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Science 15 May 1992: Vol. 256. no. 5059, pp. 1007 - 1009 DOI: 10.1126/science.256.5059.1007
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Articles
Electron-Tunneling Pathways in Cytochrome c
Deborah S. Wuttke 1,
Morten J. Bjerrum 1,
Jay R. Winkler 1, and
Harry B. Gray 1
1 Beckman Institute, California Institute of Technology, Pasadena, CA 91125
Distant Fe2+-Ru3+ electronic couplings have been extracted from intramolecular electrontransfer rates in Ru(histidinex) (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 -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 -tunneling length of the His72 pathway by roughly 10 covalent-bond units.
Submitted on December 27, 1991
Accepted on March 10, 1992
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