Structure and chiroptical properties of supramolecular flower pigments.
Research over the last 30 years has shown that at physiological concentrations of ca. 5 x 10(-3) M, flower pigments composed of anthocyanins, either alone or complexed with flavone copigments, and frequently with metals, are self-assembled into non-covalent, chiral supramolecular complexes. This serves several biological functions including color stability, protection against UV radiation and provision for specific colors to attract insects for pollination. Self-association of the monomers takes place under conditions of molecular crowding by precise matching of the pi-pi stacking interactions of the aromatic chromophores and intermolecular hydrogen bonding between the attached sugars. The resulting handedness is controlled by the chiral information provided by the sugars joined glycosidically at certain positions around the periphery of the aromatic nuclei. This review gives an overview of (i) the physicochemical evidence including circular dichroism, (1)H NMR, and X-ray analysis for the structure and supramolecular chirality of these amphiphilic complexes, (ii) the role of the sugars on directing the chirality of the resulting supramolecules, (iii) the energetics of monomer association, and (iv) the possible influence of stacking chirality on insect pollination.
Ellestad
George A
GA
Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, USA. gae2104@columbia.edu
D000872:Anthocyanins / Q000737:chemistry; D001578:Benzopyrans / Q000737:chemistry; D002109:Caffeic Acids / Q000737:chemistry; D002942:Circular Dichroism; D031806:Eichhornia / Q000378:metabolism; D035264:Flowers; D005960:Glucosides / Q000737:chemistry; D006027:Glycosides / Q000737:chemistry; D006860:Hydrogen Bonding; D046911:Macromolecular Substances / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008958:Models, Molecular; D010860:Pigments, Biological / Q000737:chemistry*; D013237:Stereoisomerism; D014466:Ultraviolet Rays; D014965:X-Rays
D000872:Anthocyanins; D001578:Benzopyrans; D002109:Caffeic Acids; D005960:Glucosides; D006027:Glycosides; D046911:Macromolecular Substances; D010860:Pigments, Biological; C414932:gentiodelphin; C040048:caffeic acid