Electronic and Structural Properties of the Double Cubane Iron-Sulfur Cluster

dc.contributor.authorElghobashi-Meinhardt, Nadia
dc.contributor.authorTombolelli, Daria
dc.contributor.authorMroginski, Maria Andrea
dc.date.accessioned2021-03-10T13:36:34Z
dc.date.available2021-03-10T13:36:34Z
dc.date.issued2021-02-12
dc.date.updated2021-03-03T04:37:53Z
dc.description.abstractThe double-cubane cluster (DCC) refers to an [Fe8S9] iron-sulfur complex that is otherwise only known to exist in nitrogenases. Containing a bridging µ2-S ligand, the DCC in the DCC-containing protein (DCCP) is covalently linked to the protein scaffold via six coordinating cysteine residues. In this study, the nature of spin coupling and the effect of spin states on the cluster’s geometry are investigated computationally. Using density functional theory (DFT) and a broken symmetry (BS) approach to study the electronic ground state of the system, we computed the exchange interaction between the spin-coupled spins of the four FeFe dimers contained in the DCC. This treatment yields results that are in excellent agreement with both computed and experimentally determined exchange parameters for analogously coupled di-iron complexes. Hybrid quantum mechanical (QM)/molecular mechanical (MM) geometry optimizations show that cubane cluster A closest to charged amino acid side chains (Arg312, Glu140, Lys146) is less compact than cluster B, indicating that electrons of the same spin in a charged environment seek maximum separation. Overall, this study provides the community with a fundamental reference for subsequent studies of DCCP, as well as for investigations of other [Fe8S9]-containing enzymes.en
dc.description.sponsorshipDFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat"en
dc.description.sponsorshipDFG, 414044773, Open Access Publizieren 2021 - 2022 / Technische Universität Berlinde
dc.identifier.eissn2073-4344
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/12784
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-11584
dc.language.isoenen
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.subject.other[Fe8−S9] iron-sulfur clusteren
dc.subject.otherdouble-cubane clusteren
dc.subject.otherbroken symmetryen
dc.subject.otherdensity function theoryen
dc.subject.otherquantum mechanicsen
dc.subject.othergeometry optimizationsen
dc.subject.otherexchange parametersen
dc.subject.othermolecular mechanicsen
dc.titleElectronic and Structural Properties of the Double Cubane Iron-Sulfur Clusteren
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.articlenumber245en
dcterms.bibliographicCitation.doi10.3390/catal11020245en
dcterms.bibliographicCitation.issue2en
dcterms.bibliographicCitation.journaltitleCatalystsen
dcterms.bibliographicCitation.originalpublishernameMDPIen
dcterms.bibliographicCitation.originalpublisherplaceBaselen
dcterms.bibliographicCitation.volume11en
tub.accessrights.dnbfreeen
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Modellierung biomolekularer Systemede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Modellierung biomolekularer Systemede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlinen
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