The influence of pH on UV/Vis spectra of gallic and ellagic acid: A combined experimental and computational study

The pH dependence of the UV/Vis spectrum of gallic and ellagic acid was measured in a buffer-free solution to obtain reliable data at wavelengths bellow 230 nm. UV/Vis absorption spectra were also calculated for all possible ionised species of gallic and ellagic acid using time dependent density functional theory (TD-DFT). From pKa values of gallic and ellagic acid the molar fraction of different ionised species was calculated for each pH value. Finally, the simulated spectra at different pH values were obtained as a weighted average of spectra of neutral, once, twice, three-times, and four-times deprotonated species. The calculated spectra were then compared to the experimental spectra, and the peaks in the experimental spectrum were explained in the terms of main electronic transitions that results in the observed absorption bands. At low pH values the agreement between the experimental and calculated spectra was excellent. At near-neutral pH values the majority of the experimental spectra features were well reproduced in the calculated spectra. A satisfactory agreement between experimental and calculated spectrum at high pH values was also achieved by incorporating the calculated spectra of the oxidised species of gallic acid as well as ellagic acid spectra with one lactone ring open. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

The pH dependence of the UV/Vis spectrum of gallic and ellagic acid was measured in a buffer-free solution to obtain reliable data at wavelengths below 230 nm. Calculated spectra were compared to experimental spectra to explain absorption peaks in terms of main electronic transitions. Good agreement was observed between experimental and calculated spectra at low and near-neutral pH values. Incorporating calculated spectra of oxidized species of gallic acid and ellagic acid with one lactone ring open also achieved satisfactory agreement at high pH values.