The occurrence of the cis/trans geometric isomerism of myxoxanthophyll and 4-ketomyxoxanthophyll in the cyanobacterium Anabaena sp. PCC7120

Abstract

The cyanobacteria of the genus Anabaena have recently been recognized as a potential source of secondary metabolites of pharmacological and biotechnological importance. In particular, myxoxanthophylls – specific carotenoid glycosides that accumulate in cyanobacterial cells, are attracting increasing interest. Anabaena (Nostoc) sp. PCC7120, a filamentous, mesophilic, nitrogen-fixing cyanobacterium, is a model organism used in biochemical and genetic studies. The carotenoid pool of Anabaena sp. PCC7120 consists of five main species of pigments, namely β-carotene, echinenone, canthaxanthin and two derivatives of myxoxanthophyll: myxoxanthophyll ((3R,2‘S)-myxol 2’-fucoside) and 4-ketomyxoxanthophyll ((3S,2’S)-4-ketomyxol 2’-fucoside). Recent findings show that the carotenoid biosynthesis pathway functions in Anabaena sp. PCC7120 cells are affected by environmental factors. Specifically, the balance between β-carotene and ketocarotenoids alters according to the temperature conditions. In this study, a new method, based on single-step liquid adsorption chromatography was developed and applied to separate a fraction containing myxoxanthophyll and 4-ketomyxoxanthophyll from Anabaena sp. PCC7120 cells. It was found that this method allowed a high purity fraction of carotenoid glycosides to be obtained from pigment pools as extracted from cyanobacterial cells. The subsequent analysis using the methods HPLC and LC/MS demonstrated that this fraction consists of a mixture of compounds with different retention times. On the basis of their fragmentation spectra and optical properties, these compounds were identified as geometrical isomers of myxoxanthophyll and 4-ketomyxoxanthophyll, including the dominant alltrans forms and less abundant cis forms. Proposals regarding the structures of myxoxanthophyll isomers are made.