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Mechanism of Mixed-Valence Fe^2.5+···Fe^2.5+ Formation in Fe₄S₄ Clusters in the Ferredoxin Binding Motif.

ABSTRACT: Most low-potential Fe₄S₄ clusters exist in the conserved binding sequence CxxCxxC (CⁿCⁿ⁺³Cⁿ⁺⁶). Fe(II) and Fe(III) at the first (Cⁿ) and third (Cⁿ⁺⁶) cysteine ligand sites form a mixed-valence Fe^2.5+···Fe^2.5+ pair in the reduced Fe(II)₃Fe(III) cluster. Here, we investigate the mechanism of how the conserved protein environment induces mixed-valence pair formation in the Fe₄S₄ clusters, F_X, F_A, and F_B in photosystem I, using a quantum mechanical/molecular mechanical approach. Exchange coupling between Fe sites is predominantly determined by the shape of the Fe₄S₄ cluster, which is stabilized by the preorganized protein electrostatic environment. The backbone NH and CO groups in the conserved CxxCxxC and adjacent helix regions orient along the Fe^Cn···Fe^C(n+6) axis, generating an electric field and stabilizing the Fe^Cn(II)Fe^C(n+6)(III) state in F_A and F_B. The overlap of the d orbitals via -S- (superexchange) is observed for the single Fe^Cn(II)···Fe^C(n+6)(III) pair, leading to the formation of the mixed-valence Fe^2.5+···Fe^2.5+ pair. In contrast, several superexchange Fe(II)···Fe(III) pairs are observed in F_X due to the highly symmetric pair of the CDGPGRGGTC sequences. This is likely the origin of F_X serving as an electron acceptor in the two electron transfer branches.

SUBMITTER: Kanda T

PROVIDER: S-EPMC9059760 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Publications

Mechanism of Mixed-Valence Fe2.5+···Fe2.5+ Formation in Fe4S4 Clusters in the Ferredoxin Binding Motif.

Kanda Tomoki T Saito Keisuke K Ishikita Hiroshi H

The journal of physical chemistry. B 20220418 16

Most low-potential Fe4S4 clusters exist in the conserved binding sequence CxxCxxC (CnCn+3Cn+6). Fe(II) and Fe(III) at the first (Cn) and third (Cn+6) cysteine ligand sites form a mixed-valence Fe2.5+···Fe2.5+ pair in the reduced Fe(II)3Fe(III) cluster. Here, we investigate the mechanism of how the conserved protein environment induces mixed-valence pair ...[more]

PMID: 35435680

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Project description:The series BaIn1-x Fe x O2.5+δ, x = 0.25, 0.50, and 0.75, has been prepared under air-fired and argon-fired conditions and studied using X-ray diffraction, d.c. and a.c. susceptibility, Mössbauer spectroscopy, neutron diffraction, X-ray near edge absorption spectroscopy (XANES), and X-ray pair distribution (PDF) methods. While Ba2In2O5 (BaInO2.5) crystallizes in an ordered brownmillerite structure, Ibm2, and Ba2Fe2O5 (BaFeO2.5) crystallizes in a complex monoclinic structure, P21/c, showing seven Fe3+ sites with tetrahedral, square planar, and octahedral environments, all phases studied here crystallize in the cubic perovskite structure, Pm3̅m, with long-range disorder on the small cation and oxygen sites. 57Fe Mössbauer studies indicate a mixed valency, Fe4+/Fe3+, for both the air-fired and argon-fired samples. The increased Fe3+ content for the argon-fired samples is reflected in increased cubic cell constants and in the increased Mössbauer fraction. It appears that the Pm3̅m phases are only metastable when fired in argon. From a slightly modified percolation theory for a primitive cubic lattice (taking into account the presence of random O atom vacancies), long-range spin order is permitted for the x = 0.50 and 0.75 phases. Instead, the d.c. susceptibility shows only zero-field-cooled (ZFC) and field-cooled (FC) divergences at ∼6 K [5 K] for x = 0.50 and at ∼22 K [21 K] for x = 0.75, with values for the argon-fired samples in [ ]. Neutron diffraction data for the air-fired samples confirm the absence of long-range magnetic order at any studied temperature. For the air-fired x = 0.50, a.c. susceptibility data show a frequency-dependent χ'(max) and spin glass behavior, while for x = 0.75, χ'(max) is invariant with frequency, ruling out either a spin glass or a superparamagnetic ground state. These behaviors are discussed in terms of competing Fe3+-Fe3+ antiferromagnetic exchange and ferromagnetic Fe3+-Fe4+ exchange. The PDF and 57Fe Mössbauer data indicate a local structure at short interatomic distances, which deviates strongly from the average Pm3̅m model. Fe Mössbauer, PDF, and XANES data show a systematic dependence on x and indicate that the Fe3+ sites are largely fourfold-coordinated and Fe4+ sites are fivefold- or sixfold-coordinated.

Dataset Information

Mechanism of Mixed-Valence Fe^2.5+···Fe^2.5+ Formation in Fe₄S₄ Clusters in the Ferredoxin Binding Motif.

Publications

Mechanism of Mixed-Valence Fe<sup>2.5+</sup>···Fe<sup>2.5+</sup> Formation in Fe<sub>4</sub>S<sub>4</sub> Clusters in the Ferredoxin Binding Motif.

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