Biomimetic self-assembly of lipase-zeolitic imidazolate frameworks with enhanced biosensing of protox inhibiting...

Protox inhibiting herbicides such as nitrofen have detrimental effects on the environment and human health. The current work aims to fabricate a Candida rugosa lipase (CRL)-based electrochemical sensor for rapid and sensitive detection of protox inhibiting herbicides (nitrofen). We proposed the use of poly(vinylpyrrolidone) (PVP) and amino-acids to promote accumulation of Zn²⁺ ions at the surfaces of Candida rugosa lipase (CRL) and subsequently induce self-assembly of a CRL-zeolitic imidazolate framework (ZIF) structure. This process can be easily and rapidly achieved via a one-pot facile self-assembly method. Steady-state fluorescence spectroscopy indicated that CRL has undergone a conformational change following encapsulation within the ZIF structure. This conformational change is beneficial as the prepared PVP/Glu/CRL@ZIF-8 exhibited enhanced catalytic activity (207% of native CRL), and higher substrate affinity (lower K_m than native CRL) and showed high stability under harsh denaturing conditions. PVP/Glu/CRL@ZIF-8 was finally used for electrochemical biosensing of nitrofen. The fabricated biosensor has a wide linear detection range (0-100 μM), a lower limit of detection and a good recovery rate.