Stimulus-Responsive Metal–Organic Framework Signal-Reporting System for Photoelectrochemical and Fluorescent Dual-Mode Detection of ATP

Dual-mode bioanalysis integrating photoelectrochemical (PEC) and other modes is emerging and allows signal cross-checking for more reliable results. Metal–organic frameworks (MOFs) have been shown to be attractive materials in various biological applications. This work presents the utilization of MOF encapsulation and stimuli-responsive decapsulation for dual-mode PEC and fluorescence (FL) bioanalysis. Photoactive dye methylene violet (MV) was encapsulated in zeolitic imidazolate framework-90 (ZIF-90) to form an MV@ZIF-90 hybrid material, and MV could be released by adenosine triphosphate (ATP)-induced ZIF-90 disintegration. The released MV not only had FL emission but also had a sensitization effect on the ZnIn2S4 (ZnInS) photoanode. Based on the MV-dependent sensitization effect and FL emission characteristic, a dual-mode PEC–FL strategy was established for ATP detection with low detection limits, that is, 3.2 and 4.1 pM for PEC and FL detection, respectively. This study features and will inspire the construction and implementation of smart MOF materials for dual-mode bioanalysis.