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Mechanism by which a single water molecule affects primary charge separation kinetics in a bacterial photosynthetic reaction center of Rhodobacter sphaeroides

  • Spectroscopy of Atoms and Molecules
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Abstract

Using quantum-chemical methods, we have studied the role played by water molecules W-A and W-B that are bound by hydrogen bonds to accessory bacteriochlorophyll molecules B A and B B in the process of primary charge separation in the reaction center of Rhodobacter Sphaeroides. We have found that the occurrence of a rotational mode of the W-A molecule at 32 cm−1 and/or its harmonics in stimulated emission of an electron donor P* and the dynamics of population of the states P+B − A and P+H − A may be related to the structural heterogeneity of the reaction center and the existence of a conformation in which the W-A molecule is predominantly involved in one hydrogen bond (with BA). Based on the calculated redox potentials B A and P, it has been shown that the appearance of the W-A molecule in the reaction center reduces the energy of the P+B − A state by ∼600 cm−1. This is somewhat smaller than the influence of the amino-acid residue TyrM210 (∼870 cm−1) and correlates well with a substantial decrease in the electron transfer rate in mutant forms of reaction centers GM203L (which do not contain W-A molecules) and YM210F (in which TyrM210 is replaced with Phe). The data obtained allow us to suggest that rotation of the water molecule with a fixed position of its H atom that is involved in a hydrogen bond with the keto carbonyl group of B A is initiated due to the charge separation between the halves of special pair P and the formation of the state P + A P − B . The large effect of this rotation on the kinetics of population of the states P+B − A and P+H − A after the excitation of P is quite consistent with its influence on the energy of the state P+B − A .

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  1. B.I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, Minsk, 220072, Belarus

    N. V. Ivashin & E. E. Shchupak

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  1. N. V. Ivashin
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Original Russian Text © N.V. Ivashin, E.E. Shchupak, 2012, published in Optika i Spektroskopiya, 2012, Vol. 113, No. 5, pp. 525–538.

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Ivashin, N.V., Shchupak, E.E. Mechanism by which a single water molecule affects primary charge separation kinetics in a bacterial photosynthetic reaction center of Rhodobacter sphaeroides . Opt. Spectrosc. 113, 474–486 (2012). https://doi.org/10.1134/S0030400X1209007X

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