Complex Structures of Monoglucosylrutin with ent-Gallocatechin-3- O-gallate and Epigallocatechin-3- O-gallate in Aqueous Solutions and the Mechanism of Color Change Induced by Complexation.

The addition of ent-gallocatechin-3- O-gallate ( ent-GCg) or epigallocatechin-3- O-gallate (EGCg) to an aqueous solution of 4G-α-glucopyranosylrutin (monoglucosylrutin, MGR) causes the color of the solution to weaken due to complexation between MGR and these flavan-3-ols. Copigmentation is a well-known color change phenomenon resulting from the complexation of flavonoids that deepens and strengthens the color of the solution, whereas MGR/catechin complexation results in the opposite change in color (i.e., weakening). In order to gain insight into the mechanism underlying the rare changes in the color of solutions of complexes between flavonoids, the structures of the MGR monomer and the complexes in aqueous solutions and their photochemical properties were investigated by computational methods. Molecular dynamics simulations and subsequent density functional theory (DFT) calculations revealed that the complex structures are stabilized through aromatic/aromatic, CH/π, and OH/O interactions as direct intermolecular forces and that many solvent water networks would contribute to the complexations. Time-dependent DFT calculations showed that the change in the color of an MGR/ ent-GCg solution is due only to a decrease in absorbance, whereas that of an MGR/EGCg solution is due to both a decrease in absorbance and a hypsochromic shift.