Achieving synergistically enhanced dual-mode electrochemiluminescent and electrochemical drug sensors via a multi-effect porphyrin-based metal-organic framework

Since the sensing methods in drug detection are commonly hampered by signal capacity limitations and sole analysis information, dual-mode sensors with high accuracy and flexibility have become more popular. Herein, we present a two-dimensional porphyrin-based metal-organic framework (ZnTCPP MOF) as a unique electrochemiluminescent (ECL) and electrochemical (EC) dual-signal indicator, combined with L-penicillamine-capped Au nanoparticles (L-Pen-Au NPs) as a specific selector, to construct an innovative dual-mode drug sensing platform. Inspired by the optical and electrocatalytic activity of 5,10,15,20-tetrakis-(4-carboxyphenyl)porphyrin (TCPP), a series of ZnTCPP MOFs have been synthesized through a facile bottom-up method. Among them, the “oval-like” ZnTCPP MOF generates higher ECL responses than TCPP monomer when acting as a near-infrared luminophore and outputs stronger EC signals when acting as a redox active probe. In addition, the ZnTCPP MOF, when employed as a nanocarrier, can load many L-Pen-Au NPs. Using L-Pen-Au NPs as selectors, synergistically enhanced dual-mode sensors for detection of the anti-inflammatory drug S-naproxen (S-NAP) exhibit versatile and superior performance and a wide linear range with an ultralow limit of detection. We believe that the applications of this dual-mode sensor can be readily expanded to become a universal platform for sensitive detection of different types of drugs by changing the selector.