In:
Angewandte Chemie, Wiley, Vol. 131, No. 41 ( 2019-10-07), p. 14845-14849
Abstract:
Nitrogenases catalyze the reduction of N 2 to NH 4 + at its cofactor site. Designated the M‐cluster, this [MoFe 7 S 9 C( R ‐homocitrate)] cofactor is synthesized via the transformation of a [Fe 4 S 4 ] cluster pair into an [Fe 8 S 9 C] 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 [Fe 8 S 8 C] and lack the “9 th 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.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v131.41
DOI:
10.1002/ange.201907593
Language:
English
Publisher:
Wiley
Publication Date:
2019
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