Magnetic Solid-Phase Extraction of Carbamate Pesticides Using Magnetic Metal-Organic Frameworks Derived from Benzoate Ligands, Followed by Digital Image Colorimetric Screening and High-Performance Liquid Chromatography Analysis

Jirasak Gamonchuang; Yanawath Santaladchaiyakit; Rodjana Burakham

doi:10.1021/acsomega.2c00596

Magnetic Solid-Phase Extraction of Carbamate Pesticides Using Magnetic Metal-Organic Frameworks Derived from Benzoate Ligands, Followed by Digital Image Colorimetric Screening and High-Performance Liquid Chromatography Analysis

ACS Omega. 2022 Mar 30;7(14):12202-12211. doi: 10.1021/acsomega.2c00596. eCollection 2022 Apr 12.

Authors

Jirasak Gamonchuang¹, Yanawath Santaladchaiyakit², Rodjana Burakham¹

Affiliations

¹ Materials Chemistry Research Center, Department of Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand.
² Department of Chemistry, Faculty of Engineering, Rajamangala University of Technology Isan, Khon Kaen Campus, Khon Kaen 40000, Thailand.

Abstract

Magnetic sorbents based on iron-aluminum-mixed metal hydroxides composited with metal-organic frameworks (MOFs) were designed and synthesized using different benzoate ligands, including terephthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 1,3,5-benzenetricarboxylic acid, and 1,2,4,5-benzenetetracarboxylic acid. The magnetic MOF derived from terephthalic acid ligand exhibited an excellent extraction efficiency, with adsorption capacities in the range of 2193-4196 mg kg^-1, and was applied for magnetic solid-phase extraction (MSPE) of carbamate pesticides, that is, bendiocarb, carbosulfan, carbofuran, carbaryl, propoxur, isoprocarb, and promecarb. Simple digital image colorimetry based on the diazotization reaction and high-performance liquid chromatography (HPLC) were utilized for fast screening and quantification purposes, respectively. A good analytical performance for a simple screening approach using portable equipment was obtained with detection limits in the range of 1.0-18.0 μg L^-1. Under the optimized MSPE-HPLC conditions, the entire developed procedure provided a wide linear range between 0.015 and 1000 μg L^-1, low limits of detection, and limits of quantitation ranging from 0.005 to 0.090 and 0.015-0.300 μg L^-1, respectively. Enrichment factors up to 184 were achieved. The intra- and interday relative standard deviations were below 6.7 and 9.4%, respectively. The proposed MSPE-digital image colorimetry and MSPE-HPLC methods were successfully applied for screening and determining carbamate pesticides in fruits and vegetables. The recoveries were obtained in a satisfactory range of 71.5-122.8%. This discovery has led to the development of integration methods using newly synthesized sorbent materials for the enrichment of carbamate pesticides prior to their analysis in complicated samples. The developed MSPE coupled with digital image colorimetry was efficient for fast carbamate contamination screening, while MSPE-HPLC offered a sensitive analytical methodology for quantifying contaminated samples.