Molecular Stark effect spectroscopy of diflavonol and inhomogeneous broadening of its electronic spectra in erythrocyte membranes

Abstract

Using spectroscopy of the molecular Stark effect and fluorescence spectroscopy, we study the characteristics of diflavonol 3,7-dihydroxy-2,8-di(4-dimethylaminophenyl)-4H,6H-pyrano[3,2-g]chromene-4,6-dione (DFME), which demonstrates intramolecular charge and proton phototransfer. In the ground state, this dye has only one form and, in the excited state, it has two forms, i.e., normal and phototautomeric. We found that, for the normal form of DFME, the transition dipole moment that is responsible for the absorption (m a ), the dipole moment in the equilibrium ground state (μ g ), and the change of the dipole moment upon transition of the molecule in the excited Franck-Condon state (Δ a μ) are parallel. In the ground equilibrium state, the dipole moments in 1,4-dioxane and cyclohexane are equal to μg = 12.2 × 10−30 C m and μ g = 11.0 × 10−30 C m, respectively. Upon excitation, they increase by Δ a μ = 61 × 10−30 C m and Δ a μ = 50.2 × 10−30 C m in these solvents. We study the spectral characteristics of DFME in organic solvents and erythrocyte membranes. A spectral inhomogeneity of DFME in erythrocyte ghosts is found. The inhomogeneous broadening of fluorescence spectra is manifested as a long-wavelength shift of the band of the normal form of DFME by 1640 cm−1 upon excitation at the red edge of the absorption spectrum.