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A Refined Model for [Fe₃S₄]⁰ Clusters in Proteins

Detlef Bentrop Dr.

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Ivano Bertini Prof.,

Ivano Bertini Prof.

[email protected]

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Marco Borsari Prof.,

Marco Borsari Prof.

Department of Chemistry, University of Modena Via Campi 183, 41100, Modena (Italy)

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Grazia Cosenza,

Grazia Cosenza

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Claudio Luchinat Prof.,

Claudio Luchinat Prof.

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Yohei Niikura,

Yohei Niikura

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Detlef Bentrop Dr.,

Detlef Bentrop Dr.

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Ivano Bertini Prof.,

Ivano Bertini Prof.

[email protected]

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Marco Borsari Prof.,

Marco Borsari Prof.

Department of Chemistry, University of Modena Via Campi 183, 41100, Modena (Italy)

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Grazia Cosenza,

Grazia Cosenza

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Claudio Luchinat Prof.,

Claudio Luchinat Prof.

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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Yohei Niikura,

Yohei Niikura

Magnetic Resonance Center University of Florence Via L. Sacconi 6, 50019 Sesto Fiorentino (Italy) Fax: (+39) 055-4209271

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First published: 13 October 2000

https://doi.org/10.1002/1521-3773(20001016)39:20<3620::AID-ANIE3620>3.0.CO;2-T

Citations: 21

This work was supported by MURST (ex 40 %) and by the European Union through the Large Scale Facility Parabio (ERBFMGECT950033) and the HCM Network (ERBCHRXCT040626). We are grateful to Prof. S. Aono for the use of the expression system of the B. schlegelii ferredoxin.

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Abstract

A “merry-go-round” of iron valences is seen in an [Fe₃S₄]⁰ cluster with cysteine ligands. This phenomena is revealed by the observation of hyperfine-shifted ¹H NMR signals from the coordinated cysteine units, and the disappearance of these signals upon protonation of the cluster at low pH values. The proton binds to each of the three μ-bridging sulfides for a fraction of time (see scheme). The protonation of one μ-S causes the two iron atoms bridged by that μ-S to form a mixed-valence pair and the exchange of the proton from one μ-S to another causes a change in the iron valences in the cluster.

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Volume39, Issue20

October 16, 2000

Pages 3620-3622

A Refined Model for [Fe₃S₄]⁰ Clusters in Proteins

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A Refined Model for [Fe₃S₄]⁰ Clusters in Proteins