Abstract
Photochemical techniques have been used to measure the kinetics of intramolecular electron transfer in Ru(bpy)2(im)(His)2+-modified (bpy = 2,2′-bipyridine; im = imidazole) cytochromec and azurin. A driving-force study with the His33 derivatives of cytochromec indicates that the reorganization energy (γ) for Fe2+→Ru3+ ET reactions is 0.8 eV. Reductions of the ferriheme by either an excited complex,*Ru2+, or a reduced complex, Ru+, are anomalously fast and may involve formation of an electronically excited ferroheme. The distance dependence of Fe2+→Ru3+ and Cu+→Ru3+ electron transfer in 12 different Ru-modified cytochromes and azurins has been analyzed using a tunneling-pathway model. The ET rates in 10 of the 12 systems exhibit an exponential dependence on metal-metal separation (decay constant of 1.06 å−1) that is consistent with predictions of the pathway model.
Similar content being viewed by others
References
Adman, E. T., and Jensen, L. H. (1981).Isr. J. Chem. 21, 8–12.
Beratan, D. N., Betts, J. N., and Onuchic, J. N. (1991).Science 252, 1285–1288.
Brown, G. M., and Sutin, N. (1979).J. Am. Chem. Soc. 101, 883–892.
Brunschwig, B. S., and Sutin, N. (1987).Comments Inorg. Chem. 6, 209–235.
Casimiro D. R., Muheim, A., Richards, J. R., Arnold, F. H., Winkler, J. R., and Gray, H. B. (1993).J. Inorg. Biochem. 51, 232.
Casimiro, D. R., Richards, J. H., Winkler, J. R., and Gray, H. B. (1993).J. Phys. Chem. 97, 13073–13077.
Casimiro, D. R., Wong, L.-L., Colón, J. L., Zewert, T. E., Richards, J. H., Chang, I.-J., Winkler, J. R., and Gray, H. B. (1993).J. Am. Chem. Soc. 115, 1485–1489.
Chang, I.-J., Gray, H. B., and Winkler, J. R. (1991).J. Am. Chem. Soc. 113, 7056–7057.
Di Bilio, A., Skov, L. K., Hill, M. G., and Gray, H. B. (1995). To be submitted for publication.
Dodsworth, E. S., and Lever, A. B. P. (1986).Chem. Phys. Lett. 124, 152–158.
Durham, B. D., Pan, L. P., Hahn, S., Long, J., and Millett, F. (1990). InACS Advances in Chemistry Series (Johnson, M. K., King, R. B., Kurtz, D. M., Kutal, C., Norton, M. L., and Scott, R. A., eds.), American Chemical Society, Washington DC, pp. 180–193.
Farid, R. S., Moser, C. C., and Dutton, P. L. (1993).Curr. Opin. Struct. Biol. 3, 225–233.
Geren, L., Hahm, S., Durham, B., and Millett, F. (1991).Biochemistry 30, 9450–9457.
Gruschus, J. M., and Kuki, A. (1993).J. Phys. Chem. 97, 5581–5593.
Heacock D. H., II, Harris, M. R., Durham, B., and Millett, F. (1994).Inorg. Chim. Acta 226, 129–135.
Hopfield, J. J. (1974).Proc. Natl. Acad. Sci. USA 71, 3640–3644.
Kalyanasundaram, K. (1982).Coord. Chem. Rev. 46, 159–244.
Karpishin, T. B., Grinstaff, M. W., Jomar-Panicucci, S., McLendon, G., and Gray, H. B. (1994).Structure 2, 415–422.
Langen, R., Chang, I.-J., Germanas, J. P., Richards, J. H., Winkler, J. R., and Gray, H. B. (1995).Science 268, 1733–1735.
Marcus, R. A., and Sutin, N. (1985).Biochim. Biophys. Acta 811, 265–322.
Matthews, C. R., Erickson, P. M., Van Vliet, D. L., and Petersheim, M. (1978).J. Am. Chem. Soc. 100, 2260–2262.
McCleskey, T. M., Winkler, J. R., and Gray, H. B. (1992).J. Am. Chem. Soc. 114, 6935–6937.
Meade, T. J., Gray, H. B., and Winkler, J. R. (1989).J. Am. Chem. Soc. 111, 4353–4356.
Millett, F., and Durham, B. (1991). InMetals in Biological Systems, (ed.), Marcel Dekker, Inc., New York, pp. 223–264.
Mines, G. A., Winkler, J. R., Gray, H. B., and Chan, S. I. (1993).J. Inorg. Biochem. 51, 236.
Mines, G. A., Bjerrum, M. J., Hill, M. G., Casimiro, D. R., Chang, I-J., Winkler, J. R., and Gray, H. B. (1995).J. Am. Chem. Soc., submitted for publication.
Moser, C. C., Keske, J. M., Warncke, K., Farid, R. S., and Dutton, P. L. (1992).Nature 355, 796–802.
Onuchic, J. N., and Beratan, D. N. (1990).J. Chem. Phys. 92, 722–733.
Onuchic, J. N., Andrade, P. C. P., and Beratan, D. N. (1991).J. Chem. Phys. 95, 1131–1138.
Onuchic, J. N., Beratan, D. N., Winkler, J. R., and Gray, H. B. (1992).Annu. Rev. Biophys. Biomol. Struct. 21, 349–377.
Pan, L. P., Hibdon, S., Liu, R.-Q., Durham, B., and Millett, F. (1993).Biochemistry 32, 8492–8498.
Regan, J. J., Di Bilio, A. J., Langen, R., Skov, L. K., Winkler, J. R., Gray, H. B., and Onuchic, J. N. (1995).Chem. Biol., in press.
Scott, J. R., Willie, A., Mark, M., Stayton, P. S., Sligar, S. G., Durham, B., and Millett, F. (1993).J. Am. Chem. Soc. 115, 6820–6824.
Scott, J. R., McLean, M., Sligar, S. G.. Durham, B., and Millett, F. (1994).J. Am. Chem. Soc. 116, 7356–7362.
Siddarth, P., and Marcus, R. A. (1993).J. Phys. Chem. 97, 13078–13082.
Sutin, N., and Creutz, C. (1978). InInorganic and Organometallic Photochemistry. (ed.), American Chemical Society, Washington, DC, pp. 1–27.
Winkler, J. R., and Gray, H. B. (1992).Chem. Rev. 92, 369–379.
Winkler, J. R., Nocera, D. G., Yocom, K. M., Bordignon, E., and Gray, H. B. (1982).J. Am. Chem. Soc. 104, 5798–5800.
Wuttke, D. S., Bjerrum, M. J., Winkler, J. R., and Gray, H. B. (1992).Science 256, 1007–1009.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Bjerrum, M.J., Casimiro, D.R., Chang, I.J. et al. Electron transfer in ruthenium-modified proteins. J Bioenerg Biomembr 27, 295–302 (1995). https://doi.org/10.1007/BF02110099
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02110099