Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9th Sulfur”
Year: 2019
Type: article
Abstract: Nitrogenases catalyze the reduction of N2 to NH4+ at its cofactor site. Designated the M‐cluster, this [MoFe7S9C(R‐homocitrate)] cofactor is synthesized via the transformation of a [Fe4S4] cluster pair into an [Fe8S9C] precursor (designated the L‐cluster) prior to insertion of Mo and homocitrate. We report the characterization of an eight‐iron cofactor precursor (designated the L*‐cluster), which is proposed to have the composition [Fe8S8C] and lack the “9th sulfur” in the belt region of the L‐cluster. Our X‐ray absorption and electron spin echo envelope modulation (ESEEM) analyses strongly suggest that the L*‐cluster represents a structural homologue to the l‐cluster except for the missing belt sulfur. The absence of a belt sulfur from the L*‐cluster may prove beneficial for labeling the catalytically important belt region, which could in turn facilitate investigations into the reaction mechanism of nitrogenases.
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2968996579