Xanthophyll pigments lutein and zeaxanthin in lipid multibilayers formed with dimyristoylphosphatidylcholine

This paper reports the research on the effect of two main carotenoid pigments present in the membranes of macula lutea of the vision apparatus of primates, including humans, lutein and zeaxanthin, on the structure of model membranes formed with dimyristoylphosphatidylcholine (DMPC). The effects observed in DMPC are compared to the effects observed in the membranes formed with other phosphatidylcholines (PC): egg yolk PC (EYPC), and dipalmitoyl-PC (DPPC). The analysis has been focused, in particular, on the following aspects of the organization of lipid-carotenoid membranes: aggregation state of pigments, an effect on a thickness of the bilayer and pigment orientation within the membranes. These problems have been addressed with the application of UV-Vis absorption spectroscopy, linear dichroism measurements and the diffractometric technique. (1) Both lutein and zeaxanthin appear in a partially aggregated form in the oriented DMPC multibilayers, even at molar fractions as low as 2 mol.% with respect to lipid. (2) Orientation of the transition dipole of both xanthophylls with respect to the axis normal to the plane of DMPC membrane is different in the case of a monomeric form (34+/-3 degrees in the case of lutein and 26+/-3 degrees in the case of zeaxanthin) but essentially the same in the case of aggregated forms of both pigments (42+/-3 degrees in the case of lutein and 40+/-5 degrees in the case of zeaxanthin). It was found that only lutein has an effect on the increase in the thickness of the DMPC membranes (by about 3 A at 25 degrees C). A similar effect was observed also in the case of DPPC at the same temperatures despite the differences in the physical state of both membrane systems. The differences between the effects of lutein and zeaxanthin observed are interpreted in terms of differences of stereochemical structure of both xanthophylls leading to the different localization in the lipid phase. The results demonstrate significant differences in the behavior of lutein and zeaxanthin in model membranes, which may contribute to their different physiological functions and different efficacy as membrane antioxidants.