Two-Dimensional 1T-Phase Transition Metal Dichalcogenides as Nanocarriers To Enhance and Stabilize Enzyme Activity for Electrochemical Pesticide Detection.

Abstract

Single or few layers lithium-exfoliated transition metal dichalcogenides (TMDs) are found to exist predominantly in the conducting metallic 1T-polymorph, which makes it desirable for numerous applications due to its large surface area, good electrical conductivity, and enhanced electrocatalytic capabilities. We demonstrated the use of tert-butyllithium exfoliated TMDs (MoS₂, MoSe₂, WS₂, WSe₂) as a platform for the indirect electrochemical detection of an organophosphate pesticide, fenitrothion, via enzymatic inhibition pathway. All four reported materials enhanced the response of the enzymatic biosensor in comparison to the corresponding biosensor in the absence of TMDs. 1T-Phase WS₂ outperforms all other TMD materials, and we proved that it serves as an excellent transducer for enhancing electron transfer in a robust model enzyme-based inhibition assay system using cross-linking immobilization with glutaraldehyde. The reported system showed a broad fenitrothion concentration range (1-1000 nM) with an excellent linearity (r = 0.987). Moreover, the system displayed high sensitivity with low limit of detection (2.86 nM) obtained, which far exceeds the required limit set by Food and Agriculture Organisation (FAO) of the United Nations (UN). The feasibility of the proposed system in real samples was demonstrated in apple juice samples with good recoveries of 80.2% and 80.3% obtained at 10 and 1000 nM fenitrothion, respectively.