Structural effects on epimerization of bacteriochlorophyll a and chlorophyll a revealed using 3-acetyl chlorophyll a

Chlorophyll (Chl) and bacteriochlorophyll (BChl) pigments, which are crucial cyclic tetrapyrroles in photosynthesis, generally have a chiral center in their exo-cyclic five-membered E-ring. Although S-epimers (primed-type) of (B)Chl pigments are rarely present in photosynthetic organisms, they play key roles in photosynthetic reaction center complexes. The epimerization mechanism of (B)Chl pigments in vivo has not been unraveled. The structural effects on the physicochemical properties of (B)Chl epimerization reactions provide useful information to tackle this question. We analyzed epimerization of three pigments, BChl a, Chl a, and 3-acetyl Chl a, to elucidate the structural factors that are responsible for epimerization reactions. We compared the epimerization kinetics of the three pigments and concluded that the bacteriochlorin skeleton (7,8,17,18-tetrahydroporphyrin) significantly retarded the epimerization kinetics. Thus, BChl a exhibited slower epimerization kinetics than Chl a in spite of the presence of the electron-withdrawing 3-acetyl group that accelerates epimerization. In contrast to the large structural effects of (B)Chl molecules on epimerization kinetics, the thermodynamic properties at equilibrium in the epimerization of the three pigments were barely influenced by their molecular structures. This study also demonstrates that a semi-synthetic pigment, 3-acetyl Chl a, is appropriate for comparative analyses of the structural effects of BChl a and Chl a on their physicochemical properties.