XES determination of the electronic structure of the over-oxidized form of the Hydrogenophilus thermoluteolus hydrogenase

DOI

Here we propose to measure Ni K-beta X-ray emission spectroscopy and XAS to unambiguously assign the electronic structure to a recently reported oxygen-protected state of the hyperthermophile hydrogenase from Hydrogenophilus thermoluteolus (HtSH). Although the crystal structure of this state indicates an unusual coordination of the Ni with three bridging cysteine residues and a terminal bidentate glutamate, two possible electronic structures have been proposed, a closed-shell singlet with a Ni(IV) and a Fe(II) at the active site, and an antiferromagnetically coupled open-shell singlet with a Ni(III) and an oxidized Fe(III). The proposed spin selective XES measurements should provide definitive evidence to assign the correct electronic structure.

Identifier
DOI https://doi.org/10.15151/ESRF-ES-2032089619
Metadata Access https://icatplus.esrf.fr/oaipmh/request?verb=GetRecord&metadataPrefix=oai_datacite&identifier=oai:icatplus.esrf.fr:inv/2032089619
Provenance
Creator Blanka DETLEFS (ORCID: 0000-0002-9768-647X); OLGA FILIMONOVA ORCID logo; Claudia TAHIRAJ ORCID logo; Vivian GUO; Olaf RUEDIGER ORCID logo
Publisher ESRF (European Synchrotron Radiation Facility)
Publication Year 2028
Rights CC-BY-4.0; https://creativecommons.org/licenses/by/4.0
OpenAccess true
Representation
Resource Type Data from large facility measurement; Collection
Discipline Particles, Nuclei and Fields