Central-cis isomers of lutein found in the major light-harvesting complex of Photosystem II (LHC IIb) of higher plants

Lutein (beta,epsilon-carotene-3,3'-diol) is the major carotenoid of the light-harvesting systems of higher plants. Lutein was isolated at 4 degrees C and in complete darkness from the bulk light-harvesting complex of Photosystem II of spinach (LHC IIb) and from BBY particles. Separation using normal-phase HPLC (with 2D detection) in comparison to the authentic isomers (prepared by iodine-sensitised isomerization) showed the presence of a number of geometrical isomers of this xanthophyll in PS II, namely all-trans (the major component); 13-cis, 13'-cis and 15-cis-lutein. Iodine-sensitised photo-isomerization of all-trans lutein produced six geometrical isomers of lutein as determined by HPLC. The configuration of five of these isomers was determined by H-1-NMR to be all-trans, 9-cis, 9'-cis, 13-cis and 13'-cis. In addition, small amounts of another isomer have been tentatively identified to be 15-cis lutein on the basis of its electronic absorption spectrum. The possible functional significance of the presence of cis-isomers of this carotenoid in LHC IIb is discussed.