Ultrasensitive photometric and visual determination of organophosphorus pesticides based on the inhibition of enzyme-triggered formation of core-shell gold-silver nanoparticles

Abstract

The authors describe a colorimetric assay for the determination of organophosphorous pesticides (OPPs) based on enzyme-triggered deposition of silver nanoparticles on the surface of gold nanoparticles (AuNP). In this method, alkaline phosphatase (ALP) catalyzes the dephosphorylation of the substrate p-aminophenyl phosphate (p-APP) to form p-aminophenol (p-AP) which is capable of reducing Ag(I) ion to Ag metal which is spontaneously deposited on the surface of AuNP to form Au@Ag NPs. As a result, the color of the colloidal solution first changes from red to yellow, and then to gray with further increases in the thickness of the Ag shell. This can be detected visually or by spectrophotometry. OPPs act as inhibitors of ALP so that the dephosphorylation of p-APP is blocked and silver deposition on the AuNP is retarded or completely suppressed. As a result, the color change from red to yellow is less distinct. This finding forms the basis for the determination of OPPs. Under optimum conditions, the absorbance at 370?nm depends linearly on the logarithm of inhibitor concentration over the ranges from 0.05 to 500 μg?L^?1 and from 0.1 to ?500 μg?L^?1, with detection limits of 0.025?μg?L^?1 for methamidophos and 0.036?μg?L^?1 for malathion (at an S/N ratio of 3). Both values are much lower than the maximum residue limits specified in the U.S. Department of Agriculture and European Union pesticide regulations. The validation and practicability of this method for the measurement of OPPs was demonstrated by analyzing (spiked) tap water and lake water.