Theoretical study on the sensing mechanism of a coumarin-based fluorescent probe for biological thiols

The sensing mechanism of a reported fluorescence probe for cysteine, homocysteine and glutathione (Yin et al., 2018) has been investigated by time-dependent density functional theory. Experimental absorption and emission spectra of the probe before and after thiol addition were reproduced well by theoretical calculations, which validated the rationality of the method. Optimized geometries showed that the probe molecule had distinctly different geometries in its ground and excited states. It corresponded to the photoisomerization process and explained the weak fluorescence of the probe molecule. Moreover, by the potential energy curve scan, photoisomerization was further confirmed to be a spontaneous process with a barrier that barely existed. Frontier orbital analysis indicated that this photoinduced isomerization of the probe molecule derived from the antibonding character for lowest unoccupied molecular orbital at its CC double bond. In contrast, probe-thiol complexes exhibited similar geometries in their ground and excited states, which was responsible for the strong fluorescence of the probe with thiols. Due to distinct excited-processes, the probe can be used to sense thiols by monitoring the fluorescent change.