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@ARTICLE{Caserta:639802,
author = {Caserta, Giorgio and Laun, Konstantin and Oudsen,
Jean-Pierre and Sergueev, Ilya and Zebger, Ingo and Lenz,
Oliver},
title = {{NRVS} {S}pectroscopy {R}esolves {D}istinct {B}ridging
{H}ydride {I}ntermediates in [{N}i{F}e]-{H}ydrogenase},
journal = {Journal of the American Chemical Society},
volume = {147},
number = {45},
issn = {0002-7863},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {PUBDB-2025-04676},
pages = {41216 - 41220},
year = {2025},
note = {Open Access},
abstract = {The active-site iron of an H2-sensing [NiFe]-hydrogenase
was selectively labeled with 57Fe, allowing the probing of
all catalytic intermediates using synchrotron-based nuclear
resonance vibrational spectroscopy. Diagnostic
metal–hydride vibrations were detected for both the Nia-C
and Nia-SR intermediates, with their assignments being
confirmed through H/D isotope substitution and in situ
hydride photolysis experiments. Interestingly, these
Fe–hydride bands are separated by a large energy gap,
reflecting distinct bonding interactions at the
metal–hydride site. Despite these differences, vibrational
analyses across all catalytically active species reveal a
conserved structural rigidity of the [NiFe] center, which
appears crucial for sustaining efficient and rapid electron
transfer in [NiFe]-hydrogenases.},
cin = {DOOR ; HAS-User / FS-PET-S},
ddc = {540},
cid = {I:(DE-H253)HAS-User-20120731 /
I:(DE-H253)FS-PET-S-20190712},
pnm = {632 - Materials – Quantum, Complex and Functional
Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3) /
FS-Proposal: I-20200452 (I-20200452) / FS-Proposal:
I-20210325 (I-20210325) / DFG project G:(GEPRIS)390540038 -
EXC 2008: Unifying Systems in Catalysis "UniSysCat"
(390540038)},
pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3 /
G:(DE-H253)I-20200452 / G:(DE-H253)I-20210325 /
G:(GEPRIS)390540038},
experiment = {EXP:(DE-H253)P-P01-20150101},
typ = {PUB:(DE-HGF)16},
doi = {10.1021/jacs.5c15408},
url = {https://bib-pubdb1.desy.de/record/639802},
}