Surface complexes of xanthophyll films with transition metal ions

Compression isotherms of astaxanthin (AX; 3,3'-dihydroxy-4,4'-dioxo-beta-carotene) monolayers, recorded at the air/water interface show, on the one hand, the collapse pressure to depend on the subphase pH, indicating the ionisation of AX at high pH values, and on the other hand, the subphase Co2+ ions to have a condensing effect upon the monolayer and to entail the increase of its collapse pressure. The latter effects are assigned to surface complex formation. The interfacial tension at the benzene/water interface (the benzene phase containing AX, the water phase Co2+ ions) exhibit a maximum at a molar ratio AX: Co of about 3.6, pleading for the formation of relatively stable Co(AX)4 type interfacial complex. Geometric model and ligand field considerations show besides the dative type sigma-bond formation, the possibility of both dative and retrodative type pi-bond formation between Co2+ and the AX ligands. Under the working conditions used, the formation of a neutral non-electrolyte type complex of the composition [Co(LH)2L2] is postulated, where LH stands for the neutral AX molecule, L- for its anion.