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FTIR spectroscopy of the reaction center of Chloroflexus aurantiacus: Photooxidation of the primary electron donor

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Abstract

Photochemical oxidation of the primary electron donor P in reaction centers (RCs) of the filamentous anoxygenic phototrophic bacterium Chloroflexus (C.) aurantiacus was examined by light-induced Fourier transform infrared (FTIR) difference spectroscopy at 95 K in the spectral range of 4000–1200 cm−1. The light-induced P+Q −A /PQA IR spectrum of C. aurantiacus RCs is compared to the well-characterized FTIR difference spectrum of P photooxidation in the purple bacterium Rhodobacter (R.) sphaeroides R-26 RCs. The presence in the P+Q −A /PQA FTIR spectrum of C. aurantiacus RCs of specific low-energy electronic transitions at ∼2650 and ∼2200 cm−1, as well as of associated vibrational (phase-phonon) bands at 1567, 1481, and 1294–1285 cm−1, indicates that the radical cation P+ in these RCs has dimeric structure, with the positive charge distributed between the two coupled bacteriochlorophyll a molecules. The intensity of the P+ absorbance band at ∼1250 nm (upon chemical oxidation of P at room temperature) in C. aurantiacus RCs is approximately 1.5 times lower than that in R. sphaeroides R-26 RCs. This fact, together with the decreased intensity of the absorbance band at ∼2650 cm−1, is interpreted in terms of the weaker coupling of bacteriochlorophylls in the P+ dimer in C. aurantiacus compared to R. sphaeroides R-26. In accordance with the previous (pre)resonance Raman data, FTIR measurements in the carbonyl stretching region show that in C. aurantiacus RCs (i) the 131-keto C=O groups of PA and PB molecules constituting the P dimer are not involved in hydrogen bonding in either neutral or photooxidized state of P and (ii) the 31-acetyl C=O group of PB forms a hydrogen bond (probably with tyrosine M187) absorbing at 1635 cm−1. Differential signals at 1757(+)/1749(−) and 1741(+)/1733(−) cm−1 in the FTIR spectrum of C. aurantiacus RCs are attributed to the 133-ester C=O groups of P in different environments.

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Abbreviations

ΔA:

change in absorbance

BChl:

bacteriochlorophyll

BPheo:

bacteriopheophytin

Em :

midpoint redox potential

FTIR spectroscopy:

Fourier transform infrared spectroscopy

HOMO:

highest occupied molecular orbital

P:

primary electron donor, a dimer of BChl molecules

PA and PB :

BChl molecules comprising P

QA :

primary quinone acceptor

RC:

reaction center

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Authors and Affiliations

  1. Institute of Basic Biological Problems, Russian Academy of Sciences, ul. Institutskaya 2, 142290, Pushchino, Moscow Region, Russia

    A. A. Zabelin, V. A. Shkuropatova, V. A. Shuvalov & A. Ya. Shkuropatov

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  1. A. A. Zabelin
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  2. V. A. Shkuropatova
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  3. V. A. Shuvalov
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  4. A. Ya. Shkuropatov
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Correspondence to A. Ya. Shkuropatov.

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Original Russian Text © A. A. Zabelin, V. A. Shkuropatova, V. A. Shuvalov, A. Ya. Shkuropatov, 2012, published in Biokhimiya, 2012, Vol. 77, No. 2, pp. 196–204.

Originally published in Biochemistry (Moscow) On-Line Papers in Press, as Manuscript BM11-267, January 8, 2012.

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Zabelin, A.A., Shkuropatova, V.A., Shuvalov, V.A. et al. FTIR spectroscopy of the reaction center of Chloroflexus aurantiacus: Photooxidation of the primary electron donor. Biochemistry Moscow 77, 157–164 (2012). https://doi.org/10.1134/S000629791202006X

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