To understand the photochemical behaviour of the polydopamine polymer in detail, one would also need to know the behaviour of its building blocks. The electronic absorption, as well as the fluorescence emission and excitation spectra of the dopamine were experimentally and theoretically investigated considering time-resolved fluorescence spectroscopy and first-principles quantum theory methods. The shape of the experimental absorption spectra obtained for different dopamine species with standard, zwitterionic, protonated, and deprotonated geometries was interpreted by considering the advanced equation-of-motion coupled-cluster theory of DLPNO-STEOM. Dynamical properties such as fluorescence lifetimes or quantum yield were also experimentally investigated and compared with theoretically predicted transition rates based on Fermi’s Golden Rule-like equation. The results show that the photochemical behaviour of dopamine is strongly dependent on the concentration of dopamine, whereas in the case of a high concentration, the zwitterionic form significantly affects the shape of the spectrum. On the other hand, the solvent pH is also a determining factor for the absorption, but especially for the fluorescence spectrum, where at lower pH (5.5), the protonated and, at higher pH (8.0), the deprotonated forms influence the shape of the spectra. Quantum yield measurements showed that, besides the radiative deactivation mechanism characterized by a relatively small QY value, non-radiative deactivation channels are very important in the relaxation process of the electronic excited states of different dopamine species.

Quercetin, one of the most abundant flavonoids in plant-based foods, commonly occurs in nature in various glycosylated forms. There is still a less explored aspect regarding the cause of diversity of its glycosides, depending on the sugar moiety attached. This work focuses on four wide-spread quercetin glycosides—hyperoside, isoquercitrin, quercitrin and rutin—by testing the property-tuning capacity of different sugar moieties and thus explains and predicts some of their functions in plant-based foods. The electron paramagnetic spectra of the semiquinone anion radicals of these glycosides were interpreted in terms of hyperfine coupling constants and linewidths, highlighting a clear link between spin density trends, the identity of the bound sugar, and their reactivity corroborated with their modelled structures. Redox potential and lipophilicity were connected to a specific flavonoid-enzyme interaction and correlated with their prooxidant reactivity assessed by oxidation of ferrous hemoglobin. Hyperoside and isoquercitin—galactose and glucose glycosides—exhibit the highest prooxidant reactivity owing to their lowest redox potential and lipophilicity whereas rutin and quercitrin—rutinose and rhamnose glycosides—behave vice versa. The ability of the tested glycosides to undergo HAT or SET-type reactions has also been tested using five different analytical assays, including inhibition of cytochrome c-triggered liposome peroxidation. In most cases, rutin proved to be the most unreactive of the four tested glycosides considering either steric or redox reasons whereas the reactivity hierarchy of the other three glycosides were rather assay dependent.