[FeFe]-Hydrogenases: maturation and reactivity of enzymatic systems and overview of biomimetic models

JT Kleinhaus, F Wittkamp, S Yadav… - Chemical Society …, 2021 - pubs.rsc.org
While hydrogen plays an ever-increasing role in modern society, nature has utilized
hydrogen since a very long time as an energy carrier and storage molecule. Among the …

Mechanism of Radical Initiation in the Radical S-Adenosyl-l-methionine Superfamily

WE Broderick, BM Hoffman… - Accounts of chemical …, 2018 - ACS Publications
Conspectus The seeds for recognition of the vast superfamily of radical S-adenosyl-l-
methionine (SAM) enzymes were sown in the 1960s, when Joachim Knappe found that the …

Direct observation of an iron-bound terminal hydride in [FeFe]-hydrogenase by nuclear resonance vibrational spectroscopy

EJ Reijerse, CC Pham, V Pelmenschikov… - Journal of the …, 2017 - ACS Publications
[FeFe]-hydrogenases catalyze the reversible reduction of protons to molecular hydrogen
with extremely high efficiency. The active site (“H-cluster”) consists of a [4Fe–4S] H cluster …

Bioassembly of complex iron–sulfur enzymes: hydrogenases and nitrogenases

RD Britt, G Rao, L Tao - Nature Reviews Chemistry, 2020 - nature.com
Nature uses multinuclear metal clusters to catalyse a number of important multielectron
redox reactions. Examples that employ complex Fe–S clusters in catalysis include the Fe …

Biosynthesis of the catalytic H-cluster of [FeFe] hydrogenase: the roles of the Fe–S maturase proteins HydE, HydF, and HydG

RD Britt, G Rao, L Tao - Chemical science, 2020 - pubs.rsc.org
[FeFe] hydrogenases carry out the redox interconversion of protons and molecular hydrogen
(2H++ 2e−⇌ H2) at a complex Fe–S active site known as the H-cluster. The H-cluster …

Trapping and Electron Paramagnetic Resonance Characterization of the 5′dAdo Radical in a Radical S-Adenosyl Methionine Enzyme Reaction with a Non-Native …

RI Sayler, TA Stich, S Joshi, N Cooper… - ACS central …, 2019 - ACS Publications
S-Adenosyl methionine (SAM) is employed as a [4Fe-4S]-bound cofactor in the superfamily
of radical SAM (rSAM) enzymes, in which one-electron reduction of the [4Fe-4S]-SAM moiety …

Radical SAM enzyme HydE generates adenosylated Fe (I) intermediates en route to the [FeFe]-hydrogenase catalytic H-cluster

L Tao, SA Pattenaude, S Joshi, TP Begley… - Journal of the …, 2020 - ACS Publications
The H-cluster of [FeFe]-hydrogenase consists of a [4Fe–4S] H-subcluster linked by a
cysteinyl bridge to a unique organometallic [2Fe] H-subcluster assigned as the site of …

Crystal Structure of the [FeFe]-hydrogenase maturase HydE bound to complex-B

R Rohac, L Martin, L Liu, D Basu, L Tao… - Journal of the …, 2021 - ACS Publications
[FeFe]-hydrogenases use a unique organometallic complex, termed the H cluster, to
reversibly convert H2 into protons and low-potential electrons. It can be best described as a …

Fully Refined Semisynthesis of the [FeFe] Hydrogenase H-Cluster

G Rao, X Yu, Y Zhang, TB Rauchfuss, RD Britt - Biochemistry, 2023 - ACS Publications
[FeFe] hydrogenases contain a 6-Fe cofactor that serves as the active site for efficient redox
interconversion between H2 and protons. The biosynthesis of the so-called H-cluster …

Proton Shuttle Mediated by (SCH2)2P═O Moiety in [FeFe]-Hydrogenase Mimics: Electrochemical and DFT Studies

LR Almazahreh, F Arrigoni, H Abul-Futouh… - ACS …, 2021 - ACS Publications
The synthesis, characterization, and protonation of [Fe2 (CO) 6 {(μ-SCH2) 2 (Et) P═ O}](1)
using the moderately strong acid CF3CO2H (p K aMeCN= 12.7) are reported. Digital …