Nitric oxide (NO) reductase from the fungus is a P450-type enzyme (P450nor) that catalyzes the reduction of NO to nitrous oxide (NO) in the global nitrogen cycle. In this enzymatic reaction, the heme-bound NO is activated by the direct hydride transfer from NADH to generate a short-lived intermediate ( ), a key state to promote N-N bond formation and N-O bond cleavage. This study applied time-resolved (TR) techniques in conjunction with photolabile-caged NO to gain direct experimental results for the characterization of the coordination and electronic structures of TR freeze-trap crystallography using an X-ray free electron laser (XFEL) reveals highly bent Fe-NO coordination in , with an elongated Fe-NO bond length (Fe-NO = 1.91 Å, Fe-N-O = 138°) in the absence of NAD TR-infrared (IR) spectroscopy detects the formation of with an N-O stretching frequency of 1,290 cm upon hydride transfer from NADH to the Fe-NO enzyme via the dissociation of NAD from a transient state, with an N-O stretching of 1,330 cm and a lifetime of ca. 16 ms. Quantum mechanics/molecular mechanics calculations, based on these crystallographic and IR spectroscopic results, demonstrate that the electronic structure of is characterized by a singly protonated Fe-NHO radical. The current findings provide conclusive evidence for the NO generation mechanism via a radical-radical coupling of the heme nitroxyl complex with the second NO molecule.
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| http://dx.doi.org/10.1073/pnas.2101481118 | DOI Listing |
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