Experimental and theoretical study of the fluorescence emission of ferulic acid: Possible insights into the fluorescence properties of humic substances

Ferulic acid ((E)-3-(4-hydroxy-3-methoxy-phenyl)prop-2-enoic acid, hereinafter FA) is a building block of plant cell walls that is commonly found in lignocellulose. As such, it is a potential component of humic substances produced by microbial degradation of plant spoils. The fluorescence excitation-emission matrix spectra of FA have an interesting humic-like shape, with bands that can be assimilated to the A and C regions of humic substances. Therefore, the study of FA photoluminescence might provide interesting insight into the still unknown processes that lay behind the fluorescence properties of humic compounds. FA is a weak diprotic acid that occurs in three different forms in aqueous solution (neutral H(2)FA, singly deprotonated HFA(-) and doubly deprotonated FA(2-)), which have slightly different absorption and emission properties. The A-like fluorescence emission of the FA species is accounted for by excitation from the ground singlet state S-0 to singlet excited states higher than the first (S-4 for H(2)FA, S-5 for HFA(-), and a state higher than S-2 for FA(2-)), followed by radiationless deactivation to the first excited singlet state (S-1), and by fluorescence emission according to the S-1 -> S-0 transition. In contrast, the C-like emission is mainly caused by S-0 -> S-1 excitation combined with S-1 -> S-0 emission, but there is also a minor contribution from the S-0 -> S-2 excitation that becomes significant for HFA(-). The uneven variations with pH of the wavelengths of the maximum FA radiation absorption and fluorescence emission can be rationalised in the framework of the energy levels of the frontier (HOMO and LUMO) molecular orbitals of the different FA species. These levels are affected by charge interaction between the relevant electrons and the neutral (protonated) or negative (deprotonated) groups of each species. (c) 2019 Elsevier B.V. All rights reserved.