Magnetic Solid-phase Extraction Adsorbent Research Articles

Magnetic solid-phase extraction of tetracyclines from milk using metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic magnetic nanoparticles

Novel metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic polydopamine-modified Fe3O4 magnetic nanoparticles (Fe3O4@PDA@MIL-101(Cr)-NH2) were synthesised and used as magnetic solid-phase extraction (MSPE) adsorbents for extracting tetracyclines (TCs) from milk samples. The integrated Fe3O4@PDA@MIL-101(Cr)-NH2 exhibited convenient magnetic separation and exceptional multi-target binding capabilities. Furthermore, the PDA coating significantly enhanced the hydrophilicity and extraction efficiency of the material, thereby facilitating the extraction of trace TCs. Various factors affecting MSPE, such as adsorbent dosage, extraction time, pH value, and desorption conditions, were optimised. The developed MSPE method coupled with high-performance liquid chromatography demonstrated good linearity (R2 ≥ 0.9989), acceptable accuracy (82.2%–106.1%), good repeatability (intra-day precision of 0.8%–4.7% and inter-day precision of 1.1%–4.5%), low limits of detection (2.18–6.25 μg L−1), and low limits of quantification (6.54–18.75 μg L−1) in TCs detection. The approach was successfully used for the quantification of trace TCs in real milk samples.

Nitrogen-doped magnetic porous carbon nanospheres derived from dual templates-induced mesoporous polydopamine coated Fe3O4 for efficient extraction and sensitive determination of volatile nitrosamines by gas chromatography-mass spectroscopy

N-nitrosamines (NAs) are highly carcinogenic compounds commonly found in food, beverages, and consumer products. Due to their wide polarity range, it is challenging to find a suitable carbon adsorbent that can simultaneously adsorb and enrich both polar and nonpolar NAs with good recovery. In this study, nitrogen-doped magnetic mesoporous carbon nanospheres (M-MCN) were prepared and employed as an adsorbent for magnetic solid-phase extraction (MSPE) to extract and concentrate four NAs. The introduction of nitrogen functional groups enhanced the hydrophilicity of the carbon material, allowing M-MCN to achieve a balance between hydrophilicity and hydrophobicity, resulting in good recovery for both polar and nonpolar NAs. A method combining MSPE with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of NAs in processed meat and alcoholic beverages. The method exhibited a good linear range (1-100 ng g-1, r2 > 0.9967) and trace-level detection (0.53-6.6 ng g-1). The recovery rates for the four NAs ranged between 85.7-110.7%, with intra-day precision expressed as relative standard deviation (RSD) between 4.1-10.7%, and inter-day precision between 4.8-12.9%. The results demonstrated not only good accuracy and precision but also provided a new adsorbent for the enrichment of trace-level NAs in processed meat and alcoholic beverage samples.

The magnetic layered double hydroxide/zeolitic imidazolate framework-8 nanocomposite coupled with HPLC-MS/MS for the detection of heterocyclic aromatic amines in thermally processed meat

In this research, a novel magnetic nanocomposite (Fe3O4@Zn/Al-LABSA-LDH/ZIF-8) was synthesized using Fe3O4 as the magnetic core, layered double hydroxide (LDH) with linear alkylbenzene sulfonic acid (LABSA) intercalation and zeolitic imidazolate framework-8 (ZIF-8) as the shell. Benefiting from the intercalation of LABSA into LDH combined with ZIF-8, the multiple interactions, including π-π stacking, hydrogen bonding, and electrostatic interactions, conferred high selectivity and good extraction capability to the material towards heterocyclic aromatic amines (HAAs). Fe3O4@Zn/Al-LABSA-LDH@ZIF-8 was used as an adsorbent for magnetic solid-phase extraction (MSPE) to enrich HAAs in thermally processed meat samples, followed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) detection. The method exhibited a low detection limit (0.021–0.221 ng/g), good linearity (R2 ≥ 0.9999), high precision (RSD < 7.2 %), and satisfactory sample recovery (89.7 % -107.5 %). This research provides a promising approach for developing novel adsorbents in sample preparation and improving analytical performance.

Synthesis of weak cation exchange/C18 bifunctional magnetic polymers for pretreatment and determination of glufosinate and its two metabolites in plasma samples

This study focuses on the purification and detection of glufosinate (GLUF) and its metabolites N-acetyl GLUF and MPP in plasma samples. A Dikma Polyamino HILIC column was used for the effective retention and separation of GLUF and its metabolites, and the innovative addition of a low concentration of ammonium fluoride solution to the mobile phase effectively improved the detection sensitivity of the target analytes. Monodisperse core-shell weak cation exchange (WCX)/C18 bifunctional magnetic polymer composites (Fe3O4@WCX/C18) were prepared in a controllable manner, and their morphology and composition were fully characterized. The Fe3O4@WCX/C18 microspheres were used as a magnetic solid-phase extraction (MSPE) adsorbent for the sample purification and detection of GLUF and its metabolites in plasma samples combined with liquid chromatography-tandem mass spectrometry (LC-MS/MS). The purification conditions of Fe3O4@WCX/C18 microspheres for GLUF and its metabolites in spiked plasma samples were optimized to achieve the best MSPE efficiency. The purification mechanisms of the target analytes in plasma samples include electrostatic attraction and hydrophobic interactions. Furthermore, the effect of the molar ratio of the two functional monomers 4-VBA and 1-octadecene in the adsorbent was optimized and it shows that the bifunctional components WCX/C18 have a synergistic effect on the determination of GLUF and its metabolites in plasma samples. In addition, the present study compared the purification performance of the Fe3O4@WCX/C18 microsphere-based MSPE method with that of the commercial Oasis WCX SPE method, and the results showed that the Fe3O4@WCX/C18 microsphere-based MSPE method established in this work had a stronger ability to remove matrix interferences. Under optimal purification conditions, the recoveries of GLUF and its metabolites in plasma were 87.6–111 % with relative standard deviations (RSDs) ranging from 0.2 % to 4.8 %. The limits of detection (LODs, S/N≥3) and limits of quantification (LOQs, S/N≥10) were 0.10–0.18 μg/L and 0.30–0.54 μg/L, respectively. The MSPE-LC-MS/MS method developed in this study is fast, simple, accurate and sensitive and can be used to confirm GLUF intoxication based not only on the detection of the GLUF prototype but also on the detection of its two metabolites.

Effective enrichment and separation of three flavonoids from Ohwia caudata (Thunberg) H. Ohashi using magnetic layered double hydroxide/ZIF-8 composites and pCEC

In this study, Fe3O4@ZnCr–layered double hydroxide/zeolitic imidazolate frameworks-8 (MLDH/ZIF-8) magnetically functionalized composites were synthesized by co-precipitation and in situ growth based on the advantages of LDHs and ZIF-8 using Fe3O4 nanoparticles as a magnetic substrate to obtain adsorbents with excellent performance. Moreover, the composite was used for the efficient enrichment of flavonoids in Chinese herbal medicines. The internal structures and surface properties were characterized by SEM, Fourier transform infrared spectroscopy, X-ray diffraction and so on. MLDH/ZIF-8 exhibited a large specific surface area and good paramagnetic properties. The MLDH/ZIF-8 magnetic composite was used as a magnetic solid-phase extraction (MSPE) adsorbent, and a MLDH/ZIF-8 MSPE–pressurized capillary electrochromatography coupling method was developed for the separation and detection of flavonoids (luteolin, kaempferol and apigenin) in a sample of the Chinese herb Ohwia caudata (Thunberg) H. Ohashi. The relevant parameters affecting the extraction efficiency were optimized to determine the ideal conditions for MSPE. 5 mg of adsorbent in sample solution at pH 6, vortex extraction for 5 min, elution with 1.5 mL of ethyl acetate for 15 min. The method showed good linearity in the concentration range of 3–50 μg mL−1 with correlation coefficients of 0.9934–0.9981, and displayed a relatively LODs of 0.07–0.09 μg mL−1. The spiked recoveries of all analytes ranged from 84.5% to 122.0% with RSDs (n=3) between 4.5% and 7.7%. This method is straightforward and efficient, with promising potential in the separation and analysis of active ingredients in various Chinese herbal medicines.

Preparation of a β-cyclodextrin grafted magnetic biochar for efficient extraction of four antiepileptic drugs in plasma samples

Simultaneous monitoring of plasma concentration levels of multiple antiepileptic drugs (AEDs) is essential for dose adjustment in comprehensive epilepsy treatment, necessitating a sensitive technique for accurate extraction and determination of AEDs. Herein, a magnetic solid-phase extraction (MSPE) technique on the basis of modified biochar (BC) is investigated to extract four AEDs from plasma, in conjunction with high performance liquid chromatography. BC derived from Zizyphus jujuba seed shells was activated by phosphoric acid (PBC) and magnetized via coprecipitation to produce MPBC. The MPBCCD obtained after modification with β-cyclodextrin (CD) was characterized and evaluated for adsorption. It exhibited fast adsorption kinetics based on second-order kinetics and satisfactory adsorption capacity for AEDs. Then it was employed as the MSPE adsorbent and the influencing parameters were optimized. The enrichment factor was 18.75. The validation analysis revealed a favorable linearity that ranged from 0.04 to 20 μg·mL−1 along with a low limit of detection of 6.85 to 10.19 ng·mL−1. The recovery of the AEDs ranged from 78.7 to 109.2 %, with relative standard deviations below 6.7 %. Using quantum chemistry theory calculations and experimental results analysis, the adsorption mechanism was investigated. It disclosed that the suggested strategy built upon MPBCCD was appropriate for the assessment of AEDs in plasma and expanded the usage of BC as the environmentally favorable matrix for the analysis of biological samples.

Rapidly enrichment and detection of per-and polyfluoroalkyl substances in foods using a novel bifunctional covalent organic framework

Per- and polyfluoroalkyl substances (PFASs) are extensively found in foods, posing potential toxicity to humans. Therefore, rapid analysis and monitoring of PFASs in foods are crucial for public health and also a challenge. To detect trace PFASs in foods, construction of sorbents with multiple interactions could be an effective approach. Herein, a cationic-fluorinated covalent organic framework (CF-COF) was prepared by post-modification and used as a magnetic solid-phase extraction adsorbent for adsorption of PFASs. By combining magnetic solid-phase extraction based on CF-COF with liquid chromatography−tandem mass spectrometry (LC − MS/MS), a novel method was developed for determination of eight long-chain PFASs in foods. Under optimized conditions, the method exhibited low detection limits (0.003–0.019 ng/g) and satisfactory recovery rates (73.5–118%) for PFASs. This study introduces a novel idea for the development of adsorbents targeting PFASs, along with a new analytical method for monitoring of PFASs in foods.

Magnetic polyimide nanocomposite for analysis of parabens in cooking wine by magnetic solid-phase extraction coupled with gas chromatography – Mass spectrometry

A magnetic polyimide (PI) nanocomposite has been synthesized by phase inversion of PI and simultaneous encapsulation of Fe3O4 nanoparticles. The Fe3O4/PI nanocomposite was characterized by a variety of characterization techniques, including infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption isotherms, and vibrating sample magnetometry. The results showed that the prepared nanocomposite had a homogeneous structure, adequate specific surface area (76.1 m2/g) and high saturation magnetization (42.9 emu/g). Using parabens as model analytes, the performance of the Fe3O4/PI nanocomposite as an adsorbent for magnetic solid-phase extraction (MSPE) was evaluated. The extracted parabens were desorbed and determined by gas chromatography–mass spectrometry (GC–MS). The parameters affecting the extraction and desorption efficiency of parabens were optimized. Under the optimal conditions, the developed MSPE/GC–MS method was successfully applied to the determination of parabens in cooking wine. The MSPE/GC–MS method exhibited broad linearity (0.2–100 µg/L), low detection limits (0.04–0.05 µg/L), and satisfactory extraction recoveries (79.2 %–113.3 %) with relative standard deviations (RSDs) ranging from 0.7 % to 10.4 %. For real cooking wine samples, the spiked recoveries ranged from 91.7 % to 118.7 % with RSDs of 1.0 %–11.2 %. The results demonstrated that the Fe3O4/PI nanocomposite was an effective adsorbent, and this work provides a novel reference for the easy preparation of magnetic adsorbent materials.

In situ growth of ZIF-67 to construct core-shell mosaic structural composites for efficient extraction of benzoylurea insecticides.

A novel mosaic structure Silica@C/Co@ZIF-67 composite was synthesized by successfully embedding Co nanoparticles on the surface of silica spheres with the help of thermoplastic polyethyleneimine by carbon-reduction. The ZIF-67 half-shell layer structure was synthesized by the in-situ growth of ZIF-67 on the surface of silica spheres through the coordination of 2-methylimidazole with Co metal nodes. The composite was used as a magnetic solid-phase extraction adsorbent combined with high performance liquid chromatography-ultraviolet detector (HPLC-UV) for the extraction and determination of benzoylurea insecticides (BUs) in vegetables and tea. Based on the presence of π-π, hydrophobic and hydrogen bonding interactions between Silica@C/Co@ZIF-67 and BUs, the BUs were rapidly captured by the composites resulting in high adsorption performance. Under the optimal extraction parameters, the linear ranges were 0.3-200µg L-1 for diflubenzuron, 0.6-200µg L-1 for chlorbenzuron, and 1.0-200µg L-1 for triflumuron, teflubenzuron, and flufenoxuron, with correlation coefficients (R2) greater than 0.9991. The limits of detection (LODs) of the method were 0.1-0.3μg L-1, and the relative standard deviations (RSDs) were 1.2-3.0% for intra-day and 2.6-4.6% for inter-day. In the spiked recovery experiments of vegetables and tea, the recoveries of the five kinds of BUs ranged from 75.8 to 112.9%. In addition, after 10 repetitions using Silica@C/Co@ZIF-67, the recoveries of the five kinds of BUs were still as high as 78.4 to 83.9%.

Developing a novel magnetic organic polymer for selective extraction and determination of 16 macrolides in water and honey samples.

A novel magnetic organic polymer Fe3O4@SiO2@Tb-PDAN was designed and synthesized, which was used as an adsorbent for magnetic solid-phase extraction (MSPE) of 16 macrolides (MALs) in water and honey. The synthesized adsorbent was characterized using techniques including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). Then several parameters of the extraction process were further optimized. Under the optimized conditions, an MSPE-LC-MS/MS method was established for extraction and determination of 16 MALs, which showed good linearity (r ≥ 0.999), low limits of detection (0.001-0.012 μg L-1 for water and 0.001-0.367 μg kg-1 for honey) and satisfactory recoveries (70.02-118.91%) with the relative standard deviations (RSDs) lower than 10.0%. This established method was then successfully applied to detect MALs in real samples, which suggested that Fe3O4@SiO2@Tb-PDAN was a potential magnetic adsorbent for efficient extraction and analysis of MALs.

Preparation and extraction property study of corn cob-like magnetic mosaic carbon materials derived from MOF-on-MOF composites

BackgroundLarge accumulations of pesticide residues in the environment eventually enter the human body with food. Based on magnetic solid-phase extraction (MSPE) technology, it is possible to achieve efficient extraction of trace pesticide residues in foodstuffs, and the construction of MSPE adsorbents with excellent magnetic properties and many active sites is still one of the main research topics. Based on this, we developed a new strategy for the preparation of "MOF-on-MOF" composites, which were carbonized and used as adsorbents for the extraction of pesticide residues in cereals. ResultsA novel corn cob core-shell composite Fe2O3@C@ZIF-8 was created by embedding ZIF-8 onto the surface of Fe2O3@C derived from MIL-88A(Fe), and used for the extraction of benzoylurea insecticides(BUs) from cereals. The adsorption behaviour between Fe2O3@C@ZIF-8 and BUs was investigated by static and kinetic experiments and the adsorption mechanism was elaborated. For the trace analysis of BUs, a magnetic solid-phase extraction combined with high performance liquid chromatography-ultraviolet detector (HPLC-UV) approach was also developed. Under the optimized experimental conditions, the limits of detection and quantification were 0.015–0.03 μg L−1 and 0.05–0.1 μg L−1, and the relative standard deviations for the intra-day and inter-day ranges were 1.82%–2.13 % and 3.85%–4.59 %, respectively. The spiked recoveries of the four cereals ranged from 82.72% to 104.45 %. After 10 cycles of use of Fe2O3@C@ZIF-8, the recoveries of BUs ranged from 77.90% to 96.74 %. SignificanceThe analytical method based on Fe2O3@C@ZIF-8 as adsorbent has a low limit of detection, a wide linear range and is highly applicable to the analysis of real samples. In addition, the strategy developed in this study for the preparation of thermoplastic polymer-assisted "MOF-on-MOF" composites has promising applications.

Synthesis of composite materials combining magnetic metal-organic frameworks and conjugated organic frameworks for selective extraction of carbendazim and thiabendazole residues from Chinese herbal medicine samples

A magnetic metal-organic framework MIL-68(Al) and a covalent organic framework were used as magnetic solid-phase extraction (MSPE) adsorbents in combination with high-performance liquid chromatography ultraviolet detection (HPLC-UV) to detect carbendazim (CBZ) and thiabendazole (TBZ). The main parameters affecting the extraction in the MSPE process were studied and optimized. Fe3O4@MIL-68(Al) coated with 1,3,5-tris(4-aminophenyl)benzene and terephthaldehyde (Fe3O4@MIL-68(Al)@TAPB-PDA-COF) was analyzed and verified. The material was proven to be suitable for adsorbing CBZ and TBZ. Various adsorption models were used to study its adsorption mechanism. The adsorption results were in good agreement with the pseudo-second-order kinetic model and Langmuir isotherm model. The maximum adsorption capacities of Fe3O4@MIL-68(Al)@TAPB-PDA-COF over CBZ and TBZ were 54.24 and 67.87 mg g−1, respectively, and the equilibrium adsorption time was 200 min. Fe3O4@MIL-68(Al)@TAPB-PDA-COF with excellent recyclability showed higher adsorption capacity and selectivity. A method based on Fe3O4@MIL-68(Al)@TAPB-PDA-COF combined with HPLC-UV was established under the optimal extraction conditions and used to separate and detect trace imidazole drugs in Chinese herbal samples, achieving a low limit of detection (0.65–1.30 μg L−1) with excellent linear correlation (r > 0.999). The recovery rate and relative standard deviation were 86.05–99.78 % and 0.15–4.90 %, respectively. Therefore, the Fe3O4@MIL-68@TAPB-PDA-COF can be regarded as an effective adsorbent for the pretreatment of CBZ and TBZ drugs in Chinese herbal samples.

Magnetic multi-walled carbon nanotubes assisted solid phase extraction and detection of neonicotinoid pesticides in honey and tea samples

In this study, magnetic multi-walled carbon nanotubes (MMWCNTs) were prepared by a one-pot solvothermal method. And they were used as the adsorbent of magnetic solid-phase extraction (MSPE) to extract NEOs. MMWCNTs exhibit good adsorption performance toward NEOs. The adsorption capacities for imidacloprid, thiacloprid, and acetamiprid are 18.4, 25.9, and 18.4 mg g−1, respectively. Also, the adsorption process takes 20 min. The adsorption isotherm fitted to the Langmuir model and the adsorption kinetics was well described by the pseudo-second-order kinetic model. Moreover, the adsorption mechanism was discussed. The MMWCNTs-based MSPE method was combined with field-enhanced sample stacking-capillary electrophoresis (FESS-CE) to realize the sensitive detection of NEOs. The detection limits of NEOs in honey and bottled green tea beverage samples ranged from 7.63 to 16.7 ng g−1. The recoveries were in the range of 84.5 ± 3.2 % to 99.2 ± 1.6 %, with relative standard deviations less than 5.5 %, suggesting the feasibility of the method in actual samples.

Simultaneous detection of heterocyclic aromatic amines and acrylamide in thermally processed foods by magnetic solid-phase extraction combined with HPLC-MS/MS based on cysteine-functionalized covalent organic frameworks.

Acrylamide (AA) and heterocyclic aromatic amines (HAAs), as classic hazards produced during food thermal processing, have been widely concerned, but because of their polarity difference, it is very difficult to detect these contaminants simultaneously. Herein, novel cysteine (Cys)-functionalized magnetic covalent organic frameworks (Fe3O4@COF@Cys) were synthesized via a thiol-ene click strategy and then used as adsorbents for magnetic solid-phase extraction (MSPE). Benefiting from the hydrophobic properties of COFs and the modification of hydrophilic Cys, AA and HAAs could be enriched simultaneously. Then, a rapid and reliable method based on MSPE coupled with HPLC-MS/MS was developed for the simultaneous detection of AA and 5 HAAs in thermally processed foods. The proposed method showed good linearity (R2≥0.9987) with satisfactory limits of detection (0.012-0.210μgkg-1) and recoveries (90.4-102.8%). Actual sample analysis showed that the levels of AA and HAAs in French fries were affected by frying time and temperature, water activity of samples, content and type of reaction precursors, and reuse of oils.

Room-temperature synthesis of imine-linked magnetic covalent organic polymers in deep eutectic solvents for the extraction of flavonoids and their determination with HPLC-MS/MS.

A novel imine-linked magnetic covalent organic polymer, Fe3O4@TAB-TFPT, was synthesized using environmentally friendly deep eutectic solvents as the reaction medium instead of conventional organic solvents. The materials were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), FT-IR, N2 adsorption-desorption isotherms, energy dispersive spectrometer (EDS), X-ray photoelectron spectra (XPS), and thermo gravimetric analysis (TGA). Subsequently, the materials were employed as an adsorbent for magnetic solid-phase extraction (MSPE) of flavonoids, including Kurarinone, Norkurarinone, Xanthohumol, and Isoxanthohumol, prior to their determination by HPLC-MS/MS. The validation results demonstrate good linearity within the concentration range 0.1-1000ng∙mL-1 (R2 ≥ 0.9963), high enrichment factors ranging from 18.9 to 30.7, and low LODs (0.01-0.05ng∙mL-1) and LOQs (0.05-0.1ng∙mL-1). Furthermore, recoveries between 80.60% and 108.40% with relative standard deviations ≤ 8.49% were achieved. The proposed MSPE-HPLC-MS/MS method was successfully applied to the determination of flavonoids in Sophora flavescens Aition sample.

Synthesis of magnetic covalent organic framework composites for effective extraction of benzimidazole fungicides from food samples

Benzimidazoles (BZDs) are widely applied and easily accumulated through the food chain and endanger human health. Effective sample pre-treatment technology is the key procedure for trace BZDs analysis. Herein, magnetic covalent organic frameworks (Fe3O4@TRITER) nanospheres, as magnetic solid-phase extraction (MSPE) adsorbent, were synthesized and well characterized. The efficient extraction of BZDs residues depended on large specific surface of COFs and π-π and hydrophobic interactions between TRITER shell and BZDs. Under the optimal MSPE conditions, the developed MSPE-HPLC based on Fe3O4@TRITER method for BZDs residues afforded good linearities (0.01–1 μg mL−1) with R2 (≥0.996) and low limit of detections (3 ng mL−1). The developed Fe3O4@TRITER based MSPE-HPLC method was evaluated and successfully applied to determine BZDs residues in orange juice, mixed juice drink and cucumber with satisfactory recoveries (76.9–117 %) and relative standard deviations (0.10–7.90 %).

Fabrication of a magnetic metal-organic framework/covalent organic framework composite for simultaneous magnetic solid-phase extraction of seventeen trace quinolones residues in meats

Effective capture of quinolones (QNs) in animal-derived food is a vital procedure for food safety monitoring. However, the lack of adsorption specificity and difficult to recycle in complex substrate conditions have been major problems for most of the adsorbents. In this work, a magnetic Fe3O4/MOF/COF composite (named Fe3O4@NH2−MIL-125@TpPa-SO3H) was successfully synthesized with good magnetic responsiveness and conspicuous affinity towards QNs. The Fe3O4/MOF/COF composite was used as a magnetic solid-phase extraction (MSPE) adsorbent for pretreatment and determination of QNs in meat samples. Under optimal MSPE conditions in combination with high performance liquid chromatography-quadrupole orbitrap high resolution mass spectrometer (HPLC-Q-Orbitrap HRMS), the proposed method had good linearity (R2 ≥ 0.9978) from 0.01 to 100ng g−1, low limits of detection (0.0016 to 0.0940ng g−1), good precision with relative standard deviations lower than 5.8%. This method was effectively applied to the detection of 17 QNs in the spiked pork, chicken and beef samples with satisfactory recoveries from 83.9 to 106.2%. The separation selectivity mainly due to the π–π interaction, hydrogen bonding, and electrostatic attraction between QNs and the sulfonic acid and amino functional groups of the composite. After verification, the stability and reusability of the composite meet the requirements of complex matrix sample pretreatment. The developed MSPE method based on the magnetic Fe3O4/MOF/COF composite provided an ideal sample pretreatment alternative for determining trace QNs in complex matrixes with selectivity, simplicity, rapidity, and efficiency.

One-pot preparation of magnetic molecularly imprinted adsorbent with dual template molecules for simultaneously specific capture of sulfonamides and quinolones in water and milk samples

Specific capture is a beneficial tactic in simultaneous monitoring of sulfonamides (SAs) and quinolones (QLs). For this purpose, a new magnetic molecularly imprinted adsorbent based on double-template molecules (DT-MIP@MNA) was facilely prepared by “one-pot” hydrothermal technique and utilized as the adsorbent of magnetic solid-phase extraction (MSPE). Molecular simulation technique was employed to quickly screen functional monomer. The recognition factors of prepared adsorbent towards templates sulfamethazine and nalidixic acid were 5.89 and 2.90, respectively, and the corresponding adsorption capacities were as high as 8.85 mg/g and 8.97 mg/g, respectively. Under the optimized parameters, the proposed DT-MIP@MNA/MSPE was combined with HPLC to simultaneously and selectively monitor trace SAs and QLs residuals in water and milk samples. The achieved limits of detection were 0.012–0.028 μg/L and 0.015–0.032 μg/kg for water and milk samples, respectively. The current supplied a sensitive, reliable and anti-interference method for simultaneously monitoring trace SAs and QLs in food.

Synthesis of Nanomagnetite/Crosslinked Carboxymethyl kappa Carrageenan Nickel Imprinted Composite

Nickel(II) ions are carcinogenic water pollutants. To increase the accuracy of instrumental analysis of Ni(II) content, several analytical preparation methods have been developed, including solid phase adsorption extraction. The development of magnetic solid phase extraction adsorbents for metal ions is required, to support the application of magnetic solid phase adsorption as a method of separating metal ions in aqueous samples. This research describes the synthesis of Magnetic Solid Phase Extraction adsorbents as Ni(II) ion adsorbents, nano magnetite/carboxymethyl kappa-carrageenan (CMKC) crosslinked bisphenol A diglycidyl ether (BADGE) imprinted Ni(II)-IIP ion composites. This research was carried out in several stages, synthesis and characterization of nano magnetite (NM), synthesis and characterization of CMKC, and synthesis of NM/CMKCNi(II)-IIP adsorbents. The results of the synthesis were analyzed for morphological characteristics, magnetic strength, spectral characteristics, crystallinity, and composition using SEM, FTIR, XRD, and XRF instruments. The adsorption ability of Ni(II) of the adsorbent was tested. Determination of Ni(II) ion content in the sample before and after adsorption was carried out using a flame atomic absorption spectrophotometer (FAAS). Based on the results of spectral character analysis, crystal diffraction patterns, magnetic strength, and morphology, it is confirmed that nano-magnetite has been successfully synthesized. The diameter of the nano magnetite grains is 21.8 nm, the adsorbent NM/CMKCNi(II)-IIP has magnetic properties and wavy surface morphology. The optimum adsorption ability of Ni(II) for the NM/CMKCNi(II)-IIP composite was 2.44 mg Ni(II)/g adsorbent. To evaluate the tendency of the adsorption ability of the adsorbent towards Ni(II) ions in the presence of competitor ions, the adsorption ability of the adsorbent to adsorp Ni(II) ions in samples containing Ni(II) ions, Pb(II) ions and a mixture of Ni(II) ions. and Pb(II) were determined, based on the results of the analysis, the ability of the adsorbent to adsorb Ni(II) ions was higher than the ability of the adsorbent to adsorb Pb(II) ions, in all types of samples.

Synthesis and application of quaternary amine-functionalized core-shell-shell magnetic polymers for determination of metabolites of benzene, toluene and xylene in human urine samples and study of exposure assessment

As production processes have evolved, airborne concentrations of benzene, toluene and xylene in many workplaces are already well below the occupational exposure limits. However, studies have shown that low levels of exposure to benzene, toluene and xylene can still cause health effects in people exposed occupationally. However, there is no literature on health risk assessment of internal exposure. In view of this, an analytical method based on quaternary amine-functionalized core-shell-shell magnetic polymers (QA-CSS-MPs) was developed for the determination of seven metabolites in urine by MSPE-UPLC-DAD-HRMS. Furthermore, an improved QuEChERS method for the extraction of seven metabolites from human urine samples was introduced for the first time and satisfactory extraction rates were achieved. In addition, QA-CSS-MPs microspheres with core-shell-shell structure were designed and synthesized, and the morphology, composition and magnetic properties of the materials were fully characterized to verify the rationality of the synthetic route. Subsequently, QA-CSS-MPs microspheres were used as magnetic solid-phase extraction (MSPE) adsorbents for the purification of urine extracts, and UPLC-DAD-HRMS was used for the detection of seven metabolites. As a result, this method allows the accurate determination of seven metabolites in urine samples over an ultra-wide concentration range (0.001–100 mg/L). Under optimal experimental conditions, i.e., 2% hydrochloric acid in urine for the hydrolysis and 20 mg of QA-CSS-MPs for 5 min purification, the spiked recoveries of the seven target metabolites ranged from 81.5% to 117.7% with RSDs of 1.0%–9.4%. The limits of detection (LODs, S/N≥3) for the established method were in the range of 0.2–0.3 μg/L. The developed method was applied to 254 human urine samples for the determination of seven metabolites. The results showed that the concentration distributions of three xylene metabolites in urine, 2-MHA, 3-MHA, 4-MHA and total MHA, showed statistically significant differences for occupational exposure (p<0.001). In addition, the results of the internal exposure assessment showed that there is a high potential health risk associated with occupational exposure processes.