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Low potential manganese ions as efficient electron donors in native anoxygenic bacteria


Low potential manganese ions as efficient electron donors in native anoxygenic bacteria

Deshmukh, Sasmit S., Protheroe, Charles, Ivanescu, Matei-Alexandru, Lag, Sarah and Kálmán, László (2018) Low potential manganese ions as efficient electron donors in native anoxygenic bacteria. Biochimica et Biophysica Acta (BBA) - Bioenergetics . ISSN 00052728 (In Press)

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Official URL: http://dx.doi.org/10.1016/j.bbabio.2018.01.002


Systematic control over molecular driving forces is essential for understanding the natural electron transfer processes as well as for improving the efficiency of the artificial mimics of energy converting enzymes. Oxygen producing photosynthesis uniquely employs manganese ions as rapid electron donors. Introducing this attribute to anoxygenic photosynthesis may identify evolutionary intermediates and provide insights to the energetics of biological water oxidation. This work presents effective environmental methods that substantially and simultaneously tune the redox potentials of manganese ions and the cofactors of a photosynthetic enzyme from native anoxygenic bacteria without the necessity of genetic modification or synthesis. A spontaneous coordination with bis-tris propane lowered the redox potential of the manganese (II) to manganese (III) transition to an unusually low value (~400 mV) at pH 9.4 and allowed its binding to the bacterial reaction center. Binding to a novel buried binding site elevated the redox potential of the primary electron donor, a dimer of bacteriochlorophylls, by up to 92 mV also at pH 9.4 and facilitated the electron transfer that is able to compete with the wasteful charge recombination. These events impaired the function of the natural electron donor and made BTP-coordinated manganese a viable model for an evolutionary alternative.

Divisions:Concordia University > Faculty of Arts and Science > Physics
Item Type:Article
Authors:Deshmukh, Sasmit S. and Protheroe, Charles and Ivanescu, Matei-Alexandru and Lag, Sarah and Kálmán, László
Journal or Publication:Biochimica et Biophysica Acta (BBA) - Bioenergetics
Date:31 January 2018
  • Natural Sciences and Engineering Research Council of Canada
  • Canada Foundation for Innovation
Digital Object Identifier (DOI):10.1016/j.bbabio.2018.01.002
Keywords:photosynthesis; electron transfer; energy conversion; evolution; manganese
ID Code:983456
Deposited On:31 Jan 2018 20:11
Last Modified:31 Jan 2019 01:00
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