. Pedone, Macromolecules, 18, 895 (1985).
I. L. Karle, M. Sukumar, and P. Balaram, Proc. Natl. Acad. Sci. U.S.A., 83, 9284 (1986).
C. Toniolo and E. Benedetti, Trends Biochem. Sci., 16, 350 (1991).
D. F. Kennedy, M. Crisma, C. Toniolo, and D. Chapman, Biochemistry, 30, 6541 (1991).
T. Forster, Discuss. Faraday Soc., 7 (1959).
Z. J. Donhauser, B. A. Mantooth, K. F. Kelly, L. A. Bumm, J. D. Monnell, J. J. Stapleton, D. W. Price, A. M. Rawlett, D. L. Allara, J. M. Tour, and P. S. Weiss, Science, 292, 2303 (2001).
H. U. Gremlich, U. P. Fringeli, and R. Schwyzer, Biochemistry, 22, 4257 (1983).
Y. Miura, S. Kimura, Y. Imanishi, and J. Umemura, Langmuir, 14, 6935 (1998).
M. Tsuboi, J. Polym. Sci., 59, 139 (1962).
E. Benedetti, B. Di Blasio, V. Pavone, C. Pedone, A. Santini, M. Crisma, and C. Toniolo, in “Molecular Conformation and Biological Interactions,” p. Balaram and S. Ramaseshan, Ed., Indian Academy of Science, Bangalore, 1991, pp 497.
C. G. Hatchard and C. A. Parker, Proc. R. Soc. London, A, 235, 518 (1956).
H. Du, R. C. A. Fuh, J. Z. Li, L. A. Corkan, and J. S. Lindsey, Photochem. Photobiol., 68, 141 (1998).
M. Sisido, S. Egusa, and Y. Imanishi, J. Am. Chem. Soc., 105, 4077 (1983).
M. Sisido, S. Egusa, and Y. Imanishi, J. Am. Chem. Soc., 105, 1041 (1983).
R. W. Woody, J. Chem. Phys., 49, 4797 (1968).
M. Sisido and Y. Imanishi, Macromolecules, 18, 890 (1985).
Y. Inai and T. Hirabayashi, Biopolymers, 59, 356 (2001).
Y. Inai, T. Oshikawa, M. Yamashita, T. Hirabayashi, and T. Hirako, Biopolymers, 58, 9 (2001).
M. D. Porter, T. B. Bright, D. L. Allara, and C. E. D. Chidsey, J. Am. Chem. Soc., 109, 3559 (1987).
C. A. Widrig, C. Chung, and M. D. Porter, J. Electroanal. Chem., 310, 335 (1991).
C. Miller, P. Cuendet, and M. Gratzel, J. Phys. Chem., 95, 877 (1991).
A. L. Plant, Langmuir, 9, 2764 (1993).
C. S. Yun, A. Javier, T. Jennings, M. Fisher, S. Hira, S. Peterson, B. Hopkins, N. O. Reich, and G. F. Strouse, J. Am. Chem. Soc., 127, 3115 (2005).
R. A. Marcus and N. Sutin, Biochim. Biophys. Acta, 811, 265 (1985).
P. Siddarth and R. A. Marcus, J. Phys. Chem., 94, 2985 (1990).
D. M. Adams, L. Brus, C. E. D. Chidsey, S. Creager, C. Creutz, C. R. Kagan, P. V. Kamat, M. Lieberman, S. Lindsay, R. A. Marcus, R. M. Metzger, M. E. Michel-Beyerle, J. R. Miller, M. D. Newton, D. R. Rolison, O. Sankey, K. S. Schanze, J. Yardley, and X. Y. Zhu, J. Phys. Chem. B, 107, 6668 (2003).
G. J. Kavarnos and N. J. Turro, Chem. Rev., 86, 401 (1986).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Morita, T., Yanagisawa, K. & Kimura, S. Enhanced Photocurrent Generation by Electron Hopping through Regularly-Arranged Chromophores in a Helical Peptide Monolayer. Polym J 40, 700–709 (2008). https://doi.org/10.1295/polymj.PJ2008062
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.PJ2008062