Molecularly Imprinted Polymeric Sorbent for Targeted Dispersive Solid-Phase Microextraction of Fipronil from Milk Samples

Muhammad Hayat; Suryyia Manzoor; Nadeem Raza; Akmal Abbas; Muhammad Imran Khan; Noureddine Elboughdiri; Khalida Naseem; Abdallah Shanableh; Abdullah M M Elbadry; Saleh Al Arni; Mhamed Benaissa; Fatma A Ibrahim

doi:10.1021/acsomega.2c05217

Molecularly Imprinted Polymeric Sorbent for Targeted Dispersive Solid-Phase Microextraction of Fipronil from Milk Samples

ACS Omega. 2022 Nov 1;7(45):41437-41448. doi: 10.1021/acsomega.2c05217. eCollection 2022 Nov 15.

Authors

Affiliations

¹ Institute of Chemical Sciences, Bahauddin Zakariya University, Multan60000, Pakistan.
² Department of Chemistry, Emerson University, Multan60000, Pakistan.
³ State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center of Energy and Research, School of Chemical Engineering, Dalian University of Technology, Dalian116024, China.
⁴ Research Institute of Sciences and Engineering (RISE), University of Sharjah, Sharjah27272, United Arab Emirates.
⁵ Chemical Engineering Department, College of Engineering, University of Ha'il, P.O. Box 2440, Ha'il81441, Saudi Arabia.
⁶ Chemical Engineering Process Department, National School of Engineers Gabes, University of Gabes, Gabes6029, Tunisia.
⁷ Department of Basic and Applied Chemistry, Faculty of Science and Technology, University of Central Punjab, Lahore54700, Pakistan.
⁸ Faculty of Pharmacy, Badr University in Cairo (BUC), Badr City, Cairo11829, Egypt.
⁹ Catalysis Research Group (CRG), Department of Chemistry, Faculty of Science, King Khalid University, P.O. Box 9004, Abha61413, Saudi Arabia.

Abstract

Fipronil, a phenyl pyrazole insecticide, is extensively used in agriculture to control insect infestation. It has the potential to assimilate into the food chain, leading to serious health concerns. We report molecularly imprinted polymer (MIP)-based dispersive solid-phase microextraction for the targeted determination of fipronil in milk samples. Designing such a sorbent is of paramount importance for measuring the accurate amount of fipronil for monitoring its permissible limit. Response surface methodology based on a central composite design following a face-centered approach was used to optimize experimental conditions. The maximum binding capacity of 47 mg g^-1 was achieved at optimal parameters of time (18 min), temperature (42 °C), pH (7), and analyte concentration (120 mg L^-1). Under these conditions, a high percentage recovery of 94.6 ± 1.90% (n = 9) and a low limit of detection (LOD) and limit of quantitation (LOQ) (5.64 × 10^-6 and 1.71 × 10^-5 μg mL^-1, respectively) were obtained. The MIP was well characterized through a scanning electron microscope (SEM) as well as Brunauer-Emmett-Teller (BET), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) methods. Adsorption kinetics of the MIP followed the pseudo-first-order model (R ² 0.99 and χ² 0.96), suggesting the MIP-analyte interaction to be a physiosorptive process, while adsorption isotherms followed the Freundlich model (R ² 0.99). The real sample analysis through high-performance liquid chromatography (HPLC) confirmed the selective determination of fipronil from milk samples.