Facile magnetization of metal–organic framework TMU-6 for magnetic solid-phase extraction of organophosphorus pesticides in water and rice samples

doi:10.1016/j.talanta.2020.121139

Talanta

Volume 218, 1 October 2020, 121139

https://doi.org/10.1016/j.talanta.2020.121139 Get rights and content

Highlights

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Fe3O4@TGA@TMU-6 was synthesized by ultrasound assisted layer-by-layer strategy.
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It was used for magnetic solid-phase extraction of some organophosphorus pesticides (OPPs).
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Separation and determination of the analytes was performed by HPLC-UV.
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They exhibit high specific surface areas and high extraction efficiency for interest OPPs.
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The method was used for successful analysis of three OPPs in rice samples.

Abstract

In the present work, a magnetic metal-organic framework composite (Fe₃O₄@TGA@TMU-6) was synthesized and used as an adsorbent for magnetic solid-phase extraction (MSPE) of some organophosphorus pesticides (phosalone, chlorpyrifos and, profenofos) in rice and environmental water samples. Extraction, separation and determination of the analytes were performed by MSPE-HPLC-UV. Due to the large surface area and unique porous structure of the metal-organic frameworks (MOFs) as well as π-π and hydrophobic interactions between the analytes and the MOF ligands, the prepared sorbents showed a high affinity towards the target analytes. The affecting parameters on the extraction efficiency, including type and volume of eluent, pH, amount of MFC, extraction time, salt effect and desorption time were investigated and optimized. Under optimum conditions, calibration curves were found to be linear in the range of 7.5–75 μg L⁻¹, 10–100 μg L⁻¹, and 10–150 μg L⁻¹ for phosalone, chlorpyrifos, and profenofos in water samples, respectively. The LODs (based on S/N = 3) were 0.5, 1 and 0.5 μg L⁻¹ for phosalone, chlorpyrifos, and profenofos in water samples, respectively.

Graphical abstract

Introduction

Organophosphorus pesticides (OPPs), which have been used as pesticides and chemical war agents [1], can cause several neurotoxic diseases in humans [2]. More than one hundred OPPs such as chlorpyrifos, profenofos and phosalone have been used worldwide [3,4]. OPPs demonstrated serious toxicity, mutagenic, carcinogenic, and have great risks for mammal's lives [5]. Some of the OPPs have residues in soil, water, and other agriculture products [6]. Thus a facile, safe, selective, rapid and sensitive analytical method for extraction and determination of OPP residues in the various matrices is critical.

OPPs have been determined in water using a variety of techniques, including; gas chromatography (GC) [7], GC coupled with mass spectrometry (GC/MS) [8], ion mobility spectrometry (IMS) [9], and high-performance liquid chromatography (HPLC) [10].

Instrumental analysis is disabled to quantify ultra-trace amounts of OPPs in real samples. Therefore, extraction and preconcentration of OPPs are required for analysis of trace amounts of OPPs in real samples.

Various sample preparation techniques were reported for OPPs from environmental water and rice samples including solid-phase extraction (SPE) [11], solid phase micro extraction (SPME) [12], dispersive liquid–liquid microextraction (DLLME) [13], liquid-phase microextraction and ultrasound-assisted emulsification microextraction (USAEME) [14].

SPE is a facile approach for sample preparation because of its high extraction recovery, high preconcentration factor, and ease of automation [15]. Magnetic solid-phase extraction (MSPE) is a new generation of SPE which can be performed using magnetic nanoparticles (MNPs) [11]. MSPE has received considerable attention mainly due to convenience, economy, efficiency, rapidity, minimal cost, simplicity and easy automation [[16], [17], [18], [19]].

In 1995 a new class of porous coordination polymers (PCPs) with high porosity, high surface area, good extraction affinity and selective extraction were synthesized. They were called metal-organic frameworks (MOFs) [[20], [21], [22]]. MOFs were made from the inorganic (metal or cluster) nodes coordinated by organic binding ligands [23,24]. By changing organic linkers of this component morphology, size, and functionality have been modified and led to more than 20,000 various MOFs being reported and studied within the past decade [21]. The water stability of these compounds is the most challenging limitation in using MOFs in analytical chemistry and sample preparation. By the way, MOFs have been suitable for analytical challenges such as; sampling, preconcentration, extraction, and chromatographic separation to improve sensitivity, selectivity, and detection limit [[26], [27], [28]]. For the MSPE of OPPs, magnetic nanoporous carbons (MNPCs) based on Zn/Co-MOFs, Zr(IV) functionalized magnetic nanocomposites, and metal-organic frameworks (MOFs) functionalized magnetic nanocomposites, have been applied as the adsorbents [ 27, 29].

Magnetic frameworks composites (MFCs) were applied as the adsorbents in MSPE. MFCs accomplished wide attention in sample preparation because of their uniform structured nanoscale cavities, high surface area, good chemical resistance, specific adsorption affinities and high selectivity [30]. Approaches have been applied to fabricate magnetic MOFs via combining magnetic particles with MOFs, such as embedding, encapsulation of magnetic nanoparticles in MOFs, or simply mixing the MOFs with magnetic nanoparticles to obtain magnetic hybrid MOFs. In addition, several researches also coated MOFs on magnetic nanoparticles through layer-by-layer strategy. Step-by-step assembly is a versatile strategy to fabricate magnetic core–shell composites. More importantly, the thickness of the outer shell MOFs can be easily adjusted by changing the cycle numbers and the obtained magnetic MOFs can preserve the shape of the pristine magnetic particles [31].

In this study, a novel, simple and efficient method was reported to synthesized MFCs by ultrasound-assisted layer-by-layer strategy [29]. This method can coat zinc-based metal-organic frameworks on a magnetic nanoparticle surface. The MFC, Fe₃O₄@TGA@TMU-6, is formed by incorporation of Fe₃O₄ and zinc nitrate, pillar ligand 4-bpmb (N,N-Bis [1-(pyridine-2-yl)ethylidene]-benzene-1,4-diamine) and acidic ligand H₂oba (4,4′-oxybis (benzoic acid)). Then, the applicability of MFCs for the extraction of trace OPPs compounds from real samples prior to their determination by HPLC-UV was investigated.

Section snippets

Chemicals and reagents

Ferric chloride hexahydrate, ferrous chloride tetrahydrate, ammonia solution, anhydrous methanol, thioglycolic acid (TGA),N,N-dimethylformamide (DMF) and toluene were purchased from Merck (Darmstadt, Germany).

Zinc acetate (Zn(CH₃COO)₂·4H₂O) and H₂oba (4,4′-oxybisbenzoic acid) were purchased from Sigma-Aldrich (St. Louis, MO, USA). OPPs (phosalone, profenofos and chlorpyrifos) (Table 1) were purchased from Shimikeshavarz (Karaj, Iran). Stock solutions of phosalone, profenofos and chlorpyrifos

Characterization of synthesized MFC

FT-IR experiments were performed to confirm the synthesis of the adsorbent. The spectra of Fe₃O₄, TMU-6 and Fe₃O₄@TGA@TMU6 are shown in Fig. 1. In Fig. 1a, the absorption peak at 590 cm⁻¹ is related to Fe–O–Fe primary stretching vibration of Fe₃O₄, and peak at 2400 cm⁻¹ could be attributed to the O–H stretching vibration of humidity on the surface of the adsorbent. In Fig. 1b, the FTIR spectra of TMU-6 and Fe₃O₄@TMU-6 the peaks appearing at 1389 and 1456 cm⁻¹ are ascribed to the stretching

Conclusions

Fe₃O₄@TGA@TMU-6 as the MFC with new morphology, nanoscale pores, large surface area, super magnetic property, excellent water stability, good extraction ability and instantly repercussion in external magnetic field was synthesized.

The Fe₃O₄@TGA@TMU-6 was used for extraction of three OPPs from rice and water samples. The proposed method has a wide linear range, low LOD, good preconcentration factor, high extraction recovery, great reusability and acceptable interday and intraday relative

CRediT authorship contribution statement

Mehrzad Shakourian: Data curation, Writing - original draft. Yadollah Yamini: Supervision, Writing - review & editing. Meysam Safari: Software, Validation.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors gratefully acknowledge financial support from Tarbiat Modares University (Tehran, Iran).

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Facile magnetization of metal–organic framework TMU-6 for magnetic solid-phase extraction of organophosphorus pesticides in water and rice samples

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals and reagents

Characterization of synthesized MFC

Conclusions

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgments

Anal. Chim. Acta

J. Hazard Mater.

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J. Food Compos. Anal.

Food Chem.

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Talanta

J. Supercrit. Fluids

Food Chem.

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J. Chromatogr. A

Anal. Chim. Acta

J. Chromatogr. A

J. Chromatogr. A

J. Colloid Interface Sci.

J. Chromatogr. A

Microchem. J.

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Ecotoxicol. Environ. Saf.

J. Chromatogr. A

Anal. Chim. Acta

J. Chromatogr. A