A time-dependent density functional theory (TD-DFT) study was carried out on tautomers of the mycotoxin citrinin in the neutral, anionic, and cationic forms to gain insight into the role of chemical structure on detection. Steady-state fluorescence studies of citrinin in micellar aqueous solutions produced unusual results for ionic surfactants and the neutral Triton X-100 enhanced fluorescence emission. Ground-state and time-dependent density functional studies were carried out on five tautomers of citrinin using the B3LYP density functional and the 6-311+G(2df,2p) basis set. The investigation revealed that deprotonation is a major factor governing the shifts in fluorescence excitation and emission maxima. Moreover, the position of the lowest unoccupied molecular orbitals is removed from the fluorophore moiety of citrinin in the dianionic state which is consistent with the diminished fluorescence of the toxin in basic solutions. The ionic characteristics of certain chemosensors can influence the structure and intrinsic spectroscopic properties of citrinin.
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