ABSTRACT
A new magnetic molecularly imprinted polymer was successfully synthesized using a ternary deep eutectic solvent derived from caffeic acid-choline chloride-formic acid as a functional monomer, thymol-menthol deep eutectic solvent as a template, ethylene glycol dimethacrylate as a cross-linker, potassium peroxodisulfate as an initiator, and aqueous ethanol solution (90% (v/v)) as a porogen. The synthesized material was characterized and applied for magnetic solid-phase extraction of dichlorodiphenyl trichloroethane and its degradation products. Optimization of the extraction condition was carried out using the central composite design and response surface methodology. The good analytical performance of magnetic solid phase extraction/gas chromatographyâmass spectrometry using the proposed adsorbent shows a wide linear range of 0.07-500 ng g-1 with R2 greater than 0.992. Low detection limits and quantitation limits were observed in the ranges of 0.01-2.00 ng g-1 and 0.07-2.50 ng g-1, respectively. The precisions shown in terms of relative standard deviations were lower than 7.0% for intraday (n=5) and 8.6% for interday (n=5 × 3) experiments. The proposed method was applied for preconcentration and determination of dichlorodiphenyl trichloroethane and its degradation products in fruit and vegetable samples. The satisfactory recoveries of the real samples at three spiked concentrations were obtained in the range of 79.1%-110.9% with RSDs lower than 7.5%. The findings highlight the importance of developing efficient sorbents for the enrichment of persistent organic pollutants in food matrices.
Subject(s)
Molecular Imprinting , Molecularly Imprinted Polymers , Solvents/chemistry , Vegetables , Deep Eutectic Solvents , Trichloroethanes , Fruit , Polymers/chemistry , Solid Phase Extraction , Magnetic Phenomena , Molecular Imprinting/methodsABSTRACT
A green solvent of ternary deep eutectic solvent (menthol-thymol-dodecanoic acid) was prepared and used as a functional reagent to modify a magnetic mixed iron hydroxide@MIL-101(Cr)-NH2 composite. The proposed sorbent (MIH@MIL-101(Cr)-NH2-TDES) was applied in magnetic solid phase extraction (MSPE) for the enrichment of organochlorine pesticides. The analytes were quantitively analyzed by GC-MS. The relationships of experimental parameters for preparing the proposed sorbent and the MSPE method were studied through a Box-Behnken design and a central composite design, respectively. Their optimized conditions were investigated using response surface methodology. Application of the MIH@MIL-101(Cr)-NH2-TDES sorbent in MSPE successfully enhanced the sensitivity of GC-MS analysis, giving enrichment factors in the range of 56-168. The MSPE/GC-MS method was developed using MIH@MIL-101(Cr)-NH2-TDES as a sorbent and was successfully employed for the preconcentration/determination of organochlorine residues in honey and tea samples. The satisfactory detection limits were in the ranges of 0.07-0.80 ng g-1 and 0.7-8.5 ng g-1 for honey and tea samples, respectively. Acceptable recoveries were obtained in the ranges of 81.7-107.3% and 85.4-109.3% for the spiked honey and tea samples, respectively, with RSDs lower than 10.0%.
ABSTRACT
A newly designed magnetic layered double hydroxide composite modified with a natural deep eutectic solvent derived from choline chloride and sucrose was synthesized and applied as a sorbent for the enrichment of organochlorine pesticides. The magnetic solid phase extraction (MSPE) procedure was optimized via a small central composite design and response surface methodology. The MSPE method was able to preconcentrate the organochlorine residues in environmental samples prior to GC-MS analysis. Good analytical performance of the proposed method was observed with an enrichment factor of up to 158 and low limits of detection in the ranges of 0.002-0.015 µg·L-1 and 0.03-0.10 ng·g-1 for water and soil, respectively. Satisfactory recoveries for spiked water and soil samples were obtained in the ranges of 80.9-104.7% (RSDs<7.9) and 88.8-104.1% (RSDs<7.3), respectively. This finding highlights the role of natural deep eutectic solvents as modifying agents for magnetic layered double hydroxides, which enhance the efficiency of extraction of the target analytes. The developed MSPE/GC-MS procedure was sensitive and reliable for the determination of trace organochlorine residues in environmental samples.
Subject(s)
Hydrocarbons, Chlorinated , Pesticides , Deep Eutectic Solvents , Hydrocarbons, Chlorinated/analysis , Hydroxides/analysis , Limit of Detection , Magnetic Phenomena , Pesticides/analysis , Soil , Solid Phase Extraction/methods , Solvents/chemistry , Water/analysisABSTRACT
A new type of magnetic material based on silica-coated mixed iron hydroxides functionalized with deep eutectic solvent was utilized for the magnetic solid-phase extraction of organochlorine pesticides prior to gas chromatography-mass spectrometry analysis. Choline chloride and phenol were selected as the hydrogen bond acceptor and donor, respectively, for preparing the deep eutectic solvent-modified magnetic surface. The modified surface possessed superior enrichment capability for organochlorine pesticides. Under optimal extraction conditions, viz., 10 mg sorbent, 5 mL sample solution, and 200 µL acetone (desorption solvent), linearity was obtained in the range 0.005-200 µg/L, with coefficients of determination greater than 0.997. The limits of detection and quantification were as low as 0.6-10 and 5-60 ng/L, respectively, whereas the enrichment factors were in the range of 31-100. The precisions evaluated in terms of the relative standard deviations of the intra- and inter-day experiments were <4.9 and 7.6%, respectively. The developed method was successfully applied for determining the organochlorine residues in agricultural products. Satisfactory recoveries in the range of 71.2-110.3% were obtained, with a relative standard deviation of <8.0%. The proposed material is a promising sorbent for the preconcentration of organochlorine residues.