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 C=C 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. (C) 2020 Elsevier B.V. All rights reserved.

Automated summary

The study used density functional theory to investigate the sensing mechanism of a fluorescence probe for cysteine and other thiols, showing that the probe molecule had different geometries in different excited states and exhibited stronger fluorescence in the presence of thiols. This can be attributed to the photoisomerization process and the distinct excited-processes of the probe, allowing it to effectively detect thiols through monitoring fluorescent changes.