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Oxaloacetate-to-malate conversion by mineral photoelectrochemistry: implications for the viability of the reductive tricarboxylic acid cycle in prebiotic chemistry

Published online by Cambridge University Press:  04 December 2008

Marcelo I. Guzman  and
Scot T. Martin
Marcelo I. Guzman
Affiliation:
School of Engineering and Applied Sciences & Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA 02138, USA e-mail: [email protected]
Scot T. Martin
Affiliation:
School of Engineering and Applied Sciences & Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA 02138, USA e-mail: [email protected]
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Abstract

The carboxylic acids produced by the reductive tricarboxylic acid (rTCA) cycle are possibly a biosynthetic core of initial life, although several steps such as the reductive kinetics of oxaloacetate (OAA) to malate (MA) are problematic by conventional chemical routes. In this context, we studied the kinetics of this reaction as promoted by ZnS mineral photoelectrochemistry. The quantum efficiency φMA of MA production from the photoelectrochemical reduction of OAA followed φMA=0.13 [OAA] (2.1×10−3+[OAA])−1 and was independent of temperature (5 to 50°C). To evaluate the importance of this forward rate under a prebiotic scenario, we also studied the temperature-dependent rate of the backward thermal decarboxylation of OAA to pyruvate (PA), which followed an Arrhenius behavior as log (k−2)=11.74–4956/T, where k−2 is in units of s−1. These measured rates were employed in conjunction with the indirectly estimated carboxylation rate of PA to OAA to assess the possible importance of mineral photoelectrochemistry in the conversion of OAA to MA under several scenarios of prebiotic conditions on early Earth. As an example, our analysis shows that there is 90% efficiency with a forward velocity of 3 yr/cycle for the OAA→MA step of the rTCA cycle at 280 K. Efficiency and velocity both decrease for increasing temperature. These results suggest high viability for mineral photoelectrochemistry as an enzyme-free engine to drive the rTCA cycle through the early aeons of early Earth, at least for the investigated OAA→MA step.

Keywords

origin of lifephotoelectrochemistryprebiotic chemistryreductive citric acid cycletricarboxylic acid cyclezinc sulphide
Type
Research Article
Information
International Journal of Astrobiology , Volume 7 , Issue 3-4 , October 2008 , pp. 271 - 278
Copyright
Copyright © 2008 Cambridge University Press

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