Redox couples of inducible nitric oxide synthase

Andrew K. Udit; Wendy Belliston-Bittner; Edith C. Glazer; Yen Hoang Le Nguyen; James M. Gillan; Michael G. Hill; Michael A. Marletta; David B. Goodin; Harry B. Gray

doi:10.1021/ja0520114

Redox couples of inducible nitric oxide synthase

Andrew K. Udit, Wendy Belliston-Bittner, Edith C. Glazer, Yen Hoang Le Nguyen, James M. Gillan, Michael G. Hill, Michael A. Marletta, David B. Goodin, Harry B. Gray

Chemistry

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

20 Citations (SciVal)

Abstract

We report direct electrochemistry of the iNOS heme domain in a DDAB film on the surface of a basal plane graphite electrode. Cyclic voltammetry reveals Fe^III/II and Fe^II/I couples at -191 and -1049 mV (vs Ag/AgCl). Imidazole and carbon monoxide in solution shift the FeIII/II potential by +20 and +62 mV, while the addition of dioxygen results in large catalytic waves at the onset of Fe^III reduction. Voltammetry at higher scan rates (with pH variations) reveals that the Fe^III/II cathodic peak can be resolved into two components, which are attributable to Fe^III/II couples of five- and six-coordinate hemes. Digital simulation of our experimental data implicates water dissociation from the heme as a gating mechanism for ET in iNOS.

Original language	English
Pages (from-to)	11212-11213
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	127
Issue number	32
DOIs	https://doi.org/10.1021/ja0520114
State	Published - Aug 17 2005

ASJC Scopus subject areas

Catalysis
Chemistry (all)
Biochemistry
Colloid and Surface Chemistry

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title = "Redox couples of inducible nitric oxide synthase",

abstract = "We report direct electrochemistry of the iNOS heme domain in a DDAB film on the surface of a basal plane graphite electrode. Cyclic voltammetry reveals FeIII/II and FeII/I couples at -191 and -1049 mV (vs Ag/AgCl). Imidazole and carbon monoxide in solution shift the FeIII/II potential by +20 and +62 mV, while the addition of dioxygen results in large catalytic waves at the onset of FeIII reduction. Voltammetry at higher scan rates (with pH variations) reveals that the FeIII/II cathodic peak can be resolved into two components, which are attributable to FeIII/II couples of five- and six-coordinate hemes. Digital simulation of our experimental data implicates water dissociation from the heme as a gating mechanism for ET in iNOS.",

author = "Udit, {Andrew K.} and Wendy Belliston-Bittner and Glazer, {Edith C.} and {Le Nguyen}, {Yen Hoang} and Gillan, {James M.} and Hill, {Michael G.} and Marletta, {Michael A.} and Goodin, {David B.} and Gray, {Harry B.}",

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doi = "10.1021/ja0520114",

language = "English",

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T1 - Redox couples of inducible nitric oxide synthase

AU - Udit, Andrew K.

AU - Belliston-Bittner, Wendy

AU - Glazer, Edith C.

AU - Le Nguyen, Yen Hoang

AU - Gillan, James M.

AU - Hill, Michael G.

AU - Marletta, Michael A.

AU - Goodin, David B.

AU - Gray, Harry B.

PY - 2005/8/17

Y1 - 2005/8/17

N2 - We report direct electrochemistry of the iNOS heme domain in a DDAB film on the surface of a basal plane graphite electrode. Cyclic voltammetry reveals FeIII/II and FeII/I couples at -191 and -1049 mV (vs Ag/AgCl). Imidazole and carbon monoxide in solution shift the FeIII/II potential by +20 and +62 mV, while the addition of dioxygen results in large catalytic waves at the onset of FeIII reduction. Voltammetry at higher scan rates (with pH variations) reveals that the FeIII/II cathodic peak can be resolved into two components, which are attributable to FeIII/II couples of five- and six-coordinate hemes. Digital simulation of our experimental data implicates water dissociation from the heme as a gating mechanism for ET in iNOS.

AB - We report direct electrochemistry of the iNOS heme domain in a DDAB film on the surface of a basal plane graphite electrode. Cyclic voltammetry reveals FeIII/II and FeII/I couples at -191 and -1049 mV (vs Ag/AgCl). Imidazole and carbon monoxide in solution shift the FeIII/II potential by +20 and +62 mV, while the addition of dioxygen results in large catalytic waves at the onset of FeIII reduction. Voltammetry at higher scan rates (with pH variations) reveals that the FeIII/II cathodic peak can be resolved into two components, which are attributable to FeIII/II couples of five- and six-coordinate hemes. Digital simulation of our experimental data implicates water dissociation from the heme as a gating mechanism for ET in iNOS.

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ER -

Redox couples of inducible nitric oxide synthase

Abstract

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