Electron tunneling in ruthenium-modified cytochromec

Deborah S. Wuttke; Morten J. Bjerrum; I. Jy Chang; Jay R. Winkler; Harry B. Gray

doi:10.1016/0005-2728(92)90204-F

Electron tunneling in ruthenium-modified cytochromec

Deborah S. Wuttke, Morten J. Bjerrum, I. Jy Chang, Jay R. Winkler, Harry B. Gray^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

56 Citations (Scopus)

Abstract

Distant Fe²⁺-Ru³⁺ electronic couplings have been extracted from intramolecular electron-transfer rates in Ru(2,2′-bipyridine)₂(imidazole)(histidine-X)²⁺ (X = 33,39,62,72,79) derivatives of cytochromec. The rates are 〉 1 · 10⁸ (79); 3.2(4) · 10⁶ (39); 2.6(3) · 10⁶ (33); 9.0(3) · 10⁵ (72); 1.0(2) · 10⁴ s⁻¹ (62); the couplings increase according to 62 (0.006) < 72 (0.057) < 33 (0.097) < 39 (0.11) < 79 (〉 0.6 cm⁻¹). 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.

Original language	English
Pages (from-to)	168-170
Number of pages	3
Journal	Biochimica et Biophysica Acta - Bioenergetics
Volume	1101
Issue number	2
DOIs	https://doi.org/10.1016/0005-2728(92)90204-F
Publication status	Published - 1992 Jul 17
Externally published	Yes

Keywords

Electron transfer
Electronic coupling
Intramolecular rate
Pathway

ASJC Scopus subject areas

Biophysics
Biochemistry
Cell Biology

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10.1016/0005-2728(92)90204-F

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title = "Electron tunneling in ruthenium-modified cytochromec",

abstract = "Distant Fe2+-Ru3+ electronic couplings have been extracted from intramolecular electron-transfer rates in Ru(2,2′-bipyridine)2(imidazole)(histidine-X)2+ (X = 33,39,62,72,79) derivatives of cytochromec. The rates are 〉 1 · 108 (79); 3.2(4) · 106 (39); 2.6(3) · 106 (33); 9.0(3) · 105 (72); 1.0(2) · 104 s−1 (62); the couplings increase according to 62 (0.006) < 72 (0.057) < 33 (0.097) < 39 (0.11) < 79 (〉 0.6 cm−1). 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.",

keywords = "Electron transfer, Electronic coupling, Intramolecular rate, Pathway",

author = "Wuttke, {Deborah S.} and Bjerrum, {Morten J.} and Chang, {I. Jy} and Winkler, {Jay R.} and Gray, {Harry B.}",

note = "Funding Information: We thank D.N. Beratan and A. Kuki for 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. This work was supported by National Science Foundation Grants CHE-8822988 and CHE-9119992.",

year = "1992",

month = jul,

day = "17",

doi = "10.1016/0005-2728(92)90204-F",

language = "English",

volume = "1101",

pages = "168--170",

journal = "Biochimica et Biophysica Acta - Bioenergetics",

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TY - JOUR

T1 - Electron tunneling in ruthenium-modified cytochromec

AU - Wuttke, Deborah S.

AU - Bjerrum, Morten J.

AU - Chang, I. Jy

AU - Winkler, Jay R.

AU - Gray, Harry B.

N1 - Funding Information: We thank D.N. Beratan and A. Kuki for 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. This work was supported by National Science Foundation Grants CHE-8822988 and CHE-9119992.

PY - 1992/7/17

Y1 - 1992/7/17

N2 - Distant Fe2+-Ru3+ electronic couplings have been extracted from intramolecular electron-transfer rates in Ru(2,2′-bipyridine)2(imidazole)(histidine-X)2+ (X = 33,39,62,72,79) derivatives of cytochromec. The rates are 〉 1 · 108 (79); 3.2(4) · 106 (39); 2.6(3) · 106 (33); 9.0(3) · 105 (72); 1.0(2) · 104 s−1 (62); the couplings increase according to 62 (0.006) < 72 (0.057) < 33 (0.097) < 39 (0.11) < 79 (〉 0.6 cm−1). 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.

AB - Distant Fe2+-Ru3+ electronic couplings have been extracted from intramolecular electron-transfer rates in Ru(2,2′-bipyridine)2(imidazole)(histidine-X)2+ (X = 33,39,62,72,79) derivatives of cytochromec. The rates are 〉 1 · 108 (79); 3.2(4) · 106 (39); 2.6(3) · 106 (33); 9.0(3) · 105 (72); 1.0(2) · 104 s−1 (62); the couplings increase according to 62 (0.006) < 72 (0.057) < 33 (0.097) < 39 (0.11) < 79 (〉 0.6 cm−1). 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.

KW - Electron transfer

KW - Electronic coupling

KW - Intramolecular rate

KW - Pathway

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Electron tunneling in ruthenium-modified cytochromec

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