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Pigment-modified reaction centers of Chloroflexus aurantiacus: chemical exchange of bacteriopheophytins with plant-type pheophytins

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Abstract

The pigment composition of isolated reaction centers (RCs) of the green filamentous bacterium Chloroflexus (Cfl.) aurantiacus was changed by chemical exchange of native bacteriopheophytin a (BPheo) molecules with externally added pheophytin a (Pheo) or [3-acetyl]-Pheo upon incubation of RC/pheophytin mixtures at room temperature and 45 °C. The modified RCs were characterized by Vis/NIR absorption spectroscopy, and the effect of pigment exchange on RC photochemical activity was assessed by measuring the photoaccumulation of the reduced pigment at the binding site HA. It is shown that both pheophytins can be exchanged into the HA site instead of BPheo by incubation at room temperature. While the newly introduced Pheo molecule is not active in electron transfer, the [3-acetyl]-Pheo molecule is able to replace functionally the photoreducible HA BPheo molecule with the formation of the [3-acetyl]-Pheo radical anion instead of the BPheo. After incubation at 45 °C, the majority (~ 90%) of HA BPheo molecules is replaced by both Pheo and [3-acetyl]-Pheo. Only a partial replacement of inactive BPheo molecules with pheophytins is observed even when the incubation temperature is raised to 50 °C. The results are discussed in terms of (i) differences in the accessibility of BPheo binding sites for extraneous pigments depending on structural constraints and incubation temperature and (ii) the effect of the reduction potential of pigments introduced into the HA site on the energetics of the charge separation process. The possible implication of Pheo-exchanged preparations for studying early electron-transfer events in Cfl. aurantiacus RCs is considered.

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Abbreviations

ΔA:

Light-induced absorbance changes

BChl:

Bacteriochlorophyll a

BA and BB :

Binding sites for monomeric BChls at the active and inactive cofactor branch, respectively

BPheo:

Bacteriopheophytin a

Cfl. :

Chloroflexus

H and HA :

Binding sites for BPheos at the active and inactive cofactor branch, respectively

ϕ B :

The inactive BPheo binding site in Cfl. aurantiacus RCs corresponding to the BChl BB site in purple bacterial RCs

LDAO:

N,N-dimethyldodecyl-amine-N-oxide

P:

Primary electron donor

Pheo:

Pheophytin a

Rba. :

Rhodobacter

RC(s):

Reaction center(s)

QA and QA :

Primary and secondary quinone acceptor, respectively

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Acknowledgements

This work was performed under State Task No. AAAA-A17030110140-5. We are grateful to V.A. Shkuropatova for the preparation of reaction centers and assistance in carrying out modification experiments.

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Correspondence to Anatoly Ya. Shkuropatov.

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Zabelin, A.A., Shkuropatov, A.Y. Pigment-modified reaction centers of Chloroflexus aurantiacus: chemical exchange of bacteriopheophytins with plant-type pheophytins. Photosynth Res 149, 313–328 (2021). https://doi.org/10.1007/s11120-021-00855-x

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