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The Chemical Evolution of a Nitrogenase Model, XXIV. Correlational Analysis of Effects of Organic Acids on in vitro MoFe-Protein Substrate Reduction Activities

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The Chemical Evolution of a Nitrogenase Model, XXIV. Correlational Analysis of Effects of Organic Acids on in vitro MoFe-Protein Substrate Reduction Activities

Gerhard N. Schrauzer and John G. Palmer

Department of Chemistry and Biochemistry, University of California, San Diego, Revelle College, La Jolla, CA 92093-0332

Reprint request to Prof. Schrauzer. Fax: 858 794 0212. E-mail: gschrauzer@ucsd.edu Z. Naturforsch.56 b,1354Ð1359 (2001); received June 5, 2001

Nitrogenase, Organic Acids, Mechanism of Action

Among 29 organic acids whose effects on thein vitroenzymatic substrate reducing activity on the MoFe-protein of nitrogenase have been investigated, 12 acids stimulate the in vitro C2H2-reducing activities in proportion to the H+-reducing activities. A second group com- prised of eight acids significantly stimulates the H+-reducing activity but has only modest stimulatory effects on C2H2- and N2-reducing activities. A third group of nine acids causes only slight increases of MoFe-protein substrate reducing activities. The stimulatory effects of acids on MoFe-protein substrate reducing activity depend on their mode of interaction with molybdenum. Hydroxycarboxylic acids acting as bidentate ligands such as homocitric acid and its derivatives leave a sufficient number of molybdenum coordination sites available for interactions with the substrates, they have the highest stimulatory effects both on the C2H2- and N2-reducing activities, and their H+-reducing activities are not inhibited by CO. Acids acting as tridentate ligands, which include citric acid, have weaker stimulatory effects on the C2H2- and especially on the N2-reducing activities, and CO inhibits their H+-reducing activity.

Whereas with the first group of acids the C2H2-reducing activities are linearly correlated with H+-reducing activities, the N2-reducing activities are directly correlated with H+-reduc- ing activitiesin the presence of CO, and the association is exponential rather than linear. This exponential dependence is consistent with a stepwise mechanism of nitrogen reduction via diazene and hydrazine as the intermediates, the latter blocking one molybdenum coordina- tion site prior to its reduction to NH3. In the reduction of C2H2to C2H4, no such blockage occurs as product C2H4does not accumulate at the active site and is not reduced further.

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