Magnetic Dispersive Solid-phase Extraction Research Articles

Coupling Miniaturized Stir Bar Sorptive Dispersive Microextraction to Needle-Based Electrospray Ionization Emitters for Mass Spectrometry: Determination of Tetrahydrocannabinol in Human Saliva as a Proof of Concept.

Direct coupling of sample preparation with mass spectrometry (MS) can speed up analysis, enabling faster decision-making. In such combinations, where the analysis time is mainly defined by the extraction procedure, magnetic dispersive solid-phase extraction emerges as a relevant technique because of its rapid workflow. The dispersion and retrieval of the magnetic sorbent are typically uncoupled stages, thus reducing the potential simplicity. Stir bar sorptive dispersive microextraction (SBSDME) is a novel technique that integrates both stages into a single device. Its miniaturization (mSBSDME) makes it more portable and compatible with low-availability samples. This article reports the direct combination of mSBSDME and MS using a needle-based electrospray ionization (NESI) emitter as the interface. This combination is applied to determine tetrahydrocannabinol in saliva samples, a relevant societal problem if the global consumption rates of cannabis are considered. The coupling requires only the transference of the magnet (containing the sorbent and the isolated analyte) from the mSBSDME to the hub of a hypodermic needle, where the online elution occurs. The application of 5 kV on the needle forms an electrospray on its tip, transferring the ionized analyte to the MS inlet. The excellent performance of mSBSDME-NESI-MS/MS relies on the sensitivity (limits of detection as low as 2.25 ng mL-1), the precision (relative standard deviation lower than 15%), and the accuracy (relative recoveries ranged from 87 to 127%) obtained. According to the results, the mSBSDME-NESI-MS/MS technique promises faster and more efficient chemical analysis in MS-based applications.

Magnetic dispersive solid-phase extraction of clarithromycin and azithromycin by Fe3O4@ionic salt g-C3N4 adsorbent and HPLC-UV

In this study, Fe3O4@ionic salt g-C3N4 was synthesized as a new adsorbent for magnetic dispersive solid phase extraction (MDSPE) of two antibiotics (clarithromycin and azithromycin) in biological samples followed by HPLC-UV. The new nanocomposite was characterized by Fourier-transform infrared (FT-IR), field emission-scanning electronic microscope (FE-SEM), transmission electron microscope (TEM), nitrogen adsorption–desorption analysis, X-ray powder diffraction (XRD), and vibrating sample magnetometer (VSM). Box-Behnken design (BBD) and response surface methodology (RSM) were used for the optimization and design of experiments. The method had a suitable linear range (1–300 µg/L), a high coefficient of determination (R2; 0.9988 and 0.9993), and a low detection limit (0.33 and 0.42 µg/L) for clarithromycin and azithromycin, respectively. The applicability of the method was evaluated by estimating the recovery of analytes from urine and blood serum samples. Recovery of more than 90.0 % and RSDs of less than 5.2 % show the acceptable accuracy and precision of the proposed method.

One-step grafting of phenyl functionalized magnetic mesoporous nanocomposites for magnetic dispersive solid-phase extraction and determination of triazole fungicide residues in strawberry fruits

In this work, phenyl-SBA-15@Fe3O4 organic phenyl functional magnetic mesoporous materials were synthesized as adsorbent for magnetic dispersive solid phase extraction (M−DSPE) sample pretreatment. Seven triazole fungicides were simultaneously analyzed by high-performance liquid chromatography coupled with ultraviolet detection (HPLC-UV). The extraction recovery was 82.7 %-88.6 %, and the concentration factor was 10.6–30.8. Under the optimized experimental conditions, the regression equations of seven triazole fungicides showed a good linear relationship, the coefficient of determination r2 was 0.9993–0.9999, and the detection limit was 0.19 ∼ 1.75 μg·L-1. Six strawberry samples were randomly purchased from different places in the market, and flesh,cortex, sepal, and pulp were detected separately. The results showed that flutriafol, triadimenol and difenoconazole were detected, of which flutriafol was detected from all of them and most of them exceeded the national standard. The extraction pretreatment technology is fast and efficient, which can meet the requirements of simultaneous analysis of triazole fungicide residues in strawberries.

Magnetic iron-based metal organic framework as an adsorbent for magnetic dispersive solid-phase extraction of pyrene and phenanthrene in water samples

ABSTRACT A dispersive magnetic solid-phase extraction by means of core-shell iron-based metal-organic framework (Fe3O4- SiO2/EN@MIL-101(Fe)) nanospheres coupled with high-performance liquid chromatographic was developed for the determination of pyrene (Pyr) and phenanthrene (Phe) in water samples. Key parameters such as sorbent amount, sample volume, pH, extraction time, type and volume of elution, and desorption time were optimised by response surface methodology (RSM). Under the optimised conditions (sample volume: 5 mL, extraction time: 3 min, eluent: 3 mL acetonitrile: propanol, and desorption time: 3 min), the developed method showed a low detection and quantification limits (0.015 and 0.040 ng mL−1, respectively), good precision (< 9.8% RSD), wide linear range (0.06 - 10,000 ng mL−1, R2 > 0.99), high enrichment factors (49–57), good matrix effect (> 93.2%), high reusability (25 times), short extraction and desorption time (3 and 3 min, respectively), and high extraction recovery (96.5%). The established method was able to recover the Pyr and Phe from spiked real water samples with an extraction efficiency of 95.71% and 96.32%, respectively (RSD ≤ 9.52%).

Development of an innovative analytical method for forensic detection of cocaine, antidepressants, and metabolites in postmortem blood using magnetic nanoparticles.

Cocaine and antidepressants rank high globally in substance consumption, emphasizing their impact on public health. The determination of these compounds and related substances in biological samples is crucial for forensic toxicology. This study focused on developing an innovative analytical method for the determination of cocaine, antidepressants, and their related metabolites in postmortem blood samples, using unmodified commercial Fe3O4 nanoparticles as a sorbent for dispersive magnetic solid-phase extraction (m-d-SPE), coupled with liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) analysis. An aliquot of 100 µL of whole blood and 5 µL of the internal standard pool were added to 30mg of nanoparticles. The nanoparticles were separated from the sample using a neodymium magnet inserted into a 3D-printed microtube rack. The liquid was then discarded, followed by desorption with 300 µL of 1/1/1 acetonitrile/methanol/ethyl acetate. The sample was vortexed and separated, and 1.5 µL of the organic supernatant was injected into the LC-MS/MS. The method was acceptably validated and successfully applied to 263 postmortem blood samples. All samples evaluated in this study were positive for at least one substance. The most frequent analyte was benzoylecgonine, followed by cocaine and cocaethylene. The most common antidepressants encountered in the analyzed samples were citalopram and fluoxetine, followed by fluoxetine's metabolite norfluoxetine. This study describes the first report of this sorbent in postmortem blood analysis, demonstrating satisfactory results for linearity, precision, accuracy, and selectivity for all compounds. The method's applicability was confirmed, establishing it as an efficient and sustainable alternative to traditional techniques for forensic casework.

Synthesis of the magnetic composite of Ni-MOF-I in aqueous medium and its application in magnetic dispersive micro solid phase extraction of plasticizers from pharmaceutical samples

For the first time, this research presents the synthesis procedure and analytical application of Ni-MOF-I magnetic composite. The synthesis method was green and done in an aqueous medium. The composite was employed as an adsorbent in a magnetic dispersive solid phase extraction process followed by dispersive liquid–liquid microextraction for the extraction and preconcentration of some plasticizers from pharmaceutical samples stored in plastic containers. The Ni-MOF-I magnetic composite was characterized by applying Fourier transform infrared spectrophotometry, vibrating sample magnetometry, scanning electron microscopy, energy-dispersive X-ray, X-ray diffraction, and nitrogen adsorption/desorption analyses. For operating the extraction procedure, initially, the plasticizers were adsorbed onto the adsorbent particles by vortexing. Then, the plasticizers were desorbed from the adsorbent surface using a mL volume of 2-proponal. Subsequently, the obtained eluate phase was mixed with a mixture of 1,2-dibromoethane and 1,1,2-trichloroethane and then injected into deionized water using a glass syringe. Afterward, centrifugation was done to isolate the extractant from the aqueous phase. Eventually, one microliter of the sedimented phase was injected into gas chromatography-flame ionization detection. Acceptable analytical results such as high enrichment factors (355–415) and extraction recoveries (71–83 %), low limits of quantification (0.76–1.08 μg L−1) and detection (0.23–0.33 μg L−1), wide linear ranges (1.08–300 μg L−1), and satisfactory relative standard deviation values of 4.0–6.3 % (intra-day precision, n = 5) and 4.9–7.4 % (inter-day precision, n = 5) were achieved. The suggested procedure was used as a productive analytical method based on the Ni-MOF-I magnetic composite for the extraction and determination of some plasticizers from different pharmaceutical samples filled in plastic containers. Elimination of centrifugation, using 2-propanol as a green desorption/disperser solvent, detection of di-(2-ethylhexyl) phthalate in boric acid alcohol drop, and applying µL-level of the extraction solvent are the advantages of this proposed method.

Development of a continuous magnetic dispersive solid phase extraction method for the extraction of seven widely used pesticides from fruit juices

Generally, food safety monitoring is vital issue to preserve human health and guarantee a longer lifespan. In present study, a continuous mode of magnetic dispersive solid phase extraction method based on using magnetic covalent organic framework@metal organic framework nanocomposite as sorbent has been proposed. The developed method has been tested for the extraction of some pesticides (pirimicarb, terbutryn, fenthion, triticonazole, hexaconazole, diniconazole, and haloxyfop-R-methyl) from commercial fruit juices prior to their analysis by high performance liquid chromatography–tandem mass spectrometry. In the current research, the properties of nanocomposite were characterized by scanning electron microscopy, Fourier–transform infrared spectrophotometry and X–ray diffraction techniques. In the next step, the synthesized nanocomposite was employed as an efficient sorbent in the developed extraction procedure that was done in a narrow bore tube. Under optimum extraction conditions, extraction recoveries were in the ranges of 67–83 %. Moreover, the limits of detection and quantification of the selected analytes were in the ranges of 17–43 and 56–143 ng L−1, respectively. Finally, the proposed method was successfully applied in the analysis of the opted pesticides in sixty fruit juice samples.

Facile Preparation of Magnetic COF-on-COF for Rapid Adsorption and Determination of Sulforaphane from Cruciferous Vegetables

Sulforaphane (SFN) is a natural isothiocyanate compound widely abundant in cruciferous vegetables with multiple bioactive functions. However, traditional analytical methods for the extraction and determination of SFN are cumbersome, time-consuming, and low sensitivity with large amounts of organic solvents. Herein, novel magnetic COF-on-COFs (MB-COFs) were fabricated using Fe3O4 as a magnetic core and COFs-1 grown with COFs-2 as a shell, and they were used as efficient adsorbents of magnetic dispersive solid-phase extraction for rapid quantification of SFN in cruciferous vegetables by combining with HPLC-MS/MS. At the optimal ratio of COFs-1 to COFs-2, MB-COFs had a spherical cluster-like structure and a rough surface, with a sufficient magnetic response for rapid magnetic separation (1 min). Due to the introduction of Fe3O4 and COFs-2, MB-COFs exhibited outstanding extraction efficiencies for SFN (92.5–97.3%), which was about 18–72% higher than that of the bare COFs. Moreover, MB-COFs showed good adsorption capacity (Qm of 18.0 mg/g), rapid adsorption (5 min) and desorption (30 s) to SFN, and favorable reusability (≥7 cycles) by virtue of their unique hierarchical porous structure. The adsorption kinetic data were well fitted by the pseudo-second-order, Ritchie-second-order, intra-particle diffusion, and Elovich models, while the adsorption isotherm data were highly consistent with the Langmuir, Temkin, and Redlich–Peterson models. Finally, under the optimized conditions, the developed method showed a wide linear range (0.001–0.5 mg/L), high sensitivity (limits of quantification of 0.18–0.31 μg/L), satisfactory recoveries (82.2–96.2%) and precisions (1.8–7.9%), and a negligible matrix effect (0.82–0.97). Compared to previous methods, the proposed method is faster and more sensitive and significantly reduces the use of organic solvents, which can achieve the efficient detection of large-scale samples in practical scenarios. This work reveals the high practical potential of MB-COFs as adsorbents for efficient extraction and sensitive analysis of SFN in cruciferous vegetables.

Application of magnetic dispersive solid phase extraction combined with solidification of floating organic droplet-based dispersive liquid–liquid microextraction and GC-MS in the extraction and determination of polycyclic aromatic hydrocarbons in honey

A magnetic dispersive solid phase extraction method combined with solidification of floating organic droplet-based dispersive liquid–liquid microextraction has been validated for the extraction of polycyclic aromatic hydrocarbons from honey samples. For this purpose, a carbonised cellulose–ferromagnetic nanocomposite was used as a sorbent through the magnetic dispersive solid phase extraction. For preparation of the sorbent, first, carbonised cellulose nanoparticles were created by treating cellulose filter paper with concentrated solution of sulfuric acid. Then, the prepared nanoparticles were loaded onto Fe3O4 nanoparticles through coprecipitation. In the extraction process, first, a few mg of the sorbent was added to the diluted honey solution and dispersed in it using vortex agitation. The particles were then separated and the adsorbed analytes were eluted with an organic solvent. The eluent was taken and after mixing with a water–immiscible extraction solvent was used in the following solidification of floating organic droplet-based dispersive liquid–liquid microextraction procedure. By performing the extraction process under the obtained optimum conditions, low limits of detection (0.08–0.17 ng g−1) and quantification (0.27–0.57 ng g−1), satisfactory precision (relative standard deviations ≤ 5.0%), and wide linear range (0.57–500 ng g−1) with great coefficients of determination (r2≥ 0.9986) were obtained.

Fe3O4@nitrogen-doped carbon core-double shell nanotubes as a novel and efficient nanosorbent for ultrasonic assisted dispersive magnetic solid phase extraction of heterocyclic pesticides from environmental soil and water samples.

Fe3O4@nitrogen-doped carbon core-double shell nanotubes (Fe3O4@N-C C-DSNTs) were successfully synthesized and applied as a novel nanosorbent in ultrasonic assisted dispersive magnetic solid phase extraction (UA-DMSPE) of tribenuron-methyl, fenpyroximate, and iprodione. Subsequently, corona discharge ion mobility spectrometry (CD-IMS) was employed for the detection of the extracted analytes. Effective parameters on theextraction recovery percentage (ER%) were systematically investigated and optimized. Under optimal conditions, UA-DMSPE-CD-IMS demonstrated remarkable linearity in different ranges within 1.0 - 700 ng mL-1 with correlation coefficients exceeding 0.993, repeatability values below 6.9%, limits of detection ranging from 0.30 to 0.90 ng mL-1, high preconcentration factors (418 - 435), and ER%values (83 - 87%). The potential of the proposed method was further demonstrated by effectively determining the targeted pesticides in various environmental soil and water samples, exhibiting relative recoveries in the range 92.1 - 102%.

A novel deep eutectic solvent modified magnetic covalent organic framework for the selective separation and determination of trace copper ion in medicinal plants and environmental samples

BackgroundPretreatment techniques should be introduced before metal ion determination because there is very low content of heavy metals in Chinese medicinal plants and environmental samples. Magnetic dispersive micro solid phase extraction (MDMSPE) has been widely used for the separation and adsorption of heavy metal pollutants in medicinal plants and environmental samples. However, the majority of MDMSPE adsorbents have certain drawbacks, including low selectivity, poor anti-interference ability, and small adsorption capacity. Therefore, modifying currently available adsorption materials has gained attention in research. ResultsIn this study, a novel adsorbent MCOF-DES based on a magnetic covalent organic framework (MCOF) modified by a new deep eutectic solvent (DES) was synthesized for the first time and used as an adsorbent of MDMSPE. The MDMSPE was combined with inductively coupled plasma optical emission spectrometry (ICP-OES) for selective separation, enrichment, and accurate determination of trace copper ion (Cu2+) in medicinal plants and environmental samples. Various characterization results show the successful preparation of new MCOF-DES. Under the optimal conditions, the enrichment factor (EF) of Cu2+ was 30, the limit of detection (LOD) was 0.16 μg L−1, and the limit of quantitation (LOQ) was 0.54 μg L−1. The results for the determination of Cu2+ were highly consistent with those of inductively coupled plasma mass spectrometry (ICP-MS), which verified the accuracy and reliability of the method. SignificanceThe established method based on a new adsorption material MCOF-DES has achieved the selective separation and determination of trace Cu2+ in medicinal and edible homologous medicinal materials (Phyllanthus emblica Linn.) and environmental samples (soil and water), which provides a promising, selective, and sensitive approach for the determination of trace Cu2+ in other real samples.

Synthesis and characterization of Restricted Access Magnetic Nanotubes (M-RACNTs) for the extraction of secondary metabolites from Lasiodiplodia sp. fermentation broth

This work proposed the synthesis and the characterization of Restricted Access Magnetic Nanotubes (M-RACNTs) to be used as sorbent in the magnetic dispersive solid-phase extraction (MDSPE) of organic compounds from the fermentation broth of the endophyte Lasiodiplodia sp. Synthesis was performed by functionalizing commercial multiple-walled carbon nanotubes with magnetic nanoparticles (M-CNTs) and by coating the M-CNTs with a layer of bovine serum albumin. The materials were characterized by infrared spectroscopy with Fourier Transform, thermogravimetry, zeta potential, and scanning electron microscopy. Different crude extracts were obtained, depending on the sample pH and the elution solvent tested. Chloroform and ethyl acetate extracts showed activity against a Gram-positive pathogen (Staphylococcus aureus). The crude extract's constitution was investigated. By GC/MS analysis were found hydrocarbons, aldehydes, alcohols, among others, while by LC-MS/MS analysis were found flavonoids, macrocyclic lactones, oleic acids, jasmonic acid derivatives and amino acids. A multivariate optimization, through fractional factorial planning, for four independent variables, was performed for a hydrocarbon (hexadecane) and one possible jasmonic acid derivative, both with antimicrobial activity related in the literature. The results showed that it was possible to obtain crude extracts with high concentrations of these analytes in a single extraction procedure. The increase in the analytical signal was 3.7 times for hexadecane and 1.4 times for the possible jasmonic acid derivative. The M-RACNTs also demonstrated their ability to prevent the adsorption of macromolecules, such as lysozyme, which was confirmed through SDS-PAGE analysis.

Synthesis of ionically imprinted Poly(Alylthiourea) in the presence of 1-(2-Pyridylazo)-2-Napthol (PAN) for preconcentration in magnetic dispersive solid phase of nickel ions in water and food samples

In the present study, a magnetic ion-imprinted polymer based on n-allylthiourea in the presence of 1-(2-pyridylazo)-2-naphthol (MIIP-PAN) was synthesized, characterized, and applied in the preconcentration of nickel ions by dispersive magnetic solid phase extraction (DMSPE) with FAAS detection. For comparison, non-imprinted polymer (MNIP-PAN) and imprinted polymer without PAN were synthesized. The characterization of the polymers was performed by FT-IR, DRX, TEM, TGA, VSM, and BET. Selectivity studies were performed comparing the competitive adsorption of Ni2+ with other cations on MIIP-PAN and MNIP-PAN, achieving higher relative selectivity coefficients for MIIP-PAN than for MNIP-PAN and NIP. Under optimized conditions, the method provided a preconcentration factor of 76.70, detection limit of 0.25 µg/L and intra-day (2.06 – 2.33 %) and inter-day (1.82 – 4.90 %) precision. The developed method was applied to samples of water, teas, and chocolate powder, and its precision was evaluated through tests of recovery and analysis of certified materials.

Automatic MDSPE Combined with DART-HRMS for the Rapid Quantitation of 21 Synthetic Cathinones in Urine.

A new, rapid, and automated method for the quantitation of 21 synthetic cathinones in urine was established using magnetic dispersive solid-phase extraction (MDSPE) in combination with direct analysis in real time-high-resolution mass spectrometry (DART-HRMS). Sample preparation and quantitation were verified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Methcathinone-D3, α-PVP-D8, and proadifen (SKF525A) were used as internal standards. Magnetic HLB extractant and NaH2PO4/NaOH buffer (0.2 M, pH 7) were used in automatic MDSPE. All 21 synthetic cathinones could be detected and analyzed by DART-HRMS in under 1 min. It was proven that the linearities of 21 synthetic cathinones were suitable (R2 > 0.99) in the concentration ranges of 0.5-100 ng/mL or 1-100 ng/mL. The precision and accuracy values were all within ±15%, and the samples were stable under various conditions. The average time of each sample from preprocessing to completion of detection was approximately 2 min, allowing for rapid sample analysis. The relative error (RE) of the concentrations obtained by DART-HRMS and LC-MS/MS were within ±13.61%, and the linear coefficient (R) was 0.9964. The results of DART-HRMS and LC-MS/MS provided equivalent values at the 95% confidence level. In summary, a simple, fast, and convenient quantitation method via DART-HRMS was established. This application can be utilized to reduce backlogs and promote rapid case processing.

A magnetic adsorbent of nitrogen-doped graphene quantum dots, zinc metal-organic framework and molecularly imprinted polymer to extract phenylureas

A highly selective composite nano-sorbent was designed and fabricated for the extraction and enrichment of phenylureas. The nano-sorbent was composed of nitrogen-doped graphene quantum dots (N-GQDs), a zinc metal-organic framework (IRMOF-1) and magnetite nanoparticles incorporated in molecularly imprinted polymer (MIP). The fabricated nano-sorbent was characterized and applied to extract and enrich three phenylureas in a dispersive magnetic solid-phase extraction (d-MSPE) process. The developed method was highly sensitive and detected the target phenylureas at trace levels. The linear range was from 1.0 to 150 µg L−1 and the limit of detection was 1.0 µg L−1. The large specific surface area of the nano-sorbent produced highly efficient adsorption. When applied to extract phenylureas in vegetable samples, recoveries were in the range of 80.2–95.8% with relative standard deviations lower than 8.0%. The developed nano-sorbent not only exhibited highly selective and efficient extraction but also good stability which can be reused four times, and ease of fabrication. The developed strategy can also be modified for the extraction and determination of other organic compounds in various complex samples.

The simultaneous measurement of atomoxetine, venlafaxine, and duloxetine in actual water and biological samples requires the creation of a unique magnetic dispersive micro solid phase extraction sorbent based on MOF-on-MOF

ABSTRACT Atomoxetine, venlafaxine, and duloxetine are three antidepressant drugs widely prescribed to treat this disorder. Determining these drugs is a major challenge due to their low concentration and high matrix effects on biological samples. Dispersive micro solid phase extraction was developed as a sample preparation strategy to extract these drugs in real water and biological samples. A novel sorbent containing a magnetic MOF-on-MOF was prepared to extract these drugs using Fe3O4 nanoparticle and Sol-gel technique. The microextraction procedure was optimised under two steps using experimental design. Three factors, including pH, sorbent amount, and desorption solvent volume, significantly affected the extraction of analytes and optimised using a central composite design. The optimum value of pH, sorbent amount, and desorption solvent volume was 29 mg, 6.5, and 150 µL. Under optimum conditions, the linear ranges for measuring atomoxetine, venlafaxine, and duloxetine in water samples were 1.42–496, 0.43–472, and 0.73–459 ng mL−1, respectively. The detection limits of atomoxetine, venlafaxine, and duloxetine were 0.4, 0.1, and 0.2 ng mL−1. High and proper preconcentration factors ranged from 462.4–511.4 in distiled water samples and 450.7–489.8 in urine samples were obtained to determine atomoxetine, venlafaxine, and duloxetine with three concentrations of 5.0, 20.0, and 100.0 ng mL−1, respectively. Inter-day and intra-day RSD% were calculated by triplicate determination of atomoxetine, venlafaxine, and duloxetine at three concentrations of 10.0, 50.0 and 100.0 ng mL−1 and were between 3.2–4.3% and 3.8–4.6% in distiled water samples, and 4.8–5.7% and 5.0–5.8% in urine samples, respectively. Analysis of tap, river water, and two urine samples as real water and biological samples under optimum conditions exhibited recovery and standard deviation in the ranges of 90.2–96.9% and 3.84–5.74%, respectively, confirmed the proper ability of the method to determine atomoxetine, venlafaxine, and duloxetine in natural water and biological samples.

Enhancing Trace Metal Extraction from Wastewater: Magnetic Activated Carbon as a High-Performance Sorbent for Inductively Coupled Plasma Optical Emission Spectrometry Analysis

A new fast, sensitive, and environmentally friendly analytical method has been developed for the simultaneous determination of Ba, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn in wastewater samples using inductively coupled plasma optical emission spectroscopy (ICP OES). A preconcentration step using a magnetic dispersive solid-phase extraction (MDSPE) technique with a new magnetic sorbent was performed. The new sorbent material was a carbon containing magnetic cobalt and nitrogen groups. This material was synthetized using controlled pyrolysis of a zeolitic imidazolate framework (i.e., ZIF-67). In order to optimize the experimental parameters that affect the MDSPE procedure, a multivariate optimization strategy, using Plackett–Burman and circumscribed central composite designs (CCD), was used. The method has been evaluated employing optimized experimental conditions (i.e., sample weight, 10 g; sample pH, 7.6; amount of sorbent, 10 mg; dispersive agent, vortex; complexing agent concentration, 0.5%; ionic concentration, 0%; eluent, HCl; eluent concentration, 0.5 M; eluent volume, 300 μL; elution time, 3 min and extraction time, 3 min) using external calibration. Limits of detection (LODs) in a range from 0.073 to 1.3 μg L−1 were obtained, and the repeatability was evaluated at two different levels, resulting in relative standard deviations below 8% for both levels (n = 5). An increase in the sensitivity was observed due to the high enrichment factors (i.e., 3.2 to 13) obtained compared with direct ICP OES analysis. The method was also validated through carrying out recovery studies that employed a real wastewater sample and through the analysis of a certified reference material (ERM®-CA713). The recovery values obtained with the real wastewater were between 94 and 108% and between 90 and 109% for the analysis of ERM®-CA713, showing negligible matrix effects.

Synthesis of novel oxytetracycline-molecularly imprinted polymer using a semi-covalent chemical imprinting approach for magnetic dispersive solid phase extraction of tetracyclines in water and milk samples

In the present study, a highly efficient analytical method based on preconcentration of tetracyclines (TCs) in water and milk samples using a magnetic molecularly imprinted polymer (Fe3O4/SiO2/MIP) synthesized by means of a novel semi-covalent synthesis for TCs and determination by HPLC-DAD was proposed. Fe3O4/SiO2/MIP showed specific superficial area of 216.0 m2/g, superior to Fe3O4/SiO2/NIP (non-imprinted material) (103.6 m2/g). Using the Fe3O4/SiO2/MIP, the magnetic dispersive solid phase extraction (MDSPE) for four TCs (chlortetracycline, doxycycline, oxytetracycline, and tetracycline) was based on the preconcentration of 40.0 mL of sample (pH 4.0) vortex-assisted with 10 mg of Fe3O4/SiO2/MIP during 60 s. The method presented a limit of detection (LOD) in the range 0.26–0.60 µg/L, and preconcentration factor in the range 52.3–87.4-fold for the TCs. The method was applied to determine TCs in samples of lake water and cow milk with recovery results ranging from 96.0 to 102.0 %.

One Pot Synthesis of Nanofiber-Coated Magnetic Composites as Magnetic Dispersive Solid-Phase Extraction Adsorbents for Rapid Determination of Tetracyclines in Aquatic Food Products.

A magnetic adsorbent based on a C-nanofiber (Fe3O4@C-NFs) nanocomposite was synthesized using a simple one-pot co-precipitation method. The characterized results showed that the obtained C-nanofiber-coated magnetic nanoparticles had many attractive features such as a large specific surface area and a highly interwoven and branched mesoporous structure, as well as distinguished magnetism. The nanocomposite was then used as an adsorbent in the magnetic solid phase extraction (MSPE) of four typical tetracyclines (oxytetracycline, tetracycline, chlortetracycline, and doxycycline) in aquatic products. The TCs in the extract were determined using ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Experimental variables of MSPE, including the sorbent amount, pH condition, adsorption and desorption time, and desorption solvent, were investigated and optimized systematically. The method validation indicated that the developed method showed good linearity (R2 > 0.995) in the range of 1.0-200 ng/mL. The average recoveries at the spiked levels ranged from 90.7% to 102.7% with intra-day and inter-day relative standard deviations (RSDs, n = 6) ranging from 3.72% to 8.17% and 4.20% to 9.69%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) for the four kinds of TCs were 0.7 μg/kg and 2.0 μg/kg, respectively. Finally, MSPE based on C-nanofiber-coated magnetic nanoparticles was successfully applied to TC analysis in real aquatic products (grass carp, large yellow croaker, snakehead, mandarin fish, Penaeus vannamei, swimming crab, etc.). Compared with traditional extraction methods, the proposed method for TC analysis in aquatic products is more sensitive, effective, recyclable, and environmentally friendly.

Studies on the extraction performance of phorate by aptamer-functionalized magnetic nanoparticles in plasma samples

Abstract Phorate, a highly toxic organophosphorus pesticide, poses significant risks due to its efficiency, versatility, and affordability. Therefore, studying pretreatment and detection methods for phorate in complex samples is crucial. In this study, we synthesized core-shell phorate aptamer-functionalized magnetic nanoparticles using solvothermal and self-assembly techniques. Subsequently, we developed a magnetic dispersive solid-phase extraction and detection method to identifying phorate in plasma samples. Under optimal conditions, we achieved quantitation of phorate within a range of 2–700 ng·mL−1 using gas chromatography-mass spectrometry. The detection limit (S/N = 3) was 0.46 ng·mL−1, and the intraday and interday relative standard deviation were 3.4% and 4.1%, respectively. In addition, the material exhibited excellent specificity, an enrichment capacity (EF = 416), and reusability (≥15). During phorate extraction from real plasma samples, spiked recoveries ranged from 86.1% to 101.7%. These results demonstrate that our method offers superior extraction efficiency and detection capability for phorate in plasma samples.