ABSTRACT
An aqueous solution of equimolecular amounts of gallated catechin (-)-epigallocatechin-3-O-gallate (EGCg) and caffeine afforded a crude precipitate by creaming, which crystallized slowly for about three months at 10°C to give a colorless block crystal. The crystal was determined to be a 2 : 2 complex of EGCg and caffeine by X-ray crystallographic analysis. The 2 : 2 complex was formed with the cooperative effect of three intermolecular interactions, π-π and CH-π interactions, and intermolecular hydrogen bonds. Upon formation of the 2 : 2 complex, a caffeine molecule was captured by a hydrophobic space formed by the aromatic rings A, B, and B' rings of two EGCg molecules. Judging from the entropy value, the shift value in the chemical shift of proton signals in (1)H-NMR spectra, the NT1 value, and nuclear Overhauser effects (NOEs), it was thought that the structure of complexes of EGCg and caffeine in aqueous solution were the same as their crystal structure.
Subject(s)
Caffeine/chemistry , Catechin/analogs & derivatives , Chemical Precipitation , Catechin/chemistry , Models, Molecular , Molecular StructureABSTRACT
The content of a crude precipitate formed by creaming, which was made from a catechin mixture and caffeine, was investigated by an integral volume of H-2 proton signals of tea catechins in the (1)H-NMR spectrum. Gallated catechins formed a crude precipitate more predominantly than non-gallated catechins. The 2,3-cis-non-gallated catechin (-)-epicatechin (EC) formed a 1:1 complex with caffeine, and 2,3-cis-gallated catechin (-)-epicatechin gallate (ECg) formed a 2:4 complex with caffeine. The π-π complexation site of EC with caffeine was only the A ring, whereas that of ECg included all aromatic rings, A, B, and B'. It was thought that the hydrophobicity of the 2:4 complex of ECg and caffeine was stronger than that of the 1:1 complex of EC and caffeine, with the result that the 2:4 complex of ECg and caffeine precipitated by creaming more predominantly than the 1:1 complex of EC and caffeine in aqueous solution.
Subject(s)
Caffeine/chemistry , Catechin/chemistry , Catechin/analogs & derivatives , Chemical Precipitation , Crystallography, X-Ray , Magnetic Resonance Spectroscopy , Models, Molecular , SolutionsABSTRACT
Crystals of the complexes of (+)-catechin (CA) of non-galloylated catechin and (-)-catechin-3-O-gallate (Cg) of galloylated catechin with caffeine were prepared, and their stereochemical structures and intermolecular interactions were determined by X-ray crystallographic analysis. CA formed a 1 : 1 complex with caffeine by intermolecular hydrogen bonds, whereas Cg formed a 1 : 2 complex with caffeine, which was formed by face-to-face and offset π-π interactions and intermolecular hydrogen bonds. A solution of two kinds of non-galloylated catechin, CA and (-)-epicatechin (EC), and caffeine (molar ratio 1 : 1 : 2) in water afforded a 1 : 1 : 2 complex, the crystal structure of which had two layers, one layer in which CA and caffeine formed alternate lines and an other layer in which EC and caffeine formed alternate lines. The 1 : 1 : 2 complex was formed by offset π-π and CH-π interactions and intermolecular hydrogen bonds.
