Visible Light-Activatable Oxidase Mimic of 9-Mesityl-10-Methylacridinium Ion for Colorimetric Detection of Biothiols and Logic Operations.

In this work, 9-mesityl-10-methylacridinium ion (Acr+-Mes) is found to act as an effective photocatalyst mimicking the function of oxidase. Upon visible light illumination, the excited Acr+-Mes is able to exhibit superior enzymatic catalytic activity for small molecular substrates as well as protein biomacromolecule (cytochrome c). The experiment results demonstrate that the Acr+-Mes oxidase mimic shows higher affinity to 3,3',5,5'-tetramethylbenzidine (TMB) than natural horseradish peroxidase or the reported molecule oxidase mimic. The reaction mechanism is ascribed to the strong oxidation property of the long-lived electron-transfer state (Acr•-Mes•+) and the electron transfer from Acr•-Mes radical to dissolved oxygen to generate superoxide radicals, which can easily oxidize various substrates. On the basis of these observations, the light-activatable Acr+-Mes with an oxidase-like activity as the probe is utilized for cost-effective, sensitive, and highly selective colorimetric detection of two biothiols (L-cysteine and L-glutathione). The lowest detectable concentrations of L-Cys and L-GSH is 100 nM, which is lower than that of most of the reported methods for biothiols. Beyond this, we construct a series of visual molecular logic gates (AND, INH, and NOR) using the oxidase mimic-involved reaction systems.