Growth model of chlorosome antenna by the environment-dependent stepwise assembly of a zinc chlorophyll derivative

A zinc chlorophyll derivative possessing an oligoethylene glycol ester at the 17-propionate residue was prepared as a model of specific pigments in chlorosomes, such as bacteriochlorophylls-c, d, and e, by chemical modification of naturally occurring chlorophyll-a. The zinc chlorophyll derivative aggregated in aqueous or hexane solutions containing 1% (v/v) ethanol to give red-shifted and broadened Soret/Qy absorption bands with intense circular dichroism signals, indicating the formation of its chlorosome-like J-type self-aggregates. The atomic force microscope images of the self-aggregates prepared in aqueous or hexane solutions showed thin tube-like (ca. 3 nm diameter) or thick rod-like aggregates (> 20 nm diameter), respectively. After standing these solutions for several days, the nanotubes or nanorods further assembled to give ribbon- or bundle-like aggregates, respectively. The latter transformation (tube to ribbon) was triggered by hydrogen bonding between oligoethylene glycol esters located outside of the tubes via water or ethanol molecules. These dynamic supramolecular transformations may also be useful for revealing the growth process of bacteriochlorophyll self-aggregates in a chlorosome.