This review (with 144 refs.) focuses on the recent advances in the preparation and application of magnetic micro/nanoparticles. Specifically, it covers (a) methods for preparation (such as by coprecipitation, pyrolysis, hydrothermal, solvothermal, sol-gel, micro-emulsion, sonochemical, medium dispersing or emulsion polymerization methods), and (b) applications such as magnetic resonance imaging, magnetic separation of biomolecules (nucleic acids; proteins; cells), separation of metal ions and organic analytes, immobilization of enzymes, biological detection, magnetic catalysis and water treatment. Finally, the existing challenges and possible trends in the field are addressed.
Graphical abstract This review focuses on the recent advances in the preparation and application of magnetic micro/nano particles. Finally, the existed problems and possible trends in the field were discussed. a: Fe3O4@SiO2-PVAm: polyvinyl amine-coated Fe3O4@SiO2 b: CTS/MMT-Fe3O4 microsphere: chitosan/montmorillonite-Fe3O4 microsphere c: MTAMs: magnetic targeted antibiotic microspheres d: SM: the code of iron oxide-silica composite microspheres e: PSt: poly styrene f: gamma-PGA- PLA: poly(gamma-glutamic acid) and poly(lactide) g: poly(-MMA–DVB–GMA) microspheres: poly(methylmethacrylate–divinylbenzene–glycidylmethacrylate) microspheres h: AEAPS: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane
The author describes the preparation of a magnetic metal organic framework of type MOF-199 containing magnetite (Fe3O4) nanoparticles carrying covalently immobilized 4-(thiazolylazo) resorcinol (Fe3O4@TAR). This material is shown to represent a viable sorbent for separation and preconcentration of Cd(II), Pb(II), and Ni(II) ions. Box-Behnken design was applied to optimize the parameters affecting preconcentration. Following elution with 0.6 mol L?1 EDTA, the ions were quantified by FAAS. The capacity of the sorbent ranged between 185 and 210 mg g?1. The limits of detection are 0.15, 0.40, and 0.8 ng mL?1 for Cd(II), Ni(II), and Pb(II) ions, respectively. The relative standard deviations are <8.5 %. The method was successfully applied to the rapid extraction of trace amounts of these ions from sea food and agri food.
Graphical abstract (a) A schematic diagram of Fe3O4 functionalization by TAR (4-(thiazolylazo) resorcinol). (b) The schematic illustration of the magnetic metal organic framework-TAR nanocomposite. H3BTC: benzene-1,3,5-tricarboxylic acid; TEA: triethylamine; 3-CPS: 3-chloropropyl triethoxysilane.
We describe a colorimetric assay for mercury(II) ion. It is based on a hybridization chain reaction (HCR) and the use of Fe3O4@Au nanoparticles (NPs). Aptamers specific for Hg(II) were immobilized on the surface of the Fe3O4@AuNPs. The presence of Hg(II) inhibits the HCR process and this enables less Methylene Blue (MB) to intercalate into the dsDNA structure. After magnetic separation of the DNA-loaded NPs carrying Hg(II), the change in the absorbance of the residual MB solution is measured at 663 nm. The respective calibration plot is linear in the 1 to 300 nM concentration range, with a 0.7 nM detection limit (at a signal-to-noise ratio of 3). The method displays excellent selectivity over other metal ions. It was applied to the analysis of Hg(II) in spiked river water.
Graphical abstract Fe3O4@Au nanoparticles (NPs) were fabricated, then aptamers were modified on the surface of Fe3O4@AuNPs. The absence of Hg2+ leads to the formation of dsDNA polymers via hybridization chain reaction (HCR) process on the surface of Fe3O4@AuNPs, Methylene Blue (MB) intercalates into these DNA polymers, which can be easily separated from MB solution by applying a magnet, thereby inducing a color change of the MB solution.
A multifunctional fluorescent probe is synthesized for the determination of adenosine 5′-triphosphate (ATP). The 6-carboxyfluorescein-labeled aptamer (FAM-aptamer) was bound to the surface of magnetite nanoparticles coated with polydopamine (Fe3O4@PDA) by π-π stacking interaction to form the multifunctional probe. The probe has three functions including recognition, magnetic separation, and yielding a fluorescent signal. In the presence of ATP, FAM-aptamer on the surface of the probe binds to ATP and returns to the solution. Thus, the fluorescence of the supernatant is enhanced and can be related to the concentration of ATP. Fluorescence intensities were measured at excitation/emission wavelengths of 494/526 nm. Response is linear in the 0.1–100 μM ATP concentration range, and the detection limit is 89 nM. The probe was applied to the quantitation of ATP in spiked human urine and serum samples, with recoveries ranging between 94.8 and 102%.
Graphical abstract A multifunctional fluorescent probe based on the use of FAM-aptamer and Fe3O4@PDA is described for the determination of ATP in spiked human urine and serum samples. FAM-aptamer: 6-carboxyfluorescein-labeled aptamer; Fe3O4@PDA: magnetite nanoparticles coated with polydopamine. ATP: adenosine 5′-triphosphate.
Photonic encoding magnetized silica microspheres were synthesized from a polydisperse system containing silica and Fe3O4 nanoparticles by using a microfluidic self-assembly device. The optical and structural properties of the magnetized microspheres were characterized by scanning electron microscopy and reflection spectra. The concentration of Fe3O4 nanoparticles in polydisperse system was found to strongly affect the characteristics of magnetized microspheres. They possess a Janus face, are porous, and possess structural color (red). The magnetic characteristic of the synthesized microspheres is not lost after they are immersed in piranha solution for 12 h. The magnetized microspheres were applied to aptamer-based enrichment of the food toxin Ochratoxin A (OTA). Methods for immobilization of OTA aptamer on the microsphere surfaces were investigated. The modified microspheres can extract up to 80% of OTA if the surface of the microspheres is loaded with 275 ng·cm?2 of aptamer and the number of microspheres is 200. The work provides a new pathway for aptamer-based enrichment of small molecules from complex matrixes.
Graphical abstract Photonically encoded magnetized silica microspheres were synthesized by using microfluidic self-assembly device. The optical, magnetic and structural properties of the microspheres were investigated. The three-dimensional porous magnetized microspheres were applied to aptamer-based enrichment of the food toxin Ochratoxin A.
A magnetic nanosorbent was prepared from Fe3O4 nanoparticles and polyacrylamide using a solvothermal process. Two functions are achieved simultaneously in this process: The first consists in the formation of a carbon layer around the Fe3O4 nanoparticles, and the second one in the functionalization with an amido group. This combination allows the protection of Fe3O4 nanoparticles from dissolution in acid medium during heavy metal adsorption. The adsorbent was characterized by SEM, TEM, EDS, FTIR, TGA, and in terms of surface area. Results showed the Fe3O4 nanoparticles to be embedded in a sheet of carbon with folded surfaces which is functionalized with amido groups. The nanosorbent was applied to the enrichment of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) via magnetic solid phase extraction (mag-SPE). The effects of pH value, eluent type and sample volume were optimized. The validation of the procedure was verified by the analysis of a wheat gluten certified reference material (8418). The limits of detection for the above ions range from 1 to 110 ng L?1. The relative standard deviations are <10%. The procedure was successfully applied to the enrichment of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) from various water and food samples.
Graphical abstract Schematic of a new magnetic nanosorbent synthesized from Fe3O4 nanoparticles and polyacrylamide using a solvothermal method. The sorbent was used for the enrichment of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) in water and food samples for their ICP-MS detection.
An amino acid derived ionic liquid, Fe3O4 nanoparticles and graphene oxide (GO) were used to prepare a material for the magnetic solid phase extraction (MSPE) of the ions Al(III), Cr(III), Cu(II) and Pb(II). The material was characterized by Fourier transform infrared spectral (FT-IR), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), magnetic analysis and isoelectric point (pI) analysis. It is shown to be a viable sorbent for the separation of these metal ions. Single factor experiments were carried out to optimize adsorption including pH values, ionic strength, temperature and solution volume. Following desorption with 0.1 M HCl, the ions were quantified by inductively coupled plasma optical emission spectrometry. Under the optimum conditions, the method provides a linear range from 10 to 170 μg· L?1 for Al(III); from 4.0 to 200 μg· L?1 for Cr(III); from 5.0 to 170 μg· L?1 for Cu(II); and from 5.0 to 200 μg· L?1 for Pb(II). The limits of detection (LOD) are 6.2 ng L?1 for Al(III); 1.6 ng L?1 for Cr(III); 0.52 ng L?1 for Cu(II); and 30 ng L?1 for Pb(II). Method performance was investigated by determination of these ions in (spiked) environmental water and gave recoveries in the range of 89.1%–117.8%.
Graphical abstract The graph shows that Al(III), Cr(III), Cu(II), Pb(II) are not adsorbed quantitatively by Fe3O4-SiO2. On the other hand, Cr(III) and Pb(II) are adsorbed quantitatively by Fe3O4-SiO2-GO while Al(III) and Cu(II) are not quantitatively retained. However, 3D–Fe3O4-SiO2-GO-AAIL adsorb all these 4 metal ions quantitatively.
The authors describe an amperometric sensor for dopamine (DA) by employing olive-like Fe2O3 microspheres (OFMs) as the electrocatalyst for DA oxidization. The OFMs were prepared by using a protein templated method. The structure and properties of the OFMs were characterized by scanning electron microscopy, X-ray powder diffraction, energy dispersive x-ray spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The OFMs possess excellent catalytic activity towards DA oxidization due to their unique morphology. The sensor responds to DA within less than 5 s. The sensor, best operated at a voltage of +0.2 V (vs. SCE) responds linearly in the 0.2 to 115 μM DA concentration range and has a 30 nM detection limit. The selectivity, reproducibility and long-term stability of the sensor are acceptable. It performs well when applied to spiked human urine samples.
Graphical abstract Olive-like Fe2O3 microspheres (OFMs), synthesized using egg white as template, display excellent catalytic activity towards dopamine (DA) oxidization due to their unique morphology. They were applied for DA detection using the amperometric technique. The electrochemical sensor exhibited a high sensitivity and a 30 nM detection limit. DAQ: dopaquinone.
A dual enhancing strategy has been employed to develop a sandwich type of electrochemical immunoassay for the prostate specific antigen (PSA). The signal is enhanced by using Pt-Cu hierarchical trigonal bipyramid nanoframes (HTBNFs) and a composite consisting of Fe3O4 nanoparticles and reduced graphene oxide in polydopamine that serve to capture the primary antibody (Ab1). This nanocomposite shows better electrical conductivity than Fe3O4 and reduced graphene oxide (RGO), respectively, alone. The Pt-Cu HTBNFs were used to label the secondary antibody (Ab2) and act as tags for signal amplification by virtue of their outstanding electrochemical reduction activity towards H2O2. At a working potential of +0.1 V (vs. SCE), the interference by dissolved oxygen can be avoided. This immunoassay is highly sensitive, with a linear range that extends from 0.1 pg?mL?1 to 5 ng?mL?1 and an ultralow detection limit of 0.03 pg?mL?1.
Graphical abstract Schematic of the dual amplification strategy in the immunosensor for the prostate specific antigen (PSA) that is based on the use of a first antibody (Ab1) conjugated to a Fe3O4-reduced graphene oxide nanocomposite (Fe3O4-RGO), and of Pt-Cu trigonal bipyramid nanoframes as a label for the second antibody (Ab2).
The authors describe magnetic nanoparticles consisting of an Fe3O4 core and a poly(methacrylic acid) coating for dispersive solid phase extraction (DSPE) of arsenic prior to its determination by hydride-generation microwave plasma AES (HG-MP-AES). The particles have an average size of 25 nm, can be prepared at low costs, and provide improved operational safety in combination with plasma generation. The methods allows arsenic to be determined with detection limits (at 3σ/m) of 3.0 ng?L?1 for As(III) and of 10.0 ng?L?1 of As(V). Recoveries of (spiked) samples range from 99.0 to 102%. This is the first report on the use of HG-MP-AES for speciation and preconcentration of arsenic using DSPE. The method displays detection limits that come close to those of ICP-OES and ICP-MS.
Graphical abstract A core/shell Fe3O4@poly(methacrylic acid) coated sorbent was synthesised and employed to the speciation of arsenic prior to its determination by hydride-generation microwave plasma atomic emission spectrometry.
The authors describe the synthesis of a multifunctional nanocomposite with an architecture of type Fe3O4@SiO2@graphene quantum dots with an average diameter of about 22 nm. The graphene quantum dots (GQDs) were covalently immobilized on the surface of silica-coated magnetite nanospheres via covalent linkage to surface amino groups. The nanocomposite displays a strong fluorescence (with excitation/emission peaks at 330/420 nm) that is fairly selectively quenched by Hg2+ ions, presumably due to nonradiative electron/hole recombination annihilation. Under the optimized experimental conditions, the linear response to Hg2+ covers the 0.1 to 70 μM concentration range, with a 30 nM lower detection limit. The high specific surface area and abundant binding sites of the GQDs result in a good adsorption capacity for Hg2+ (68 mg?g?1). The material, due to its superparamagnetism, can be separated by using a magnet and also is recyclable with EDTA so that it can be repeatedly used for simultaneous detection and removal of Hg2+ from contaminated water.
Graphical abstract A schematic view of preparation process for the Fe3O4@SiO2@graphene quantum dots nanocomposite (denoted as Fe3O4@SiO2@GQDs). The graphene quantum dots were covalently immobilized on the surface of silica-coated magnetite nanospheres (Fe3O4@SiO2) via covalent linkage to surface amino groups.
The authors describe a voltammetric immunoassay for the carcinoembryonic antigen (CEA). It is based on the use of a self-assembled magnetic nanocomposite as multifunctional signal amplification platform. The core of the nanocomposite consists of Fe3O4 microspheres, and the shell of zirconium hexacyanoferrate loaded with gold nanoparticles (AuNPs@ZrHCF@Fe3O4). The material was synthesized by an electrostatic self-assembly process which is caused by the strong interaction between cyano groups and AuNPs. The surface of the Fe3O4 microspheres was functionalized with amino groups to facilitate the immobilization of ZrHCF which acts as an electron mediator. The nanocomposite was placed on a glassy carbon electrode which then displays noteworthy electrocatalytic activity toward the reduction of hydrogen peroxide (H2O2). The AuNPs serve as a support for the immobilization of antibodies by the interaction between AuNPs and amino groups on antibodies to construct a covalent Au-N bond. This facilitates electron transfer on the electrode surface using H2O2 as the electrochemical probe. Square wave voltammetry (measured typically at +0.2 V vs. SCE) was carried out to record the electrochemical behavior. Under the optimal conditions, a response is linear in the 0.5 pg·mL?1 to 50 ng·mL?1 CEA concentration range, and the detection limit is as low as 0.15 pg·mL?1 (S/N =?3). The method is selective, highly stable and acceptably reproducible.
Graphical abstract A self-assembly magnetic nanocomposite for voltammetric immunoassay of CEA. GCE glassy carbon electrode; Au NPs gold nanoparticles; ZrHCF zirconium hexacyanoferrate; CEA carcinoembryonic antigen; Anti-CEA CEA antibody; BSA bovine serum albumin; SWV square wave voltammetry. A high sensitive voltammetric immunoassay method has been used for detecting CEA, It is based on a self-assembled magnetic nanocomposite (Au NPs@ZrHCF@Fe3O4) as multifunctional signal amplification platform.
Graphite-like carbon nitride ? Fe3O4 magnetic nanocomposites were synthesized by a chemical co-precipitation method. The nanocomposites were characterized by transmission electron microscopy, X-ray diffraction, FTIR spectroscopy, X-ray photoelectron spectroscopy and magnetization hysteresis loops. The nanocomposites exhibit enhanced peroxidase-like activity (compared to that of graphite-like carbon nitride or Fe3O4 NPs). More specifically, they are capable of catalyzing the oxidation of different peroxidase substrates (such as TMB, ABTS or OPD) by H2O2 to produce the typical color reactions (blue, green or orange). The nanocomposites retain their magnetic properties and can be separated by an external magnet. On the basis of these findings, a highly sensitive and selective method was applied to the determination of H2O2 and glucose (by using glucose oxidase). It was successfully applied to the determination of glucose in (spiked) human serum. Compared to other nanomaterial-based peroxidase mimetics, the one described here provides distinctly higher sensitivity for both H2O2 and glucose, with detection limits as low as 0.3 μM and 0.25 μM, respectively.
Graphical abstract The magnetic carbon nitride nanocomposite exhibits enhanced peroxidase-like activity that is much larger than that of graphite-like carbon nitride or Fe3O4 NPs alone. This finding was applied to design a highly sensitive and selective colorimetric assay for H2O2 and glucose.
Magnetic molecularly imprinted nanoparticles (MMIPs) with improved dispersity and an increased number of adsorption sites are described. Uniform silica layers were first deposited on the surface of Fe3O4 nanoparticles (Fe3O4 NPs) in order to improve the dispersity of magnetic nanoparticles. Then, 4-formylphenylboronic acid (FPBA) as functional monomer was immobilized on the magnetic carriers to improve the efficiency of template eluting and rebinding. A thin layer of polyaniline imprinted with horseradish peroxidase (HRP) as a model glycoprotein was then placed on the magnetic nanoparticles to enhance the dispersity of the resultant MMIPs. These exhibit high adsorption capacity (62 mg g?1), a satisfactory imprinting factor ( 3.78) and short adsorption equilibrium time (40 min) toward HRP, and the limit of detection is 18.7 μg L?1. This kind of MMIPs, therefore, is deemed being a useful tool for extracting low-abundance glycoproteins from even complex samples.
Graphical abstract Schematic of the preparation of magnetic molecular imprinted nanoparticles using Fe3O4 nanoparticles as carriers, 4-formylphenylboronic acid as functional monomer, aniline as cross linker and horseradish peroxidase as template. TEOS: tetraethyl orthosilicate; APTES: 3-aminopropyltriethoxysilane; FPBA: 4-formylphenylboronic acid; HRP: horseradish peroxidase.
An electrochemical microsensor for chloramphenicol (CAP) was fabricated by introducing magnetic Fe3O4 nanoparticles (NPs) onto the surface of activated carbon fibers. This microsensor exhibited increased electrochemical response toward CAP because of the synergetic effect of the Fe3O4 NPs and the carbon fibers. Cyclic voltammograms were acquired and displayed three stable and irreversible redox peaks in pH 7.0 solution. Under optimized conditions, the cathodic current peaks at ?0.67 V (vs. Ag/AgCl). The calibration plot is linear in the 40 pM to 1 μM CAP concentration range, with a 17 pM detection limit (at a signal-to-noise ratio of 3). The sensor was applied to the determination of CAP in spiked sediment samples. In our perception, this electrocatalytic platform provided a useful tool for fast, portable, and sensitive analysis of chloramphenicol.
Graphical abstract A sensitive carbon fiber microsensor modified with Fe3O4 nanoparticles is found to display two cathodic peaks when detecting chloramphenicol at 100 mV·s?1 and at pH 7.0. The sensor was applied to the determination of chloramphenicol in sediment samples.
Diphenyl diselenide was immobilized on chitosan loaded with magnetite (Fe3O4) nanoparticles to give an efficient and cost-effective nanosorbent for the preconcentration of Pb(II), Cd(II), Ni(II) and Cu(II) ions by using effervescent salt-assisted dispersive magnetic micro solid-phase extraction (EA-DM-μSPE). The metal ions were desorbed from the sorbent with 3M nitric acid and then quantified via microflame AAS. The main parameters affecting the extraction were optimized using a one-at-a-time method. Under optimum condition, the limits of detection, linear dynamic ranges, and relative standard deviations (for n?=?3) are as following: Pb(II): 2.0 ng·mL?1; 6.3–900 ng·mL?1; 1.5%. Cd(II): 0.15 ng·mL?1; 0.7–85 ng·mL?1, 3.2%; Ni(II): 1.6 ng·mL?1,.6.0–600. ng·mL?1, 4.1%; Cu(II): 1.2 ng·mL?1, 3.0–300 ng·mL?1, 2.2%. The nanosorbent can be reused at least 4 times.
Graphical abstract Fe3O4-chitosan composite was modified with diphenyl diselenide as a sorbent for separation of metal ions by effervescent salt-assisted dispersive magnetic micro solid-phase extraction.
A nanocomposite consisting of cetyltrimethylammonium bromide (CTAB), Fe3O4 nanoparticles and reduced graphene oxide (CTAB-Fe3O4-rGO) was prepared, characterized, and used to modify the surface of a glassy carbon electrode (GCE). The voltammetric response of the modified GCE to 4-nonylphenol (NPh) was investigated by cyclic voltammetry and revealed a strong peak at around 0.57 V (vs. SCE). Under optimum conditions, the calibration plot is linear in the ranges from 0.03 to 7.0 μM and from 7.0 to 15.0 μM, with a 8 nM detection limit which is lower that that of many other methods. The modified electrode has excellent fabrication reproducibility and was applied to the determination of NPh in spiked real water samples to give recoveries (at a spiking level of 1 μM) between 102.1 and 99.1%.
Graphical abstract A nanocomposite consisting of cetyltrimethylammonium bromide (CTAB), Fe3O4 nanoparticles and reduced graphene oxide (CTAB-Fe3O4-rGO) was prepared and used to modify the surface of a glassy carbon electrode (GCE) for the differential pulse voltammetric (DPV) determination of 4-nonylphenol (NPh).
Magnetic knitting aromatic polymers (Fe3O4/KAPs) are introduced here as a new kind of sorbents. KAPs are hyper-cross-linked-polymers that were prepared via a Friedl-Crafts reaction from triphenylphosphine and benzene as building blocks. The Fe3O4/KAP composite was obtained by coprecipitation of KAP with magnetite nanoparticles. The resulting Fe3O4/KAP is shown to be a viable magnetic sorbent for various organic materials such as the phenylurea herbicides (PUHs), including metoxuron, monuron, chlortoluron, monolinuron and buturon, and also for various phthalates, polycyclic aromatic hydrocarbons and chlorophenols. The Fe3O4/KAP was characterized by means of Brunauer-Emmett-Teller surface area measurements, Fourier-transform infrared spectroscopy, thermogravimetry, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Following desorption with acetonitrile, the analytes were quantified by using HPLC with UV detection. The effects of adsorbent dosage, extraction time, sample pH, ionic strength, desorption solvent and desorption time were optimized for the PUHs. Under optimal conditions, response is linear from 0.5–1.0 up to 50 ng·mL?1 for the five PUHs. Lower limits of detection range between 0.05 and 0.30 ng·mL?1. Other figures of merit include (a) high enrichment factors (60–297), (b) good recoveries (91.8–106.5%), and (c) relative standard deviations of <8.4%. The method was successfully applied to analysis of the PUHs in real samples (bottled mixed juice, milk and soymilk). The results indicate that such Fe3O4/KAPs have a wide application scope as an adsorbent for use in magnetic solid phase extraction.
Graphical abstract A magnetic knitting aromatic polymer based nanocomposite (Fe3O4/KAP) was prepared by a one-pot method and explored as an absorbent for magnetic solid-phase extraction (MSPE) of phenylurea herbicides (PUHs) from bottled mixed juice, milk and soymilk samples before quantitation by HPLC with UV detection.
The article describes the synthesis of core-shell magnetic nanoparticles (MNPs) of the type Fe3O4@MIL-100 (MIL standing for Material Institut Lavoisier), and their application as sorbent for magnetic solid-phase extraction (MSPE) of triclosan. The MNPs were prepared via circular self-assembly of ferric chloride and benzenetricarboxylic acid. The functionalized MNPs were characterized by transmission electron microscopy, FTIR and thermogravimetry. Following extraction, triclosan was eluted with ammoniacal methanol and then submitted to HPLC with UV detection. The amount of magnetic microspheres, sample pH and ionic strength, adsorption time, desorption time, desorption solvent and the volume of the eluent were optimized. Under optimum conditions, the method showed good linearity in the 0.1 to 50 mg·kg?1 triclosan concentration range in toothpaste samples. Other features include (a) intra-day and inter-day relative standard deviations (RSD, for n = 4) of <5.5 %, (b) a 30 μg·kg?1 limit of detection, and (c) extraction recoveries between 90.86 % and 101.1 %. The method was successfully applied to the determination of triclosan in children’s toothpaste.
Graphical abstract The article describes the synthesis of core-shell magnetic nanoparticles (MNPs) of the type Fe3O4@MIL-100, and their application as sorbent for magnetic solid-phase extraction (MSPE) of triclosan.
Magnetite nanoparticles were surface-modified with mercaptoacetic acid (MAA), complexed with Zn(II), and then treated with the dual Schiff base (referred to as imine-based ligand; IBL; obtained by reaction of p-aminobenzoic acid and 2,3-butanedione) to give particles with an architecture of type Fe3O4@MAA@IBL. These are shown to be viable sorbents for magnetic solid phase extraction of organochlorine pesticides (OCPs) from seawater samples. Efficient extraction of the OCPs probably is due to lone pair-π, π-complexation and π-interactions. The sorbent was characterized by transmission electron microscopy, scanning electron microscopy, FT-IR and energy-dispersive X-ray spectroscopy. The effects of the volumes of sample, sorbent dosage and eluent, adsorption and desorption times, and the salinity of the sample on the extraction efficiencies were optimized. The OCPs (heptachlor, aldrin, dieldrin, p,p’-DDE and p,p’-DDT) were quantified by gas chromatography with microelectron capture detection. Under optimal conditions, the limit of detections range was between 1.0 and 1.9 ng L?1. The enrichment factors are between 84.1 and 99.9 %. The sorbent was applied to the rapid extraction of trace quantities of OCPs from seawater samples and gave good relative recoveries (78 to 108 %) and relative standard deviations (<8.3 %).
Graphical Abstract Fe3O4 nanoparticles were functionalized with mercaptoacetic acid. The carboxylate was coordinated with Zn(II) and the ligands were immobilized via coordination with Zn(II). The lone pair-π, π-complexation and π-interaction of modified magnetite nanoparticles made this sorbent effective for extraction of organochlorine pesticides.
