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Stereoselective self-aggregation of synthetic zinc 31-epimeric bacteriochlorophyll-d analogs possessing a methylene group at the 132-position as models of green photosynthetic bacterial chlorosomes

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Abstract

Zinc bacteriochlorophyll-d analogs possessing a methylene group at the 132-position were prepared by chemical modification of naturally occurring chlorophyll-a. The synthetic 31-epimers were successfully separated by reverse phase HPLC to give diastereomerically pure samples. The stereochemistry of the chiral C31-center in the separated bacteriochlorophyll-d analogs was determined by HPLC analysis of the authentic stereoisomers prepared stereospecifically. Both the epimers were monomeric in tetrahydrofuran to give sharp absorption bands, while they self-aggregated to form chlorosomal oligomers with red-shifted bands in an aqueous Triton X-100 micelle solution. The resulting large oligomers deaggregated by addition of Triton X-100 to give monomeric species. Their aggregation and deaggregation were dependent on the 31-stereochemistry, indicating that each epimer produced self-aggregates that were supramolecularly different. The substitution with the 132-methylene group enhanced their self-aggregation abilities and the stability of their resulting self-aggregates.

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  1. Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, Shiga, 525-8577, Japan

    Yoshiki Fujiwara & Hitoshi Tamiaki

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  1. Yoshiki Fujiwara
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Correspondence to Hitoshi Tamiaki.

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Fujiwara, Y., Tamiaki, H. Stereoselective self-aggregation of synthetic zinc 31-epimeric bacteriochlorophyll-d analogs possessing a methylene group at the 132-position as models of green photosynthetic bacterial chlorosomes. Photochem Photobiol Sci 18, 1218–1227 (2019). https://doi.org/10.1039/c8pp00535d

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