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We report a new ready-to-use sensor for simultaneous determination of paraquat (PQ) and glyphosate (GLY) based on a graphite screen-printed electrode modified with a dual-molecularly imprinted polymer coated on a mesoporous silica-platinum core. Amino-mesoporous silica nanoparticles (MSN-NH2) were first synthesized by a simple co-condensation method using tetraethyl orthosilicate and 3-aminopropyltrimethoxysilane. PtNPs were then decorated on the surface of MSN-NH2by chemical reduction. Finally, the dual-MIP was successfully coated on the MSN-PtNP core. This 3D-surface-imprinting strategy enhances the conductivity and monodispersity of the MSN-PtNPs@d-MIP. Quantitative analysis was performed by differential pulse voltammetry with an oxidation current appearing at −0.95 V for PQ and +0.97 V for GLY. The dual-MIP sensor shows good linear calibration curves in the range of 0.025–500 μM for both analytes with detection limits of 3.1 nM and 4.0 nM for PQ and GLY, respectively. The dual-MIP sensor shows high selectivity and specificity, attributed to the increased affinity of the imprinted cavities formed on the polymer film for the target PQ and GLY molecules. The proposed dual-MIP sensor was successfully applied to detect PQ and GLY concentrations simultaneously in water samples. The ready-to-use dual-MIP sensor is well suited for water-quality control and on-site applications without sophisticated instrumentation.

Nanoscale imprinting significantly increases the specific surface area and recognition capabilities of a molecularly imprinted polymer by improving accessibility to analytes, binding kinetics, and template removal. Herein, we present a novel synthetic route for a dual molecularly imprinted polymer (dual-MIP) of the carcinogen oxidative stress biomarkers 3-nitrotyrosine (3-NT) and 4-nitroquinolin-N-oxide (4-NQO) as coatings on graphene quantum-dot capped gold nanoparticles (GQDs-AuNPs). The dual-MIP was successfully coated on the GQDs-AuNPs core via a (3-mercaptopropyl) trimethoxysilane (MPTMS) linkage and copolymerization with the 3-aminopropyltriethoxysilane (APTMS) functional monomer. In addition, we fabricated a facile and compact three-dimensional electrochemical paper-based analytical device (3D-ePAD) for the simultaneous determination of the dual biomarkers using a GQDs-AuNPs@dual-MIP-modified graphene electrode (GQDs-AuNPs@dual-MIP/SPGE). The developed dual-MIP device provides greatly enhanced electrochemical signal amplification due to the improved electrode-specific surface area, electrocatalytic activity, and the inclusion of large numbers of dual-imprinted sites for 3-NT and 4-NQO detection. Quantitative analysis used square wave voltammetry, with an oxidation current appearing at −0.10 V for 4-NQO and +0.78 V for 3-NT. The dual-MIP sensor revealed excellent linear dynamic ranges of 0.01 to 500 μM for 3-NT and 0.005 to 250 μM for 4-NQO, with detection limits in nanomolar levels for both biomarkers. Furthermore, the dual-MIP sensor for the simultaneous determination of 3-NT and 4-NQO provides high accuracy and precision, with no evidence of interference from urine, serum, or whole blood samples.