Singlet-oxygen generated by a metal–organic framework for electrochemical biosensing

Abstract

Enzyme-based electrochemical biosensors have been widely employed for analyte detection for several years. However, for wide application, there are many challenges to overcome, such as the sensitivity of the catalytic activity, and the reproducibility and stability of enzymes. In this work, an enzyme-free sensing strategy based on two-dimensional (2D) metal–organic frameworks (MOFs) as photosensitizers and singlet-oxygen (¹O₂) as the oxidant has been designed via photocatalysis and electrochemical analysis. To be specific, MOF sheets (Zn–ZnMOF) were prepared with Zn as the node and zinc(II)tetraphenylporphyrin (TCPP(Zn)) as the ligand, which could generate ¹O₂ from air under light illumination, and sequentially the generated ¹O₂ could oxidize analytes to form their oxidation state which could be detected and reduced on the electrode, completing a redox cycle and amplifying electrochemical signals. Thanks to the morphology and superior quantum yield of ¹O₂ of the Zn–ZnMOF, this method could overcome the limitation of enzymes and afford selective detection, such as of hydroquinone with a detection limit of 0.8 μM in 0.1 M PBS (pH = 7.4). Furthermore, the method does not require additional reactive reagents but only with air and on/off light switching. Thirdly, the method detects the target without washing and enzyme-labelled. With these merits, this work provides a new platform for MOFs as photosensitizers for electrochemical sensors and further development of sensitive, selective, and stable electroanalytical devices for bio-application.