Comparative Study of Fluorescence Emission of Fisetin, Luteolin and Quercetin Powders and Solutions: Further Evidence of the ESIPT Process

Abstract

Fisetin and Luteolin are important flavonoids produced in plants and known for their antioxidant, anti-inflammatory, neuroprotective, and analgesic properties. They are also good candidates for different types of biosensors. The model used to describe the fluorescence (FL) emission of these flavonoids involves an excited-state intermolecular proton transfer (ESIPT) process that causes a change in the molecule configuration and a corresponding decrease in the emission energy. Due to the different molecular structures of Fisetin and Luteolin, only one possible proton transfer within the molecule is allowed for each of them: transfer of the H3 proton for Fisetin and of the H5 for Luteolin. Here, we compare their calculated emission wavelengths, obtained using TDDFT/M06-2X/6-31++G(d,p), with their FL emission spectra measured on the corresponding powders and solutions and show that the experimental data are consistent with the presence of the ESIPT process. We also compare the emission wavelengths found for Fisetin and Luteolin with those calculated and measured for Quercetin, where, under photoexcitation, the transfers of both H3 and H5 protons are possible. We analyze the difference in the processes associated with the H3 and H5 proton transfers and discuss the reason for the predominance of the H5 proton transfer in Quercetin. Additionally, a new system of notation for flavonoid molecules is developed.