Response Characteristics of Bisphenols on a Metal-Organic Framework-Based Tyrosinase Nanosensor.

Bisphenols (BPs), which have more than ten kinds of structural analogues, are emerging as the most important endocrine disrupting chemicals that adversely affect human health and aquatic life. A tyrosinase nanosensor based on metal-organic frameworks (MOFs) and chitosan was developed to investigate the electrochemical response characteristics and mechanisms of nine kinds of BPs for the first time. The developed tyrosinase nanosensor showed a sensitive response to bisphenol A, bisphenol F, bisphenol E, bisphenol B, and bisphenol Z, and the responsive sensitivities were highly dependent on their respective log Kow values. However, the nanosensor showed no response to bisphenol S (BPS), bisphenol AP (BPAP), bisphenol AF (BPAF), or tetrabromobisphenol A, although BPS, BPAP, and BPAF have structures similar to those of the responsive BPs. The obtained results reveal that the electrochemical response of different BPs is affected not only by the molecular structure, especially the available ortho positions of phenolic hydroxyl groups, but also by the substituent group properties (electron acceptor or electron donor) on the bisphenol framework. The electronic cloud distribution of the phenolic hydroxyl groups, which is affected by the substituent group, determines whether the available ortho positions of phenolic hydroxyl groups can be oxidized by the tyrosinase biosensor. These response mechanisms are very significant as they can be used for predicting the response characteristics of many BPs and their various derivatives and metabolites on biosensors. The unexpected anti-interference ability of the biosensor to nine heavy metal ions was also discovered and discussed. The MOF-chitosan nanocomposite proves to be a promising sensing platform for the construction of diverse biosensors for selective detection of targets even in the presence of a high concentration of heavy metal ions.