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Isomerization kinetics of bacteriochlorophyll b and bacteriopheophytin b under acidic conditions

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Abstract

Bacteriochlorophyll (BChl) b has a unique π-conjugation system, in which the bacteriochlorin macrocycle is conjugated with the C8-ethylidene group. This π-system is converted easily to the chlorin macrocycle. However, the effects of the central magnesium in BChl b on this conversion are unclear. In this study, the isomerization kinetics of BChl b and its demetalated pigment, bacteriopheophytin (BPhe) b, was analyzed under weakly acidic conditions. BChl b exhibited faster acid-induced isomerization than BPhe b. These results were attributed to the stabilization of a cationic intermediate, whose C8-ethylidene group is protonated, during the isomerization of BChl b compared to BPhe b because of a difference in the electron densities of the π-conjugation systems between BChl b and BPhe b. High-performance liquid chromatography analyses indicated that BChl b was primarily isomerized to 3-acetyl Chl a, followed by demetalation. The reaction order was due to the slower demetalation kinetics of metallobacteriochlorins than metallochlorins. These results will be helpful for handling unstable BChl b and BPhe b. The reaction properties of BChl b and BPhe b demonstrated here will be helpful for understanding the in vivo formation of BPhe b, which acts as the primary electron acceptor in photosynthetic reaction center complexes in BChl b-containing purple photosynthetic bacteria.

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Abbreviations

AcChl:

3-Acetyl chlorophyll

AcPhe:

3-Acetyl pheophytin

BChl:

Bacteriochlorophyll

BPhe:

Bacteriopheophytin

Chl:

Chlorophyll

ESI:

Electrospray ionization

HPLC:

High-performance liquid chromatography

MS:

Mass spectrometry

RC:

Reaction center

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Funding

This work was partially supported by Grants-in-Aid for Scientific Research (C) (JP18KT0094 and JP21K06104) from the Japan Society for the Promotion of Science.

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  1. Department of Chemistry, Faculty of Science and Engineering, Kindai University, Higashi-Osaka, Osaka, 577-8502, Japan

    Yusuke Takashima & Yoshitaka Saga

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  1. Yusuke Takashima
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  2. Yoshitaka Saga
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Correspondence to Yoshitaka Saga.

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Takashima, Y., Saga, Y. Isomerization kinetics of bacteriochlorophyll b and bacteriopheophytin b under acidic conditions. Photochem Photobiol Sci 21, 1193–1199 (2022). https://doi.org/10.1007/s43630-022-00207-1

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  • DOI: https://doi.org/10.1007/s43630-022-00207-1

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