Solid-phase Extraction Method Research Articles

Synthesis and characterization of Novel Igepal Co-520 surfactant coated Fe3O4 Nanoparticles: An evaluation of Vanadium enrichment in spice samples

In this study, novel Fe3O4 nanoparticles coated with surfactant Igepal Co-520 (polyoxyethylene (5) nonylphenylether) as adsorbent were synthesized, and total vanadium recovery was performed by magnetic solid phase extraction (MSPE) method. Fe3O4 nanoparticles coated with Igepal Co-520 were employed in the investigation of vanadium enrichment. The synthesized nanoparticles were characterized by Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray Analysis (EDX), X-Ray Diffraction Analysis (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), and Thermogravimetric Analysis (TGA), and total vanadium concentration was determined by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The corresponding values for the pH, adsorbent amount, and contact time were 3, 5 mg, and 120 min. Total vanadium was recovered from an aqueous solution under the optimum conditions. Langmuir and Freundlich adsorption isotherms, pseudo-first and pseudo-second order adsorption kinetics, foreign ion studies, desorption, and analytical value studies were performed. In isotherm studies, the effect on adsorption was examined by varying the vanadium concentration between 1 mg/L and 100 mg/L. The Langmuir model (R2>0.99) seems to be more compatible with vanadium adsorption than the Freundlich model (R2<0.87). Pseudo−first-order and pseudo-second-order equations were used to evaluate adsorption kinetic models. It has been observed that the pseudo-quadratic equation (R2>0.89) was more suitable for modeling than the pseudo-first-order equation (R2<0.56). The analytical performance parameters of the method were calculated as enrichment factor (EF) 114, the limit of detection (LOD) 8.3 µg/L, the limit of quantification (LOQ) 28.3 µg/L, and relative standard deviation (RSD) 1.20 %. At various molarities, the effects of acidic (HCl) and basic (NaOH) agents on the desorption of total vanadium ions adsorbed on the magnetic Fe3O4 surface were examined and compared. It was observed that the maximum recovery (100 %) was obtained using HCl as the desorption agent. The total vanadium concentration in spice samples was measured in an actual sample analysis. All the results demonstrate that the Fe3O4@Igepal Co-520 was successfully synthesized and has the potential to be a useful tool for heavy metal recovery.

Sensitivity and quantitativeness of large-volume injection combined with liquid chromatography/high-resolution mass spectrometry for target screening analysis of emerging contaminants

Solid phase extraction (SPE) has been widely used for pretreatment in target screening (TS) analysis. However, some compounds are difficult to recover by SPE or their recovery is unstable for environmental samples. In this study, we tested large-volume injection (LVI) without SPE for TS analysis of 103 compounds listed by the Ministry of the Environment (Japan)—so-called ‘items to be surveyed’—using liquid chromatography high-resolution mass spectrometry. We evaluated the limit of quantification (LOQ) by LVI and compared this LOQ with the LOQ by SPE pretreatment using a hydrophilic-lipophilic balance (HLB) combined with activated carbon, which was found previously to afford the best SPE cartridges for target compounds recovery. The LOQ generally decreased as the injection volume increased, and the LOQ was at least 250 times lower for a 500-μL injection than for a 2-μL injection for half of the compounds. LVI provided LOQs lower than the predicted no effect concentration for more compounds than the SPE method. The average matrix effect (ME) by LVI was in the range 70%–130% for 69 out of 97 compounds. The ME was higher or lower for some of the remaining compounds, but the ME was in the range 10%–1000% for all 18 water samples for 84 of the 97 compounds. Comparing the ME by LVI and the recovery ratio by the SPE method showed that LVI achieved more accurate quantitation than the SPE method for a larger number of compounds. Therefore, LVI provides better sensitivity and quantitativeness than the SPE method using HLB and activated carbon for TS analysis of as many ‘items to be surveyed’ as possible.

Quantitative analysis of organosulphur compounds in crude oil samples using magnetic solid phase extraction based on Au-Fe3O4 adsorbent and gas chromatography with time-of-flight mass spectrometry

AbstractThis study focused on the development of a magnetic solid phase extraction (m-SPE) method using Au-Fe3O4 as an adsorbent followed by GC-ToFMS analysis for the determination of organosulphur compounds (OSCs) in fuel samples. The m-SPE using Au-Fe3O4 NPs was preferred because of the low toxicity of the adsorbent1, high separation efficiency using external magnet2 and greater extraction selectivity between sulphur and Au atom3. The Au-Fe3O4 NPs were characterized using XRD, UV–Vis, TEM, SEM and FTIR. This method was optimized using multivariate analysis based on a two-level full factorial and central composite designs. The conditions which produced optimum efficiency were found to be 150 mg mass of sorbent, 100 µL eluent volume, 50 min extraction time and 6,5 pH of the sample. These optimum conditions showed a relatively low limit of detection in the range of 0.02–0.199nµg/g and limit of quantification of 0.08–0.602 µg/g. Furthermore, a relative standard deviation of triplicates analysis was between 0.8 and 2.3% with good linearity of 0.9816–0.9961. The percentage recovery for thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene ranged from 76 to 95% for the spiked samples. The optimized m-SPE method was then applied in real fuel oil samples. The concentration of thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene in crude oil, gasoline, diesel and kerosene ranged from 0.43–1.94 µg/g, 0.78–1.63 µg/g, 0.95–4.31 µg/g to 1.55–2.09 µg/g, respectively. The m-SPE, followed by GC-ToFMS method, proved to be efficient, inexpensive and an alternative method for OSCs analysis in fuel oils.

Synthesis of Magnetic Attapulgite Nanoparticles Via a Novel Surface Covalent Reaction Method and its Application in the Magnetic Solid Phase Extraction.

In this study, the attapulgite nanoparticle was immobilized on the surface of magnetic nanoparticle Fe3O4 via a novel surface covalent reaction method for the magnetic solid phase extraction (MSPE) for the first time. The surface covalent reaction method has the advantages of controllable steps, and can make the magnetic attapulgite nanoparticle (MANP) have good homogeneity and high stability. Field emission scanning electron microscopy, equipped with an energy dispersive spectrometer, Nitrogen adsorption BET, X-ray diffraction and Fourier transform infrared spectroscopy were applied to characterize the prepared MANP, confirming that the attapulgite nanoparticle could be effectively immobilized on the surface of magnetic nanoparticle Fe3O4 via covalent reactions. Under optimal conditions of the MSPE experiment based on the MANP, the limits of detection were found to be 10ng/mL for melamine and 3ng/mL for cyromazine with a relative standard deviation < 10% by a high-performance liquid chromatography system. Meanwhile, 0.1mg/mL melamine in milk and 0.1mg/mL cyromazine in cucumber can also be detected according to our MSPE procedure. More importantly, the MANP still has good magnetism and enrichment efficiency after several decades of use. These results showed that the MANP prepared by our method is a kind of promising material for the MSPE.

Switchable metal extractant integrated miniaturized 3D-printed device: A semi-online multi-metal separation system for matrix-free ICP-MS analysis

BackgroundThis study tackles the critical challenges in metal analysis by presenting an innovative miniaturized metal extraction device prototype. This device features a functional nanocomposite (FNC) enhanced 3D-printed polylactic acid (PLA) metal extractant (FNC@3D PLA). The research is motivated by the constraints of traditional solid-phase extraction (SPE) methods, specifically their limitations in handling competitive metal ion environments and matrix interference during inductively coupled plasma mass spectrometry (ICP-MS) analysis. The designed prototype aims to overcome these challenges and enhance the extraction efficiency of diverse metals. ResultsThe FNC, designed to incorporate various functional groups critical for metal ion extraction efficiency, was meticulously engineered through the reaction of acid-treated and delaminated graphitic carbon nitride nanosheets (Thiol-gCN NSs) with 3-mercaptopropyl trimethoxysilane (MPTMS). The competitive metal ion extraction efficiency of FNC@3D PLA was demonstrated, showcasing notable limit of detection values of 3.2 ± 0.7 ng mL-1 and 8.57 ± 3.05 ng mL-1 for Cu and Ag, respectively. Furthermore, the miniaturized 3D-printed metal-preconcentration setup incorporating FNC@3D PLA exhibited favorable intraday relative standard deviation (RSD) percentage (%) values ranging from 1.23 to 8.6 for both Cu and Ag. Interday RSD % between 1.41 and 8.14 were observed under spiked real urine sample conditions. The sustainability and robustness of the proposed approach were underscored by substantial recovery % values exhibited by FNC@3D PLA, even after eight consecutive regeneration processes. SignificanceThis study significantly contributes to the advancement of analytical methodologies by providing a reliable and efficient platform for metal extraction and preconcentration in practical metal analysis applications. Developed FNC@3D PLA system demonstrates its potential to address the challenges associated with SPE in metal analysis, especially in complex sample matrices. We believe implications of this research can be extended to various fields, from environmental monitoring to clinical diagnostics, where accurate and reliable metal analysis is paramount.

Modifying of magnetic UiO-66-NH2 as a new nanosorbent by thermo-alkali-hydrolysis technology for highly efficient enrichment and determination of quercetin in apple peel

For rapid separation of quercetin from apple peel, a novel magnetic nanomaterial was prepared by a simple and economical thermal alkaline hydrolysis method in this work. This magnetic nanomaterial was obtained by mixing magUiO-66-NH2 (magnetic University of Oslo 66-NH2) with 0.05 mol·L-1 KOH aqueous solution and then heated, and was named magUiO-66-NH2-MH0.05 (magUiO-66-NH2-mixed heating0.05), which has better magnetic properties, thermal stability, pore capacity and average pore size than magUiO-66-NH2. The obtained magUiO-66-NH2-MH0.05 had strong adsorption capacity for quercetin, and the maximum adsorption capacity was 65.30 mg·g−1. MagUiO-66-NH2-MH0.05 tends to be monolayer-layer adsorption for quercetin, and electron sharing or transfer may occur during the adsorption process. Compared with naringenin, naringin and gallic acid, magUiO-66-NH2-MH0.05 showed good recognition ability for quercetin, and the recoveries were good. After 7 cycles, the adsorption capacity of magUiO-66-NH2-MH0.05 for quercetin was 96.3 % of the initial adsorption capacity. A magnetic solid-phase extraction method coupled with High-Performance Liquid Chromatography based on magUiO-66-NH2-MH0.05 was successfully used for rapid separation and determination of quercetin in apple peel. This study will help to discover the experimental law of the treatment of UiO-66-NH2 nanomaterials by hot alkaline hydrolysis, reveal the reaction mechanism, and expand the application of UiO-66-NH2 nanomaterials in food analysis.

Covalent organic frameworks as dispersive solid-phase extraction adsorbents for β-lactam detection in aquatic environments

Currently, antibiotic residues in the environment pose a serious public health risk; therefore, new sensitive approaches for detecting the presence of antibiotics are urgently needed. Ionic-type covalent organic frameworks (TAPB-(TFIT)+Cl−-COFs) were designed and prepared in this work, and these imine-linked COFs were characterized by several techniques, proving of porous structure and rich of nitrogen. The materials were applied to the extraction of β-lactams from aqueous samples, and the important parameters of the adsorption–desorption conditions were optimized. A dispersive solid-phase extraction method coupled with ultrahigh-performance liquid chromatography-tandem mass spectrometry (TAPB-(TFIT)+Cl−-COFs-d-SPE-UPLC-MS/MS) was proposed and utilized to determine the levels of 11 antibiotics in the β-lactams in the extracted samples. Good linearity (1.0–200.0 μg·L−1, r > 0.9999) was achieved together with limits of detection and quantification of 0.01–0.92 μg·L−1 and 0.05–2.78 μg·L−1, respectively; recoveries ranged from 75.57 to 114.20 %, conferring relative standard deviations < 8.99 % and negligible matrix effects (84.88–109.40 %). The synthesized TAPB-(TFIT)+Cl−-COFs were demonstrated to have good reusability and high stability. Furthermore, the proposed method was clearly shown to be sensitive and separable for the reliable simultaneous detection of 11 β-lactam residues in aquatic environments.

Global analysis of N-myristoylation and its heterogeneity by combining N-terminomics and nanographite fluoride-based solid-phase extraction

N-myristoylation is one of the most widespread and important lipidation in eukaryotes and some prokaryotes, which is formed by covalently attaching various fatty acids (predominantly myristic acid C14:0) to the N-terminal glycine of proteins. Disorder of N-myristoylation is critically implicated in numerous physiological and pathological processes. Here, we presented a method for purification and comprehensive characterization of endogenous, intact N-glycine lipid-acylated peptides, which combined the negative selection method for N-terminome and the nanographite fluoride-based solid-phase extraction method (NeS-nGF SPE). After optimizing experimental conditions, we conducted the first global profiling of the endogenous and heterogeneous modification states for N-terminal glycine, pinpointing the precise sites and their associated lipid moieties. Totally, we obtained 76 N-glycine lipid-acylated peptides, including 51 peptides with myristate (C14:0), 10 with myristoleate (C14:1), 6 with tetradecadienoicate (C14:2), 5 with laurate (C12:0) and 4 with lauroleate (C12:1). Therefore, our proteomic methodology could significantly facilitate precise and in-depth analysis of the endogenous N-myristoylome and its heterogeneity.

MOF@N–doped carbon dots–based dispersive solid phase extraction combined dispersive liquid–liquid microextraction of several aflatoxins from raw cow’s milk samples prior to HPLC–FLD

A dispersive solid-phase extraction method based on metal–organic framework and nitrogen–doped carbon dot nanocomposite combined with magnetic ionic liquid-based dispersive liquid–liquid microextraction was established for the extraction of aflatoxins from raw milk samples. For this purpose, the proteins in the sample were precipitated using a zinc sulfate solution. After vortexing (for 5 min) and centrifuging, 35 mg of the sorbent were added into the aqueous phase obtained from previous step, and the mixture was vortexed for five minutes. In the following, the sorbent particles were separated and eluted with methanol in the presence of vortex agitation (4 min). After centrifuging, the eluent phase was mixed with magnetic ionic liquid (1- octyl-3-methylimidazolium tetrachloroferrate) and rapidly injected into deionized water to perform the dispersive liquid–liquid microextraction procedure. Finally, the magnetic solvent was separated in the presence of a magnet and injected into a high-performance liquid chromatography-fluorescence detector after diluting with the mobile phase. Referring to the results, the limits of detection and quantification of the studied aflatoxins were in the range of 0.69–1.09 and 2.31–3.63 ng/L, respectively. Extraction recoveries were in the range of 61 to 73 %. At the end, the suggested approach was employed in the analysis of the aflatoxins in the raw cow’s milk samples collected from different regions of East Azarbaijan and AFM1 was found in several samples (34 out of 60 samples). Also, AFB1 was found in three samples.

Pompon mum-like ionic covalent organic framework nanocomposites for efficient solid-phase extraction of nonsteroidal anti-inflammatory drugs

Molecularly imprinted ionic covalent organic framework nanocomposites (MI-IC-COF@SnO2) were prepared as potential adsorbents for the enhanced adsorption of nonsteroidal anti-inflammatory drugs (NSAIDs) from aqueous solution. The resulting material exhibited a pompon mum-like structure, featuring a large surface area, and well-defined mesopores. The presence of uniform positive ions within the three-dimensional skeleton of MI-IC-COF@SnO2 facilitated a rapid adsorption rate and high adsorption capacity for target analytes. Thermodynamic fitting revealed the adsorption process of NSAIDs to be feasible, endothermic, and spontaneous. Additionally, the adsorbent material exhibited respectable selectivity, as evidenced by imprinting factor values ranging from 2.8 to 6.7. Utilizing MI-IC-COF@SnO2 as the sorbent, a solid-phase extraction method coupled with high-performance liquid chromatography-ultraviolet detection (SPE-HPLC-UV) was developed and optimized. The proposed method demonstrated good linear range with determination coefficients of 0.998-0.999, and low limit of detection (0.18-1.35 µg L−1). Recoveries of NSAIDs in urine and river water samples were 78.1%–106.1%, with relative standard deviations lower than 12.5%. This rapid and sensitive method enables the determination of NSAIDs at trace levels in complex matrices, providing reliable and reproducible results.

Preconcentration of Cu2+, Cr3+, Co2+, and Ni2+ by Solid-Phase Extraction Using a Recently Developed Mixed-Mode Sorbent

The enrichment and simultaneous analysis of Cu2+, Cr3+, Co2+, and Ni2+ by solid-phase extraction method were performed using a stationary phase containing amide functional groups, an aromatic benzene ring, and aliphatic groups in a silica-based structure that we had synthesized for HPLC separations in our previous studies. Solid-phase extraction was performed using a column system and the results obtained were analysed by ICP-OES. Effects of pH, amount of sorbent, amount of eluting solvent, sample volume, flow rates of the eluent and the sample, and interfering ions were evaluated in recovery processes for the metals in the sample solutions. Linear range, detection limit, and relative standard deviation (% RSD) values were calculated for each metal. The linear range (ng/mL) was between 0.01 and 0.25 for all ions, while the limit of detection (ng/mL) was found to be 0.64, 1.7, 0.44, and 0.51 and % RSD was 2.8, 2.4, 2.6, and 2.9 for Cu2+, Cr3+, Co2+, ve Ni2+, respectively.

Application of Magnetic Materials Combined with Echo® Mass Spectrometry System in Analysis of Illegal Drugs in Sewage.

The aim of this study is to solve the problems of the complicated pretreatment and high analytical cost in the detection technology of trace drugs and their metabolites in municipal wastewater. A high-performance magnetic sorbent was fsynthesized for the enrichment of trace drugs and their metabolites in wastewater to develop a magnetic solid-phase extraction pretreatment combined with the acoustic ejection mass spectrometry (AEMS) analytical method. The magnetic nanospheres were successfully prepared by magnetic nanoparticles modified with divinylbenzene and vinylpyrrolidone. The results showed that the linear dynamic range of 17 drugs was 1-500 ng/mL, the recovery was 44-100%, the matrix effect was more than 51%, the quantification limit was 1-2 ng/mL, and the MS measurement was fast. It can be seen that the developed magnetic solid-phase extraction (MSPE) method is a good solution to the problems of the complicated pretreatment and analytical cost in the analysis of drugs in wastewater. The developed magnetic material and acoustic excitation pretreatment coupled with mass spectrometry analysis method can realize the low-cost, efficient enrichment, and fast analysis of different kinds of drug molecules in urban sewage.

Facile construction of a stable core-shell spherically magnetic polyimide covalent organic framework for efficient extraction of phenylurea herbicides

Efficient enrichment is crucial for the highly sensitive monitoring of phenylurea herbicides (PUHs) in various environmental waters. In this work, a stable core-shell spherically magnetic polyimide covalent organic framework (COF) was synthesized via a simple template-mediated precipitation polymerization method under mild conditions using tri(4-aminophenyl)amine (TAPA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) as the building units (denoted as Fe3O4@TAPA-BPDA). The Fe3O4@TAPA-BPDA exhibits remarkable adsorption performance for PUHs with an optimized adsorption time of only 10 min. The adsorption of PUHs by Fe3O4@TAPA-BPDA followed the pseudo-second-order kinetic model and the Langmuir model. Furthermore, hydrogen bonding, halogen bonding, hydrophobic interaction, electro donor-acceptor interaction and π-π interactions are identified as the dominant mechanisms contributing to excellent adsorption performance. It was demonstrated that halogen bonds play an important role in the adsorption of substances containing chlorine atoms. The Fe3O4@TAPA-BPDA is easy to operate and highly regenerable. A simple magnetic solid-phase extraction (MSPE) method based on the Fe3O4@TAPA-BPDA was then developed for the rapid extraction of five PUHs in real samples, coupled with high-performance liquid chromatography (HPLC) determination. The analytical method developed has a linear range of 0.5–50 ng/mL, and the limit of detection (LOD) ranges from 0.06 to 0.10 ng/mL. The method exhibits good accuracy with recoveries ranged from 74.5 % to 111.4 %. The analytical method was successfully applied to the highly sensitive detection of PUHs in environmental water samples, which highlighting the potential application of the Fe3O4@TAPA-BPDA in the sample pretreatment.

Simultaneous determination of picomolar level of dissolved silver with other key trace metals in seawater samples using solid phase extraction and isotope dilution methods

Simultaneous determination of dissolved silver (dAg) with other key GEOTRACES trace metals is difficult because dAg in seawater tends to form negatively charged chloride species that result in only 75% recovery efficiency with commonly used NOBIAS PA-1 chelating resins. In this study, we developed a method using solid phase extraction coupled with isotope dilution that enables full quantification (97.9 ± 2.1%) of dAg along with other major trace metals including cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni), and lead (Pb) (recovery efficiency = 100% to 102%) in seawater samples. Seawater samples were first spiked with Ag-109 and allowed to reach isotopic equilibrium before extraction using NOBIAS PA-1 chelating resin. Then, dAg isotope ratios (Ag-109/Ag-107) before and after solid phase extraction were determined and used to quantify dAg. Determination of dAg with dissolved Cd, Cu. Mn, Ni, and Pb in reference seawater material CASS-6 resulted in deviations of between 1.0% and 8.8% from the consensus values, which are well within the standard error of measurement. We then successfully determined the concentrations of dissolved Cd (0.05–0.2 nM), Cu (0.5–13 nM), Mn (10–140 nM), Ni (2–12 nM), Pb (5–110 nM), and Ag (10–40 pM) in Otsuchi Bay, Japan and its surrounding rivers. Evaluation of the behavior of dAg under a salinity gradient using estuarine samples collected from Samunsam River, Malaysia shows increasing dAg concentration with salinity (R2 = 0.68), which suggests release of sedimental Ag under high ambient chloride concentrations. Our new method enables rapid and simultaneous measurements of dAg with other key GEOTRACES trace metals in a single analysis, which is expected to expedite analysis and increase availability of oceanic dAg data globally.

Natural kapok fiber as a green and efficient adsorbent for in-syringe solid-phase extraction in the determination of antidepressants in biofluids

Effective antidepressant monitoring is crucial for safe treatment, with liquid chromatography being the primary detection method. Due to the complexity of biofluids, meticulous sample preparation is vital to remove interferences and concentrate analytes. In this study, a novel solid-phase extraction method utilizing unprocessed kapok fiber (KF) as an eco-friendly and efficient sorbent, ingeniously incorporated within an in-syringe device for the extraction of antidepressants from biofluids was introduced. The extraction process displayed several advantages, including simplicity and rapidity (less than 3 min with minimal manual intervention), as well as the potential for automation, which represents significant advancements in sample preparation techniques. The method demonstrated excellent analytical performance when coupled with high-performance liquid chromatography-ultraviolet detection, achieving good linearity (R2 ≥ 0.991), excellent relative recovery (92.6–107.5 %), high precision in intraday and interday analyses (RSDs within 0.8–6.0 % and 1.2–7.9 %, respectively), and good sensitivity with limits of quantification between 5–10 ng/mL. Notably, given the use of a renewable and biodegradable material with KF, and a low-toxicity desorption solvent with ethanol, the developed method stands out for its environmental sustainability, aligning with green analytical chemistry principles. Its application to real biological samples validates its efficacy as a rapid and reliable tool for clinical and forensic monitoring of antidepressants. Moreover, the low cost of this method facilitated by the economical nature of KF and the reusability of syringes further enhances its practicability. This study presents a unique approach by employing natural and renewable KF as adsorbents, thereby eliminating the need for complex material synthesis and making a pioneering contribution to the field of analytical chemistry for drug analysis in complex matrices.

Selective solid phase extraction of phototoxic furanocoumarins using molecularly imprinted polymers

Furanocoumarins are secondary plant metabolites found in citrus plants. Essential oils from these plants are widely used in cosmetic products. They have attracted attention for their phototoxicity, which can even lead to skin burns. Therefore, the furanocoumarin concentration is controlled by the European Union according to Regulation (EC) No. 1223/2009, where a limit of 1 mg kg−1 is specified in sun protection and bronzing agents. This study describes the synthesis of two molecularly imprinted polymers (methacrylamide and methacrylic acid as monomers) as novel materials for solid phase extraction. After optimisation of the extraction protocol, both polymers gave satisfying recovery results for a furanocoumarin standard mixture containing the six markers proposed by the International Fragrance Association (IFRA). Furthermore, spiked sun oil samples were extracted using an adapted extraction protocol. Since the studies showed promising results including 75–149 % recovery and 100 % loading efficiency for the methacrylic acid polymer, a validation of the analytical method was performed. Analysis was performed using HPLC-MS/MS in high specificity multi-reaction monitoring mode. The validation showed acceptable results for most parameters. In addition, a comparison with commercially available Strata-X cartridges was completed, revealing superior recovery performance of the molecularly imprinted polymer. In conclusion, molecularly imprinted polymers represent a novel and efficient method for selective solid-phase extraction of phototoxic furanocoumarins.

Improved preconcentration workflow for organic explosive traces in aqueous samples using solvent-assisted dispersive solid-phase extraction

The present study deals with the development of a solvent-assisted dispersive solid phase extraction method for the extraction of HMX, RDX, and TNT from aqueous samples. Benzophenone and methanol were selected as explosives sorbent and dispersive solvent respectively. Extraction parameters like pH, extraction time, amount of sorbent, volume and type of the disperser solvent and centrifuge time were optimized. Dispersion of 0.5 mL dispersive solution (4% (w/v) benzophenone in methanol) was performed by injection into the 5 mL aqueous sample (pH=7) using a 1.0 mL syringe. After centrifuge, the extracted explosives were analyzed by high performance liquid chromatography with ultraviolet detection (HPLC-Uv). The results indicated that the linear ranges with the correlation coefficients of 0.99 ≤ R2 were 1.6–204.6 μg L−1, 1.4–213.7 μg L−1 and 1.3–225.9 μg L−1 for HMX, RDX and TNT respectively. The limit of detection and limit of quantification obtained for each explosive were: 0.3 μg L−1 and 0.8 μg L−1 for HMX, 0.3 μg L−1 and 0.9 μg L−1 for RDX and 0.2 μg L−1 and 0.7 μg L−1 for TNT. Finally, the practical applicability of the developed method was evaluated for the extraction of some organic explosives in water samples followed their determination by HPLC-Uv.

Application of continuous magnetic solid phase extraction in the extraction of tetracycline antibiotics from honey samples

This study aimed to develop a continuous magnetic solid phase extraction method in a narrow bore tube for the extraction of tetracycline antibiotics from honey samples before their determination with high performance liquid chromatography–diode array detector. In this work, a magnetic covalent organic framework is used as the sorbent. The extraction method is performed in a narrow bore tube by adding 25 mg of a magnetic sorbent prepared from melamine, barbituric acid, and Fe3O4 into the diluted honey sample solution. By using a magnet, the sorbent is moved up and down through the narrow bore tube for five times to improve extraction efficiency. After adsorption the analytes, they are eluted from the sorbent surface using 2,2–dimethoxypropane under vortexing. Then, by using a magnet, the eluent containing the extracted analytes are taken and evaporated with continuous flow of nitrogen. Finally, the residue containing the enriched analytes is reconstituted in microliter–level of mobile phase and injected into chromatographic system for quantitative analysis. Based on the outcomes, the method demonstrated good linearity (0.37–1000 ng g−1), high enrichment factors (175–203), good extraction recoveries (70–81 %), low LODs (0.11–0.18 ng g−1) and LOQs (0.37–0.60 ng g−1). The proposed method is effectively applied for quantification of tetracyclines in twenty–four honey samples. Considering the results, none of the honey samples was contaminated with the studied antibiotics. Regarding to the above–mentioned analytical advantages of the proposed method, its simplicity and rapidity, and green synthesis of the magnetic sorbent particles, the suggested method can be used as a routine method for the extraction of tetracyclines from honey samples.

Fluorine-functionalized magnetic amino microporous organic network for enrichment of perfluoroalkyl substances

Perfluoroalkyl substances (PFAS) are persistent organic pollutants that pose significant risks to human health and the environment. Efficient and selective enrichment of these compounds was crucial for their accurate detection and quantification in complex matrices. Herein, we report a novel magnetic solid-phase extraction (MSPE) method using fluorine-functionalized magnetic amino-microporous organic network (Fe3O4@MONNH2@F7) adsorbent for the efficient enrichment of PFAS from aqueous samples. The core-shell Fe3O4@MONNH2@F7 nanosphere was synthesized, featuring magnetic Fe3O4 nanoparticles as the core and a porous amino-functionalized MONs coating as the shell, which was further modified by fluorination. The synthesized adsorbent material exhibited high specific surface area, hydrophobicity, and abundant fluorine groups, facilitating efficient and selective adsorption of PFAS via electrostatic attraction, hydrophobic-hydrophobic interactions, fluorine-fluorine interactions, π-CF interactions and hydrogen bonding. Furthermore, the MSPE method coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) allowed for the rapid, sensitive, and accurate determination of ultra-trace PFAS in real water samples, human serum, and human follicular fluid. Under optimal conditions, the established MSPE method demonstrated a linear range (2 to 2000 ng L−1), with a correlation coefficient exceeding 0.9977, low limits of detection ranging from 0.54 to 1.47 ng L−1, with a relative standard deviation (RSD) < 9.1%. Additionally, the method showed excellent performance in complex real samples (recovery ratio of 81.7 to 121.6 %). The adsorption mechanism was investigated through kinetic, isotherm, and molecular simulation studies, revealing that the introduction of fluorine groups enhanced the hydrophobic interaction and fluorine-fluorine attraction between the adsorbent and PFAS. This work provides a proof-of-concept strategy for designing adsorbent materials with high efficiency and selectivity by post-modification, which has great potential for the detection and analysis of PFAS in complex samples.

Concentrations of per- and polyfluoroalkyl substances in vegetables from Sydney and Newcastle, Australia.

This study investigated per- and polyfluoroalkyl substances (PFASs) in 53 fruit and vegetable samples collected from a local wholesale and retail market in Sydney and a local supermarket in Newcastle. As there is limited information about PFAS levels in vegetables on the market, this study aimed to fill this gap and assess potential risks for humans through consumption of these vegetables. QuEChERS extraction - a solid-phase extraction method, a portmanteau word formed from 'quick, easy, cheap, effective, rugged and safe' - followed by enhanced matrix removal-lipid cleaning and liquid chromatography-tandem mass spectrometry analysis were used to detect 30 PFASs in vegetables. PFOA was detected in 7 out of the 53 samples, with concentrations of 0.038-1.996 ng g-1 fresh weight; PFOS was detected in 2 samples only, with concentrations ranging from 0.132 to 0.911 ng g-1 fresh weight. PFHxS was not detected in any sample in this study. PFOA and PFOS concentrations measured in vegetables in this study constituted daily intake of 2.03 ng kg-1 body weight (BW) and 1.98 ng kg-1 BW, respectively, according to recommended daily vegetable intake and BW data from the Australian Bureau of Statistics. The most sensitive population group is girls of 4-8 years of age. These estimated exposure levels represent up to 1.3% of the tolerable daily intake for PFOA (160 ng kg-1 BW) and 9.9% for PFOS (20 ng kg-1 BW) according to Food Standards Australia New Zealand. Consumption of the vegetables from the study locations poses a marginal risk to human health. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.