A cerium-based metal–organic framework having inherent oxidase-like activity applicable for colorimetric sensing of biothiols and aerobic oxidation of thiols

• Published in: CrystEngComm Vol. 19; no. 39; pp. 5915 - 5925
• Main Authors: Dalapati, Rana, Sakthivel, Balasubramanian, Ghosalya, Manoj K., Dhakshinamoorthy, Amarajothi, Biswas, Shyam
• Format: Journal Article
• Language: English
• Published: 2017
• ISSN: 1466-8033; 1466-8033
• DOI: 10.1039/C7CE01053B

A cerium-based metal–organic framework (MOF; 1 ) with a UiO-66 (UiO: University of Oslo) framework topology was synthesized solvothermally by employing 3,4-dimethylthieno[2,3- b ]thiophene-2,5-dicarboxylic acid as a ligand. The MOF was thoroughly characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction, infrared spectroscopy, and thermogravimetric and N 2 sorption analyses. The activated material ( 1′ ) retained its structural integrity in water, acetic acid and 1 M HCl solution. XPS investigation reveals the presence of both Ce( iii ) and Ce( iv ) ions in 1 . Owing to the presence of mixed-valence cerium ions, 1′ was able to oxidize the chromogenic peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) or 2,2′-azinobis(3-ethylbenzothizoline-6-sulfonic acid) (AzBTS) in the absence of an external oxidizing agent. Thus, it showed inherent oxidase-like catalytic properties. Inspired by the excellent oxidase-mimicking activity of 1′ , a protocol was developed for the rapid colorimetric sensing of biothiols in NaAc buffer (0.2 M, pH = 4). The sensing ability of 1′ towards cysteine was also demonstrated in human blood plasma. Furthermore, the redox-active cerium ions enabled 1′ to exhibit excellent heterogeneous catalytic performance in aerobic oxidation catalysis of thiol compounds. The material is reusable (both as a sensor and as a catalyst), low-cost and highly stable, which renders it a promising candidate for the monitoring of biothiols in immunoassays and medical diagnosis as well as for industrial oxidation catalysis.