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Electron-Tunneling Pathways in Cytochrome c

Wuttke, Deborah S. and Bjerrum, Morten J. and Winkler, Jay R. and Gray, Harry B. (1992) Electron-Tunneling Pathways in Cytochrome c. Science, 256 (5029). pp. 1007-1009. ISSN 0036-8075. doi:10.1126/science.256.5059.1007.

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Distant Fe2+-Ru3+ electronic couplings have been extracted from intramolecular electron-transfer rates in Ru(histidine^x) (where X = 33, 39, 62, and 72) derivatives of cytochrome c. The couplings increase according to 62 (0.0060) < 72 (0.057) < 33 (0.097) < 39 (0.11 per wave numbers); however, this order is out of line with the histidine to heme edge-edge distances [62 (14.8) > 39 (12.3) > 33 (11.1) > 72 (8.4 angstroms)]. The rates (and the couplings) correlate with the lengths of σ-tunneling pathways comprised of covalent bonds, hydrogen bonds, and through-space jumps from the histidines to the heme group. Space jumps greatly decrease couplings: One from Pro71 to Met80 extends the σ-tunneling length of the His^72 pathway by roughly 10 covalent-bond units.

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 1992 American Association for the Advancement of Science. 27 December 1991; accepted 10 March 1992. We thank D. N. Beratan for assistance with the pathway analyses and for many helpful discussions. D.S.W. acknowledges an NSF predoctoral fellowship and a fellowship from the Parsons Foundation. M.J.B. was the Carlsberg Foundation Scholar in the Beckman Institute during 1990-91. Supported by National Science Foundation grants CHE-8822988 and CHE-9119992.
Funding AgencyGrant Number
NSF Predoctoral FellowshipUNSPECIFIED
Ralph M. Parsons FoundationUNSPECIFIED
Carlsberg FoundationUNSPECIFIED
Issue or Number:5029
Record Number:CaltechAUTHORS:20150121-092819858
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Official Citation:Wuttke, D. S., Bjerrum, M. J., Winkler, J. R., & Gray, H. B. (1992). Electron-Tunneling Pathways in Cytochrome c. Science, 256(5059), 1007-1009. doi: 10.1126/science.256.5059.1007
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:53928
Deposited On:21 Jan 2015 20:33
Last Modified:10 Nov 2021 20:24

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