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1.
Food Chem ; 441: 138325, 2024 May 30.
Article in English | MEDLINE | ID: mdl-38183727

ABSTRACT

An eco-friendly biomass waste-derived magnetic material coated with a dual-dummy-template molecularly imprinted polymer was fabricated using aqueous ethanol as a green porogen, lower amounts of toxic compounds as template molecules, and tyrosine and tryptophan as biocompatible binary monomers. The binding characteristics and selectivity of the material toward pesticides were assessed. High adsorption capacities ranging from 150.11 to 509.09 mg g-1 and imprinting factors reaching 2.2 were achieved within just 30 s. The material was applied for extraction of organophosphorus and carbamate pesticides prior to HPLC analysis. Under the optimum conditions, low limits of detection and quantitation were achieved, with ranges of 0.05-1.49 µg/L and 0.18-5.00 µg/L, respectively. The established approach enables efficient analysis of vegetable and fruit samples, yielding satisfactory recoveries ranging between 80 and 110 %. The method showed promise as an analytical method for the sensitive enrichment of pesticide residues in vegetable and fruit samples.


Subject(s)
Molecular Imprinting , Pesticides , Molecularly Imprinted Polymers , Polymers/chemistry , Biomass , Pesticides/analysis , Adsorption , Carbamates , Magnetic Phenomena , Molecular Imprinting/methods , Solid Phase Extraction/methods , Chromatography, High Pressure Liquid/methods
3.
Talanta ; 270: 125536, 2024 Apr 01.
Article in English | MEDLINE | ID: mdl-38101032

ABSTRACT

Biodegradable molecularly imprinted polymer-coated paper (MIP@paper) was effectively produced by polymerization using azinphos-methyl as a template molecule, terephthalic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linker, and aqueous ethanol as a green porogenic solvent. The material was subsequently composited onto cellulose paper, which served as the natural substrate, by dip coating with the aid of chitosan and citric acid natural adhesive. The properties, such as static and dynamic adsorption, selectivity, and reusability, were assessed. At rapid adsorption equilibrium (10 min), the MIP@paper had a high adsorption capacity in the range of 2.5-3.7 mg g-1 and good recognition with imprinting factors up to 2.1. In addition, the proposed MIP@paper was utilized efficiently as a sorbent for dispersive solid phase extraction (d-SPE) of eight organophosphorus pesticides (OPPs) prior to high-performance liquid chromatography (HPLC) analysis. The d-SPE-HPLC method displayed low detection limits of 1.2-4.5 µg kg-1 and significant enrichment factors (up to 320-fold). The proposed method was effectively applied for the determination of OPP residues in agricultural products, including fruits, vegetables, and cereal grains, with satisfactory spiked recoveries (80.1-119.1 %). Thus, the MIP@paper material provided a selective and environmentally favorable method for extracting and determining organophosphorus pesticides.


Subject(s)
Molecular Imprinting , Pesticides , Pesticides/analysis , Vegetables/chemistry , Molecularly Imprinted Polymers/analysis , Organophosphorus Compounds/analysis , Edible Grain/chemistry , Fruit/chemistry , Solid Phase Extraction/methods , Molecular Imprinting/methods , Adsorption , Chromatography, High Pressure Liquid/methods
4.
J Chromatogr A ; 1712: 464494, 2023 Dec 06.
Article in English | MEDLINE | ID: mdl-37951046

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 chromatography‒mass 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/methods
5.
RSC Adv ; 13(13): 8863-8872, 2023 Mar 14.
Article in English | MEDLINE | ID: mdl-36936839

ABSTRACT

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%.

6.
Food Chem ; 418: 136045, 2023 Aug 30.
Article in English | MEDLINE | ID: mdl-36996646

ABSTRACT

An eco-friendly magnetic dual-dummy-template molecularly imprinted polymer (MDDMIP) was prepared by a "one-pot" green synthesis using mixed-valence iron hydroxide as the magnetic material, a deep eutectic solvent as the coporogen, and caffeic acid and glutamic acid as binary monomers. The adsorption properties toward organophosphorus pesticides (OPPs) were investigated. High adsorption capacities (269.65-304.93 mg g-1), quick adsorption times (20 s), and high imprinting factors (2.28-3.83) were obtained. The proposed MDDMIP was utilized for magnetic solid phase extraction (MSPE) of OPPs prior to quantification by high performance liquid chromatography (HPLC). The developed method exhibited outstanding linearity (0.05-500 µg L-1), low detection limits (0.003-0.015 µg L-1), and excellent enrichment factors (940-1310 folds). The MSPE-HPLC method was successfully applied for the detection of OPPs in vegetable, fruit, and grain samples with acceptable recoveries (80-119%). This method is a good potential method for the analysis of pesticide residues in complex matrices.


Subject(s)
Molecular Imprinting , Pesticides , Solvents/chemistry , Molecularly Imprinted Polymers , Deep Eutectic Solvents , Organophosphates , Polymers/chemistry , Organophosphorus Compounds , Solid Phase Extraction/methods , Adsorption , Magnetic Phenomena , Molecular Imprinting/methods , Chromatography, High Pressure Liquid/methods
7.
ACS Omega ; 7(39): 34877-34887, 2022 Oct 04.
Article in English | MEDLINE | ID: mdl-36211057

ABSTRACT

An eco-friendly sample preparation method that is based on the use of a modified peanut shell as an efficient biosorbent for the extraction of triazole residues before their analysis by high-performance liquid chromatography was reported. The four triazole fungicides were separated on a Purospher STAR RP-18 endcapped (4.6 × 150 mm, 5 µm) column with a mobile phase of 50% (v/v) acetonitrile at a flow rate of 1.0 mL min-1 and detection wavelength set at 220 nm. Peanut shells modified by didodecyldimethylammonium bromide were selected as an effective biosorbent material in the microextraction method. Scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to characterize the biosorbent. The effect of dominant parameters on the proposed microextraction method including the amount of sorbent, kind and concentration of surfactant, sodium hydroxide concentration, kind and amount of salt, sample volume, adsorption time, kind and volume desorption solvent, and desorption time was studied. Under the optimum condition, a good analytical performance for the proposed microextraction method was obtained with a wide linear range within the range of 9-1000 µg L-1, and low limits of detection (0.03 µg L-1 for all analytes) were obtained. Enrichment factors were achieved within the range of 30-51. The intra and interday precision values were evaluated in terms of percentage relative standard deviations (%RSD) and were less than 0.09 and 5.34% for the retention time and peak area, respectively. The proposed microextraction methods were used for extraction and analysis of triazole fungicides in water and honey samples. The recoveries in a satisfactory range of 70.0-118.8% were obtained.

8.
Molecules ; 27(19)2022 Sep 23.
Article in English | MEDLINE | ID: mdl-36234806

ABSTRACT

An in situ coacervative extraction (IS-CAE) based on a double-solvent supramolecular system coupled to liquid-liquid microextraction is investigated for extraction and enrichment of triazole fungicides. The formation of a double-solvent supramolecular system was generated by in situ formation and used as an extraction solvent for the coacervative extraction method. No disperser solvent was required. This new double-solvent supramolecular system has a higher extraction ability than any of its components alone. The different factors that could affect the extraction capability were studied and optimized, including the type of double extractant and its volume, salt addition, vortex time, and centrifugation time. Under optimum extraction conditions, this method provides high enrichment factors (EFs) of 73-318 with low limits of detection (LODs) of 0.3-1 µg L-1 and limits of quantitation (LOQs) of 1-3 µg L-1. In addition, the proposed method was prosperously applied for the determination of triazole fungicides in water, fruit juice, and soy milk samples.


Subject(s)
Fungicides, Industrial , Liquid Phase Microextraction , Chromatography, High Pressure Liquid , Fungicides, Industrial/analysis , Liquid Phase Microextraction/methods , Solvents/chemistry , Triazoles/analysis , Water/analysis
9.
J Chromatogr A ; 1673: 463111, 2022 Jun 21.
Article in English | MEDLINE | ID: mdl-35525191

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/analysis
10.
ACS Omega ; 7(14): 12202-12211, 2022 Apr 12.
Article in English | MEDLINE | ID: mdl-35449973

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.

11.
Food Chem ; 384: 132475, 2022 Aug 01.
Article in English | MEDLINE | ID: mdl-35189433

ABSTRACT

A water-compatible magnetic dual template molecularly imprinted polymer using a ternary deep eutectic solvent as a functional monomer was synthesized via a green synthesis method based on one-pot reversible addition/fragmentation chain transfer precipitation polymerization. The resulting material, DES-MDMIP, shows excellent adsorption capacity (218.62 mg g-1) in rapid adsorption time (30 s) and outstanding selectivity factors of 4.45 for organophosphorus pesticides. The sorbent was applied in magnetic solid-phase extraction prior to HPLC analysis. The developed methodology provides linearity between 0.05 and 2000.00 µg L-1. Low detection limits of 0.015-0.030 µg L-1 and enrichment factors of up to 691 were achieved. The applicability of the method facilitates the efficient determination of fruit and vegetable samples with satisfactory recoveries in the range of 80-117%. The newly designed water-compatible DES-MDMIP sorbent, along with a simple and rapid extraction process, demonstrated a powerful analytical approach for the practical analysis of pesticide residues.


Subject(s)
Molecular Imprinting , Pesticides , Adsorption , Deep Eutectic Solvents , Fruit/chemistry , Magnetic Phenomena , Molecularly Imprinted Polymers , Organophosphorus Compounds/analysis , Pesticides/analysis , Solid Phase Extraction , Solvents/chemistry , Vegetables , Water
12.
Anal Chim Acta ; 1186: 339128, 2021 Nov 22.
Article in English | MEDLINE | ID: mdl-34756263

ABSTRACT

A magnetic dual-template molecularly imprinted polymer (DMIP) was successfully prepared in an aqueous medium and used as a sorbent for the selective extraction of organophosphorus pesticides prior to analysis by high-performance liquid chromatography (HPLC). The binding properties and selectivity of DMIP toward organophosphorus were evaluated and compared with those of a non-imprinted polymer. The established magnetic dispersive solid-phase extraction (MDSPE) method using DMIP exhibited fast enrichment of the target analytes within 60 s for adsorption and 30 s for desorption. Good linearities in the range of 0.5-2000 µg L-1 with coefficients of determination (R2) greater than 0.9930 were observed. The method provides low limits of detection of 0.062-0.195 µg L-1 and limits of quantification of 0.210-0.640 µg L-1 with relative standard deviations of less than 9.5% for intra- and inter-day analyses. The enrichment factors ranged from 464 to 621. Satisfactory recoveries ranged from 81.3 to 110.0% with relative standard deviations below 11%.


Subject(s)
Molecular Imprinting , Pesticides , Chromatography, High Pressure Liquid , Fruit/chemistry , Limit of Detection , Magnetic Phenomena , Molecularly Imprinted Polymers , Organophosphorus Compounds , Pesticides/analysis , Solid Phase Extraction , Vegetables
13.
ACS Omega ; 6(41): 27007-27016, 2021 Oct 19.
Article in English | MEDLINE | ID: mdl-34693120

ABSTRACT

A novel mixed iron hydroxide molecularly imprinted polymer (MIH-MIP) was synthesized via polymerization using mixed-valence iron hydroxide as a magnetic supporter, glyphosate as a template, acrylamide as a functional monomer, and ethylene glycol dimethacrylate as a cross-linker. The resulting material was characterized and applied as a sorbent for the selective enrichment of glyphosate, aminomethylphosphonic acid, and glufosinate by magnetic solid-phase extraction (MSPE) prior to high-performance liquid chromatography. MIH-MIP possessed a high adsorption capacity in the range of 2.31-5.40 mg g-1 with good imprinting factors ranging from 1.52 to 7.59. The Langmuir model proved that the recognition sites were distributed as a monolayer on the surface of MIH-MIP. Scatchard analysis showed two types of binding sites on MIH-MIP. The kinetic characteristics of MIH-MIP suggested that the binding process of all analytes fit well with the pseudosecond-order model. The developed methodology provides good linearity in the range of 72.0-2000.0 µg L-1. Low detection limits of 21.0-22.5 µg L-1 and enrichment factors of up to 18 were achieved. The precision in terms of relative standard deviations of the intra- and interday experiments was better than 7 and 9%, respectively. The applicability of the developed MSPE facilitates the accurate and efficient determination of water, soil, and vegetable samples with satisfactory recoveries in the range of 86-118%. The results confirmed the suitability of the MIH-MIP sorbent for selective extraction and quantification of glyphosate, aminomethylphosphonic acid, and glufosinate.

14.
J Sep Sci ; 44(19): 3636-3645, 2021 Oct.
Article in English | MEDLINE | ID: mdl-34355518

ABSTRACT

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.

15.
Food Chem ; 363: 130254, 2021 Nov 30.
Article in English | MEDLINE | ID: mdl-34120039

ABSTRACT

A novel liquid colorimetric sensor based on deep eutectic solvent (DES) was developed for the preconcentration and detection of Pb2+ in fruit juice, milk and cereal samples. The colorimetric probe was simply fabricated by adding dithizone (DZ) into DES, prepared from choline chloride and phenol. Pb2+ was formed complex with DZ in the probe, providing hydrophobic complex of [Pb-DZ] which was simultaneously extracted into DES and the color was changed from light orange to carmine red. The enriched [Pb-DZ] in DES was detected using spectrophotometer at 520 nm and naked-eyes. In addition, a smartphone in combination with an Image J program was used as an alternative detection device. Under optimal conditions, the enrichment factor was 92 with LOD of 2.1 µg L-1 and the linear range was 0.007-0.075 mg L-1. The proposed liquid colorimetric sensor was successfully applied for Pb2+ detection in various food samples and the results were in good agreement with those obtained by FAAS. The advantages of this method are simple, rapid, environmental friendly and low cost.


Subject(s)
Liquid Phase Microextraction , Animals , Colorimetry , Limit of Detection , Milk , Solvents
16.
Heliyon ; 7(5): e06964, 2021 May.
Article in English | MEDLINE | ID: mdl-34007936

ABSTRACT

In this work, the magnetic sorbents based on different surfactant-coupled titanium dioxide coated iron-aluminium mixed metal hydroxide were investigated as sorbent for extraction of bisphenol compounds. The structure, morphology, and magnetic property of the synthesized sorbents were investigated. The cetyltrimethylammonium bromide-titanium dioxide coated iron-aluminium mixed metal hydroxide (Fe-Al MMH@TiO2-CTAB) exhibited excellent extraction performance toward bisphenols and was selected as the sorbent for development of magnetic solid phase extraction (MSPE) method. The entire MSPE process was optimized, and the extract was analyzed by high performance liquid chromatography with photodiode array detector. The method provided wide linear calibration ranges for bisphenols between 0.3-6000 µg L-1 with maximum enrichment factors of 280. The limits of detection and limits of quantification were in the ranges of 0.08-0.3 and 0.3-1.0 µg L-1, respectively. The proposed MSPE method was tested for determination of bisphenols in carbonated beverages. The studied carbonated beverages were mostly free of bisphenol contamination; however, BPS, BPA and BPB were detected in samples taken from defective cans. The relative recoveries ranging of 80.2-118.9% were obtained. The as-prepared Fe-Al MMH@TiO2-CTAB sorbent provided high sorption capacities in the range of 2215-2451 mg kg-1 and could be a promising material for bisphenols in beverage samples.

17.
Anal Sci ; 37(11): 1547-1552, 2021 Nov 10.
Article in English | MEDLINE | ID: mdl-33952865

ABSTRACT

A magnetic starch modified with 3,5-diaminobenzoic acid and 3-aminopropyltriethoxysilane (Fe-starch@DABA-APTES) was synthesized and applied as adsorbent for the extraction of organochlorine pesticides (OCPs). Magnetic solid-phase extraction was developed using 75 mg of the sorbent and 15 mL of a sample solution. Extraction was conducted on a vortex mixer for 40 s. The adsorbent was collected using an external magnet before eluting the analytes using 0.5 mL of methanol. Quantification of the analytes was performed using gas chromatography with a micro-electron capture detector. The linearity was obtained for the studied OCPs in the range between 0.01 - 2.00 µg L-1. The detection and quantification limits were obtained in ranges of 0.5 - 4.0 and 1.5 - 15.0 ng L-1, respectively, with enrichment factors of up to 39. The precision in terms of the intra- and inter-day relative standard deviations (RSDs) were below 4.75, and 9.25%, respectively. The developed method has been applied in natural water and agricultural product samples. The recoveries ranged between 59.83 - 132.67% (RSDs < 10.73%).


Subject(s)
Pesticides , Starch , Limit of Detection , Magnetic Phenomena , Pesticides/analysis , Solid Phase Extraction
18.
J Chromatogr A ; 1643: 462071, 2021 Apr 26.
Article in English | MEDLINE | ID: mdl-33761435

ABSTRACT

Mixed iron hydroxides (MIHs) modified with different amino-based polymeric materials, including aminopropyltriethoxysilane, polydopamine, diaminobenzoic acid, polyaniline, and polyphenylenediamine, were comparatively investigated as sorbents for the extraction of phenol compounds. Polyphenylenediamine-modified mixed iron hydroxides (MIH@PPDA) showed high adsorption capability for most target analytes. Its ferromagnetic behavior, with a magnetization of 17.38 emu g-1, was sufficient for subsequent use in magnetic solid-phase extraction (MSPE). The functional groups, morphology, and magnetic properties of this magnetic nanomaterial were investigated using Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, X-ray diffraction, and CHN analysis. High-performance liquid chromatography with a photodiode array detector was used to quantify phenol compounds. The experimental parameters affecting the efficiency of the entire MSPE process were optimized. Good linearity in the range of 0.5-1000 µg L-1 was obtained (depended on the compound). The detection and quantitation limits varied from 0.01 to 0.3 µg L-1 and 0.03 to 0.9 µg L-1, respectively. The enrichment factors for all phenol compounds were in the range of 80-285. The precision in terms of intra- and inter-day relative standard deviations were below 5.8% and 6.2%, respectively. The developed MSPE method was applied to analyze phenol compounds in diverse samples, including soil, drinking water, and fruit. Relative recoveries of 76.7-130.1% were obtained. The MIH@PPDA magneto-polymeric sorbent exhibits good stability and is reliable for a variety of phenol compounds.


Subject(s)
Ferric Compounds/chemistry , Magnetics , Phenol/analysis , Polymers/chemistry , Solid Phase Extraction/methods , Adsorption , Chromatography, High Pressure Liquid , Fresh Water/analysis , Hydrogen-Ion Concentration , Limit of Detection , Phenol/isolation & purification , Reproducibility of Results , Soil Pollutants/analysis
19.
Molecules ; 27(1)2021 Dec 22.
Article in English | MEDLINE | ID: mdl-35011271

ABSTRACT

A single-step preconcentration procedure using the in-situ formation of modified nickel-zinc-layered double hydroxides (LDHs) prior to high-performance liquid chromatography (HPLC) is investigated for the determination of neonicotinoid insecticide residues in honey samples. The LDHs could be prepared by the sequential addition of sodium hydroxide, sodium dodecyl sulfate, nickel nitrate 6-hydrate and zinc nitrate 6-hydrate, which were added to the sample solution. The co-precipitate phase and phase separation were obtained by centrifugation, and then the precipitate phase was dissolved in formic acid (concentrate) prior to HPLC analysis. Various analytical parameters affecting extraction efficiency were studied, and the characterization of the LDHs phase was performed using Fourier-transformed infrared spectroscopy and scanning electron microscopy. Under optimum conditions, the limit of detection of the studied neonicotinoids, in real samples, were 30 µg L-1, for all analytes, lower than the maximum residue limits established by the European Union (EU). The developed method provided high enrichment, by a factor of 35. The proposed method was utilized to determine the target insecticides in honey samples, and acceptable recoveries were obtained.


Subject(s)
Hydroxides/chemistry , Insecticides/chemistry , Neonicotinoids/chemistry , Nickel/chemistry , Zinc Compounds/chemistry , Zinc/chemistry , Chromatography, High Pressure Liquid , Honey/analysis , Insecticides/analysis , Neonicotinoids/analysis , Spectroscopy, Fourier Transform Infrared
20.
Molecules ; 25(12)2020 Jun 16.
Article in English | MEDLINE | ID: mdl-32560233

ABSTRACT

A green, simple and sensitive hydrophobic DES-based dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography (HPLC) was developed for the analysis of neonicotinoid insecticide residues in various samples. A hydrophobic deep eutectic solvent (DES) was synthesized using decanoic acid as a hydrogen bond donor and tetrabutylammonium bromide (TBABr) as a hydrogen bond-acceptor. DESs were synthesized and characterized by Fourier transform-infrared (FTIR) spectroscopy. Two disperser solvents were substituted with surfactants and acetonitrile, which could afford more effective emulsification and make the extraction relatively greener. The hydrophobic DES extraction phase occurred 10 min after centrifugation, being easy to be collected for analysis. Several parameters were investigated and optimized. Under the optimum condition, the calibration curve of this method was linear in the range of 0.003-1.0-µg·mL-1, with a correlation coefficient (R2) higher than 0.99 and a good repeatability, with the relative standard deviations (RSDs) were less than 5.00%. The limits of detection were in the range of 0.001-0.003 µg·mL-1; the limits of quantitation were in the range of 0.003-0.009 µg·mL·mL-1. Finally, the presented method was implemented to determine the neonicotinoid insecticide residues in water, soil, egg yolk samples and acceptable recoveries were obtained.


Subject(s)
Egg Yolk/chemistry , Insecticides/analysis , Neonicotinoids/analysis , Pesticide Residues/analysis , Soil/chemistry , Water/analysis , Liquid Phase Microextraction , Spectroscopy, Fourier Transform Infrared
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