English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Spectroscopic methods and density functional theory (DFT) calculations are used to determine the geometric and electronic structure of Cu Z °, an intermediate form of the Cu 4 S active site of nitrous oxide reductase (N 2 OR) that is observed in single turnover of fully reduced N 2 OR with N 2 O. Electron paramagnetic resonance (EPR), absorption, and magnetic circular dichroism (MCD) spectroscopies show that Cu Z ° is a 1-hole (i.e., 3Cu I Cu II ) state with spin density delocalized evenly over Cu I and Cu IV . Resonance Raman spectroscopy shows two Cu-S vibrations at 425 and 413 cm -1 , the latter with a -3 cm -1 O 18 solvent isotope shift. DFT calculations correlated to these spectral features show that Cu Z ° has a terminal hydroxide ligand coordinated to Cu IV , stabilized by a hydrogen bond to a nearby lysine residue. Cu Z ° can be reduced via electron transfer from Cu A using a physiologically relevant reductant. We obtain a lower limit on the rate of this intramolecular electron transfer (IET) that is &gt;10 4 faster than the unobserved IET in the resting state, showing that Cu Z ° is the catalytically relevant oxidized form of N 2 OR. Terminal hydroxide coordination to Cu IV in the Cu Z ° intermediate yields insight into the nature of N 2 O binding and reduction, specifying a molecular mechanism in which N 2 O coordinates in a μ-1,3 fashion to the fully reduced state, with hydrogen bonding from Lys397, and two electrons are transferred from the fully reduced μ 4 S 2- bridged tetranuclear copper cluster to N 2 O via a single Cu atom to accomplish N-O bond cleavage.

Spectroscopic Definition of the CuZ° Intermediate in Turnover of Nitrous Oxide Reductase and Molecular Insight into the Catalytic Mechanism

Spectroscopic Definition of the Cu_Z° Intermediate in Turnover of Nitrous Oxide Reductase and Molecular Insight into the Catalytic Mechanism