Detection and Characterization of Exchangeable Protons Bound to the Hydrogen-Activation Nickel Site of Desulfovibrio gigas Hydrogenase: A 1H and 2H Q-Band ENDOR Study

Chaoliang Fan; Miguel Teixeira; Jose Moura; Isabel Moura; Boi Hanh Huynh; Jean Le Gall; Harry D. Peck; Brian M. Hoffman

doi:10.1021/ja00001a003

Detection and Characterization of Exchangeable Protons Bound to the Hydrogen-Activation Nickel Site of Desulfovibrio gigas Hydrogenase: A ¹H and ²H Q-Band ENDOR Study

Chaoliang Fan, Miguel Teixeira, Jose Moura, Isabel Moura, Boi Hanh Huynh, Jean Le Gall, Harry D. Peck, Brian M. Hoffman^*

^*Corresponding author for this work

Chemistry

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

101 Scopus citations

Abstract

This paper presents a Q-band ENDOR study of the nickel site of the as-isolated (Ni-A), H₂-reduced (Ni-C), and reoxidized (Ni-A/Ni-B) states of Desulfovibrio gigas hydrogenase. Through proton and deuteron ENDOR measurements we detect and characterize the possible products of heterolytic cleavage of H₂, namely two distinct types of exchangeable protons, bound to the Ni-C site. One proton, H(l), has a hyperfine coupling, A^H(1) = 16.8 MHz and appears to interact directly with Ni-C. The other proton, H(2), has A^H(2) ≈ 4.4 MHz and could be associated with H₂0 or OH⁻ bound to nickel. We discuss possible binding modes for H(l) and H(2). One type of exchangeable deuteron(s), D(2), associated with the Ni-C center remains associated with the Ni-B center after oxidation of the Ni-C. In addition we confirm that the Ni-A site is inaccessible to solvent protons.

Original language	English (US)
Pages (from-to)	20-24
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	113
Issue number	1
DOIs	https://doi.org/10.1021/ja00001a003
State	Published - Jan 1 1991

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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Fan, C., Teixeira, M., Moura, J., Moura, I., Huynh, B. H., Gall, J. L., Peck, H. D., & Hoffman, B. M. (1991). Detection and Characterization of Exchangeable Protons Bound to the Hydrogen-Activation Nickel Site of Desulfovibrio gigas Hydrogenase: A ¹H and ²H Q-Band ENDOR Study. Journal of the American Chemical Society, 113(1), 20-24. https://doi.org/10.1021/ja00001a003

Fan, Chaoliang ; Teixeira, Miguel ; Moura, Jose ; Moura, Isabel ; Huynh, Boi Hanh ; Gall, Jean Le ; Peck, Harry D. ; Hoffman, Brian M. / Detection and Characterization of Exchangeable Protons Bound to the Hydrogen-Activation Nickel Site of Desulfovibrio gigas Hydrogenase : A ¹H and ²H Q-Band ENDOR Study. In: Journal of the American Chemical Society. 1991 ; Vol. 113, No. 1. pp. 20-24.

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title = "Detection and Characterization of Exchangeable Protons Bound to the Hydrogen-Activation Nickel Site of Desulfovibrio gigas Hydrogenase: A 1H and 2H Q-Band ENDOR Study",

abstract = "This paper presents a Q-band ENDOR study of the nickel site of the as-isolated (Ni-A), H2-reduced (Ni-C), and reoxidized (Ni-A/Ni-B) states of Desulfovibrio gigas hydrogenase. Through proton and deuteron ENDOR measurements we detect and characterize the possible products of heterolytic cleavage of H2, namely two distinct types of exchangeable protons, bound to the Ni-C site. One proton, H(l), has a hyperfine coupling, AH(1) = 16.8 MHz and appears to interact directly with Ni-C. The other proton, H(2), has AH(2) ≈ 4.4 MHz and could be associated with H20 or OH− bound to nickel. We discuss possible binding modes for H(l) and H(2). One type of exchangeable deuteron(s), D(2), associated with the Ni-C center remains associated with the Ni-B center after oxidation of the Ni-C. In addition we confirm that the Ni-A site is inaccessible to solvent protons.",

author = "Chaoliang Fan and Miguel Teixeira and Jose Moura and Isabel Moura and Huynh, {Boi Hanh} and Gall, {Jean Le} and Peck, {Harry D.} and Hoffman, {Brian M.}",

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Detection and Characterization of Exchangeable Protons Bound to the Hydrogen-Activation Nickel Site of Desulfovibrio gigas Hydrogenase : A ¹H and ²H Q-Band ENDOR Study. / Fan, Chaoliang; Teixeira, Miguel; Moura, Jose; Moura, Isabel; Huynh, Boi Hanh; Gall, Jean Le; Peck, Harry D.; Hoffman, Brian M.

In: Journal of the American Chemical Society, Vol. 113, No. 1, 01.01.1991, p. 20-24.

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

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T1 - Detection and Characterization of Exchangeable Protons Bound to the Hydrogen-Activation Nickel Site of Desulfovibrio gigas Hydrogenase

T2 - A 1H and 2H Q-Band ENDOR Study

AU - Fan, Chaoliang

AU - Teixeira, Miguel

AU - Moura, Jose

AU - Moura, Isabel

AU - Huynh, Boi Hanh

AU - Gall, Jean Le

AU - Peck, Harry D.

AU - Hoffman, Brian M.

PY - 1991/1/1

Y1 - 1991/1/1

N2 - This paper presents a Q-band ENDOR study of the nickel site of the as-isolated (Ni-A), H2-reduced (Ni-C), and reoxidized (Ni-A/Ni-B) states of Desulfovibrio gigas hydrogenase. Through proton and deuteron ENDOR measurements we detect and characterize the possible products of heterolytic cleavage of H2, namely two distinct types of exchangeable protons, bound to the Ni-C site. One proton, H(l), has a hyperfine coupling, AH(1) = 16.8 MHz and appears to interact directly with Ni-C. The other proton, H(2), has AH(2) ≈ 4.4 MHz and could be associated with H20 or OH− bound to nickel. We discuss possible binding modes for H(l) and H(2). One type of exchangeable deuteron(s), D(2), associated with the Ni-C center remains associated with the Ni-B center after oxidation of the Ni-C. In addition we confirm that the Ni-A site is inaccessible to solvent protons.

AB - This paper presents a Q-band ENDOR study of the nickel site of the as-isolated (Ni-A), H2-reduced (Ni-C), and reoxidized (Ni-A/Ni-B) states of Desulfovibrio gigas hydrogenase. Through proton and deuteron ENDOR measurements we detect and characterize the possible products of heterolytic cleavage of H2, namely two distinct types of exchangeable protons, bound to the Ni-C site. One proton, H(l), has a hyperfine coupling, AH(1) = 16.8 MHz and appears to interact directly with Ni-C. The other proton, H(2), has AH(2) ≈ 4.4 MHz and could be associated with H20 or OH− bound to nickel. We discuss possible binding modes for H(l) and H(2). One type of exchangeable deuteron(s), D(2), associated with the Ni-C center remains associated with the Ni-B center after oxidation of the Ni-C. In addition we confirm that the Ni-A site is inaccessible to solvent protons.

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