Solid-phase Extraction Sorbent Research Articles

Hydroxyl-functionalized cationic porous organic polymers for efficient enrichment and detection of phenolic endocrine disrupting chemicals in water and snapper

Endocrine-disrupting chemicals (EDCs) can disrupt the normal functioning of the endocrine system in organisms, leading to various health issues. Therefore, monitoring EDCs in the environment and food is of significant importance. In this study, a hydroxyl-functionalized ionic porous organic polymer (OH-IPOP) has been synthesized for the first time using 2-benzimidazolemethanol as a monomer. The OH-IPOP exhibited excellent adsorption performance towards phenolic EDCs. An efficient method for determination of phenolic EDCs (p-tert-butylphenol, bisphenol B, bisphenol A and bisphenol F) in environmental water and snapper samples was successfully established by with OH-IPOP as solid-phase extraction sorbent and determination with high-performance liquid chromatography-ultraviolet detection. The method showed good linearity (r2 > 0.998), low detection limits (0.008–0.020 ng mL−1 for lake water, 1.00–3.00 ng/g for snapper), high recovery rates (82.3–106 %), and good precision (relative standard deviation < 6.6 %), making it a highly efficient adsorbent for the enrichment of EDCs in complex sample matrices.

Novel Application of Metal-Organic Frameworks as Efficient Sorbents for Solid-Phase Extraction of Chemical Warfare Agents and Related Compounds in Water Samples.

In this work, we test metal-organic frameworks (MOFs) as sorbents in the solid-phase extraction (SPE) technique to determine chemical warfare agents (CWAs) and their related compounds in water samples. During this study, we used 13 target compounds to test the selectivity of MOFs thoroughly. Three MOFs were used: MIL-100(Fe), ZIF-8(Zn), and UiO-66(Zr). The obtained materials were characterized using FT-IR/ATR, SEM, and XRD. CWA's and related compounds were analyzed using gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). The effect of the type of elution solvent and the amount of sorbent (MOFs) in the column on the efficiency of the conducted extraction were verified. The LOD ranged from 0.04 to 7.54 ng mL-1, and the linearity range for the analytes tested extended from 0.11/22.62 (depending on the compound) to 1000 ng mL-1. It was found that MOFs showed the most excellent selectivity to compounds having aromatic rings in their structure or a "spread" spatial structure. The best recoveries were obtained for DPAA, CAP, and malathion. Environmental water samples collected from the Baltic Sea were analyzed using an optimized procedure to verify the developed method's usefulness.

Three-birds-with-one-stone: An eco-friendly and renewable humic acid-derived material application strategy for macrolide antibiotic detection and multifunctional composite film preparation

This research proposes a simple and novel strategy for the green detection of antibiotics along with the reduction of microplastic and humic acid (HA) hazards. The entire process is based on a single-step solvent-sieving method to separate HA into insoluble (IHA) and soluble (SHA) components, subsequently recombining and designing the application according to the original characteristics of selected fractions in accordance with the zero-waste principle. IHA was applied as a dispersive solid phase extraction (DSPE) sorbent without chemical modification for the enrichment of trace MACs in complex biological matrices. The recovery of MACs was 74.06–100.84 % in the range of 2.5–1000 μg∙kg−1. Furthermore, SHA could be combined with biodegradable polyvinyl alcohol (PVA) to prepare multifunctional composite films. SHA endows the PVA film with favorable mechanical properties, excellent UV shielding as well as oxidation resistance performance. Compared with pure PVA, the tensile strength, toughness, antioxidant and UV-protection properties were increased to 157.3 Mpa, 258.6 MJ·m−3, 78.6 % and 60 % respectively. This study achieved a green and economically valuable utilization of all components of waste HA, introduced a novel approach for monitoring and controlling harmful substances and reducing white pollution. This has significant implications for promoting sustainable development and recovering valuable resources.

Validation of LC-MS/MS method for opioid monitoring in Valencia City wastewater: Assessment of synthetic wastewater as potential aid

In this study, a comprehensive and sensitive method for the simultaneous detection of 17 opioids (OPs) and their human metabolites in wastewater using high-performance liquid chromatography coupled to tandem mass spectrometry was validated. The chromatographic separations of opioids were carried out on a Kinetex® Biphenyl column (1.7 μm, 100 Å, 50 × 2.1 mm). A synthetic wastewater approach was used for recovery studies to mimic a contaminant-free matrix. Two solid-phase extraction (SPE) sorbents (hydrophilic-lipophilic balance and mixed mode with the previous phase and a weak cationic exchange) were studied to optimize sample treatment and obtain higher recoveries. The mixed mode was chosen because the recoveries of 17 target analytes at three spiked concentrations (25, 50, and 100 ng mL−1) were > 80 % for 75 % of the analytes in a simulated wastewater. The intra- and inter-day relative standard deviations (RSDs) were between ±1 % and ±20 %. The method limits of quantification ranged from 5 to 25 ng L−1, the only exceptions being heroin (275 ng L−1) and morphine-3β-glucuronide (250 ng L−1). Suppression/enhancement is comparable between the synthetic and the influent wastewater. The analytical method was applied to the OPs analysis in twenty-one influent samples collected from the treatment plants treating the wastewater of Valencia City (Spain). Twelve OPs were detected with total daily concentrations ranging from 1 ng L−1 to 2135 ng L−1. The widespread presence of these compounds in water suggests potential widespread exposure, highlighting the need for increased environmental awareness. Furthermore, the estimated daily intake results raise concerns about opioid use as a potential future health and social issue.

Synthesis and characterization of magnetic molecularly imprinted polymers for the rapid and selective determination of clofazimine in blood plasma samples

Clofazimine (CLF) is a riminophenazine derivative and a new therapeutic option with high efficacy for patients with rifampicin-resistant tuberculosis (TB). The blood levels of CLF are low and suboptimal, so therapeutic drug monitoring is required. Prior to this study, there were no molecular imprinting–based solid phase extraction (SPE) sorbents that could be used to determine the blood CLF levels. Hence, we prepared a magnetic molecularly imprinted polymer (MMIPs) to capture CLF. We employed computational selection of a functional monomer and crosslinker and confirmed these selections based on the association constant (Ka) and a Job plot. We synthesised MMIPs with two surface modifiers and characterized the polymers. Our computational analysis based on the bond energy revealed that methyl methacrylate (MMA) was the most suitable functional monomer at a CLF-to-MMA molar ratio of 1:4. Based on the bond energy, the most suitable crosslinker was trimethylolpropane trimethacrylate (TRIM) at a CLF-to-TRIM molar ratio of 1:1. We determined the Ka of MMA and TRIM in different solvents. Isopropanol produced the highest Ka. The Job plot showed that a template-to-MMA-to-TRIM molar ratio of 1:4:20 was optimal to synthesize imprinted polymer in isopropanol. We prepared MMIPs using two different modifiers, namely aminopropyltrimethoxysilane (APTES) and oleic acid (OA), using the ratio determined from the Job plot. Physical characteristic tests carried out using FT-IR, SEM-EDS, PSA, BET and VSM, showed that the synthesis was success with a spherical and uniform agglomeration of particles, also a flat surface with many holes with a particle size of MMIP-APTES and MMIP-OA respectively 0.14 μm and 0.28 μm, showed a surface area for MMIP-APTES is 2874.51 m2/g and MMIP-OA 2913.07 m2/g, exhibiting superparamagnetic properties with a saturation magnetization value of MMIP-APTES 21.1 emu/g−1 and MMIP-OA 49.9 emu/g−1. Adsorption capacity result showed that MMIP-OA fits well with the Langmuir model, while MMIP-APTES fits better with the Freundlich. Application of MMIP-SPE (Magnetic Molecular Imprinted Polymer-Solid Phase Extraction) APTES resulted 92.3 ± 6.1 % and MMIP-SPE-OA 51.5 ± 8.1 % for recovering CLF in blood. The result of selectivity test also showed that MMIP-SPE-APTES is better than MMIP-SPE-OA and selectively recover CLF from human blood plasma existed together with other TB-Drugs. The study result shows that MMIPs with APTES modification can be used for CLF determination in human blood plasma.

A fungal hyphae-derived biomass carbon for magnetic solid-phase extraction of the organochlorine pesticides in water samples, tea beverages, and Chinese traditional medicines before gas chromatography-tandem mass spectrometry determination

A magnetic biochar nanomaterial derived from fungal hyphae was introduced into the sample preparation field. The magnetic fungal hyphae-derived biomass carbon (MFHBC) could be produced by a controllable hydrothermal method. In order to obtain the best sorbent for magnetic solid-phase extraction (MSPE), the reaction conditions containing temperature, time and the consumption of fungal hyphae were investigated. A series of MFHBC materials were characterized by vibrating sample magnetometers, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. A material with a satisfactory saturation magnetization (21.58 emu g-1) and largest surface area (88.06 m2 g-1) was selected as the sorbent to extract ten typical organochlorine pesticides (OCPs). The extraction conditions were optimized as 20 mL of sample solution with 70 mg of sorbent and 2.0 g of NaCl oscillated at 50 °C for 5.0 min. And the optimum desorption was performed by oscillating sorbent in 1.0 mL acetonitrile for 5.0 min. Then, the MFHBC-based MSPE-GC–MS/MS methods were established for different samples including water samples, tea beverages, and Chinese traditional medicines. The linearities were 10–2500 ng L−1 or 100–25,000 ng kg−1, and the limits of detection were 0.3–13.9 ng L−1 for water sample, 0.1–9.7 ng L−1 for tea beverage samples, 0.1–21.4 ng L−1 for Shenqi Fuzheng injection samples, and 7.2–278.3 ng kg−1 for Astragali Radix decoction pieces. Except for satisfactory repeatability (RSDs ≤13.8%) in intra-day and inter-day tests (n = 3), the reproducibility (RSDs ≤13.5%, n = 3) of MFHBC was acceptable. The methods were applied in the determination of OCPs from above real samples, with the recoveries of 80.5–117.2% and the RSDs (n = 3) <8.9%. The methods were suitable in the sensitive determination of OCPs from simple to complex matrix samples.

Quaternary ammonium salt modified magnetic solid-phase extraction beads with different chain lengths for efficient enrichment of five types of folates in blood

This study used quaternary ammonium functionalized magnetic beads (QAMBs) as magnetic solid-phase extraction (MSPE) sorbents and liquid chromatography-tandem mass spectrometry (LC-MS) to analyze five folates in a way that was both effective and sensitive. The developed magnetic beads had high BET surface areas up to 434.4 m2/g and strong positive zeta potentials above 40 mV. The conditions for MSPE were optimized. Under the chosen conditions, the linear ranges of the studied folates were 10–10000 ng/L, and the LODs were found to be 1 ng/L. This method was also successfully applied to analyze human plasma samples, giving satisfactory results (recovery of 86.4–98.8 %) and accomplishing it in a short time (i.e., 5 min). The proposed method would be employed for detecting other acids in blood.

Functionalized ionic liquids as an efficient sorbent for solid-phase extraction of tetracyclines in bovine milk

In this research, a novel ionic liquid-based sorbent, N,N,N-trimethyl-3-(triethoxysilyl)propan-1-aminium bromide silica gel (SiO2-NH2), was successfully synthesized through chemical interaction. The synthesized adsorbent was first applied as a stationary phase for the preconcentration of tetracycline antibiotics (TCAs) at trace level from milk samples via solid-phase extraction. The structure of SiO2-NH2 was studied by Fourier-transform Infrared Spectroscopy (FTIR), Thermogravimetric Analysis (TGA), Energy-Dispersive X-ray Spectroscopy (EDX), and Scanning Electron Microscopy (SEM) to verify the successful synthesis based on the existence of ionic liquid on the surface of silica gel. The factors impacting a solid-phase extraction procedure were investigated, such as types of material, sample volume, breakthrough volume, and elution conditions. In addition, we also compared self-synthetic SPE cartridges with commercial cartridges with the assistance of LC-MS/MS. The SiO2-NH2 effectively retained and separated all three tetracycline antibiotics, including tetracycline (TC), oxytetracycline (OT), and chlortetracycline (CT), with a recovery efficiency of 99.4 % to 100 %. The maximum recovery was obtained when the analytes were eluted using a suitable mixture of acetonitrile, methanol, and acetic acid (2:2:1, v/v/v) for a volume of 1 mL. The enrichment factors of TC, OT, and CT were 110 mL, 150 mL, and 100 mL, respectively. The detection limits for TC, OT, and CT were 0.360, 0.279, and 0.390 mgL−1, corresponding with lower than 5 % relative standard deviation (RSD).

Sorption of Pt(II) on inactive biomass of Aspergillus Niger O-5 treated with cetyltrimethylammonium bromide

Platinum-group cytostatic have been found in natural waters due to the current inefficiency of wastewaters treatment plants. This study was aimed to the assessment of inactive biomass of Aspergillus niger O-5 treated with cetyltrimethylammonium bromide as sorbent for solid phase extraction of [PtCl4]2-complex from aqueous dissolutions for the subsequent development of new water treatment technologies. Maximum sorption capacity of 54 mg·g−1 was achieved at 25 °C under the following experimental conditions: pH of dissolution = 5, biomass mass = 10 mg, dissolution volume = 10 mL, Pt(II) mass = 0.5 mg and contact time = 30 min. The good fitting of the model of Ho and the increase of sorption capacity up to 102 mg·g−1 with temperature suggested the chemisorption as predominant mechanism. The mean free energy of adsorption was higher than 8 kJ·mol−1 for all temperatures, which also indicated the chemical character of the interaction. The absolute value of the standard molar Gibbs free energy of formation increased from 3.032 to 8.336 kJ· mol−1 with temperature signifying that the sorption was thermodynamically favored, occurred spontaneously and the degree of spontaneity increased with temperature. The positive value (32.3 kJ·mol−1) of the standard molar enthalpy qualified the sorption as an endothermic process, after which the adsorbent/sorbate system became more thermodynamically stable.

Alien species water hyacinth realizes waste into treasure: The preparation of biomass sorbent to determine benzoylurea insecticides in tea products.

A fast and effective analytical method with biomass solid-phase microextraction sorbent combined with a high-performance liquid chromatography-ultraviolet detector was proposed for the determination of benzoylurea (BU) insecticides in tea products. The novel sorbent was prepared by activating and then carbonizing water hyacinth with a fast growth rate and low application value as raw material and showed a high specific surface area and multiple interactions with analytes, such as electrostatic action, hydrogen bonding, and π-π conjugation. After optimizing the three most important extraction parameters (pH [X1], sample loading rate [X2], and solution volume [X3]) by Box-Behnken design, the as-established analytical method showed good extraction performance: excellent recovery (80.13%-106.66%) and wide linear range (1-400µg/L) with a determination coefficient of 0.9992-0.9999, a low limit of detection of 0.02-0.1µg/L and the satisfactory practical application results in tea products. All these indicate that the water hyacinth-derived material has the potential as a solid-phase extraction sorbent for the detection and removal of BU insecticides from tea products, and at the same time, it can also achieve the effect of rational use of biological resources, maintaining ecological balance, turning waste into treasure, and achieving industrial production.

Use of Commercial Mixed-Mode Stationary Phases and Sorbents in the High-Performance Liquid Chromatography Analysis and Solid-Phase Extraction of Ionized and Hydrophilic Bioactive Compounds.

Mixed-mode high-performance liquid chromatography (HPLC) is increasingly used for the analysis of ionic and highly hydrophilic drugs, which are difficult to separate by conventional single-mode HPLC. In the former case, chromatographic separation is achieved using one of the several commercially available mixed-mode stationary phases, typically combinations of reversed and ion-exchange phases. Moreover, mixed-mode stationary phases can be used as solid-phase extraction (SPE) sorbents. This review focuses on the recent applications of mixed-mode stationary phases in the chromatographic analysis of bioactive compounds, such as drugs, herbicides, and pesticides. Specifically, we briefly summarize HPLC methods utilizing mixed-mode stationary phases and SPE pretreatment procedures utilizing mixed-mode sorbents developed in the last decade, thus providing a reference work for overcoming the difficulties in analyzing ionized or hydrophilic drugs by conventional reversed-phase chromatography.

Development of a smartphone-integrated microfluidic paper-based optosensing platform coupled with molecular imprinting technique for in-situ determination of histamine in canned tuna

We reported the development of a smartphone-integrated microfluidic paper-based optosensing platform for in-situ detection and quantification of histamine in canned tuna. Molecularly imprinted polymers were synthesized via precipitation polymerization and utilized as dispersive solid phase extraction sorbent to selectively extract histamine from canned tuna. Carbon quantum dots functioning as a fluorescent probe were synthesized and introduced onto the microzones of the microfluidic paper device. This facilitated a noticeable fluorescence color change from dark red to vivid blue upon the addition of histamine. The change in fluorescence on the paper device was converted into specific RGB values using a portable UV light box combined with a smartphone. This assay achieved the limit of detection of 14.04 mg/kg with the linear range from 20 to 100 mg/kg of histamine in canned tuna. The entire molecular imprinting-microfluidic optosensing test could be completed in 45 min including sample preparation.

Novel dummy molecularly imprinted polymer for simultaneous solid-phase extraction of stanozolol metabolites from urine

Stanozolol, a synthetic derivative of testosterone, is one of the common doping drugs among athletes and bodybuilders. It is metabolized to a large extent and metabolites are detected in urine for a longer duration than the parent compound. In this study, a novel dummy molecularly imprinted polymer (DMIP) is developed as a sorbent for solid-phase extraction of stanozolol metabolites from spiked human urine samples. The optimized DMIP is composed of stanozolol as the dummy template, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker in a ratio of 1:10:80. The extracted analytes were quantitively determined using a newly developed and validated ultrahigh-performance liquid chromatography tandem mass spectrometry method, where the limits of detection and quantitation were 0.91 and 1.81 ng mL−1, respectively, fulfilling the minimum required performance limit decided on by the World Anti-Doping Agency. The mean percentage extraction recoveries for 3’-hydroxystanozolol, 4β-hydroxystanozolol, and 16β-hydroxystanozolol are 97.80% ± 13.80, 83.16% ± 7.50, and 69.98% ± 2.02, respectively. As such, the developed DMISPE can serve as an efficient cost-effective tool for doping and regulatory agencies for simultaneous clean-up of the stanozolol metabolites prior to their quantification.Graphical abstract

Application of a novel deep eutectic solvent modified carbon nanotube for pipette-tip micro solid phase extraction of 6-mercaptopurine

Background6-mercaptopurine (6-MP) is a chemotherapy drug mainly used to treat leukemia. It is a persistent organic pollutant and can remain in the environment for a long period of time. The presence of 6-MP in the environment poses a number of hazards and needs to be assessed to monitor its potential risk to human health and the environment. However, due to its trace amount in complicated matrices, a clean-up and preconcentration step before its determination is compulsory.ResultsAs a highly efficient adsorbent for the extrication of 6-mercaptopurine (6-MP), a novel carbon nanotube doped with camphor: decanoic acid deep eutectic solvent was synthesized and applied as a packing material for the pipette-tip micro solid phase extraction sorbent of 6-MP from tap, wastewater and seawater samples before its spectrophotometric determination. Characteristics and structure of this adsorbent was fully investigated. Factors affecting extraction, including type and volume of the eluent, ionic strength and pH of the sample solution, amount of adsorbent, and number of extraction and elution cycles were optimized using one-factor-at-a-time and response surface methodologies. The method was found to be linear in the range of 1 to 1000 µg/L with a limit of detection and quantification of 0.2 and 0.7 µg/L, respectively. Reproducibility as relative standard deviation was better than 4.6%.ConclusionApplication of deep eutectic solvent modified carbon nanotube indicated suitable microextraction results and good potential for rapid extraction of trace amounts of 6-MP from different aqueous samples. The amount of sample required for the analysis was less than 10 mL and only 1.5 mg of the adsorbent was used. The total analysis time, including extraction was less than 15 min and the adsorbent could be used for at least 10 times, without significantly losing its adsorption ability. Compared to using unmodified usual carbon nanotubes, deep eutectic solvent doped carbon nanotubes showed 19.8% higher extraction ability.

Retraction Note: Application of Polypropylene Amine Dendrimers (POPAM)-Grafted MWCNTs Hybrid Materials as a New Sorbent for Solid-Phase Extraction and Trace Determination of Gold(III) and Palladium(II) in Food and Environmental Samples

Retraction Note: Application of Polypropylene Amine Dendrimers (POPAM)-Grafted MWCNTs Hybrid Materials as a New Sorbent for Solid-Phase Extraction and Trace Determination of Gold(III) and Palladium(II) in Food and Environmental Samples

Covalent organic framework aerogel for high-performance solid-phase extraction of tetracycline antibiotics: Experiment and simulated calculation on adsorption behavior

Three-dimensional sponge-architecture covalent organic frameworks (COFs)-aerogel was successfully designed and synthesized via a freeze-drying template approach, and utilized as an efficient sorbent in solid-phase extraction (SPE). A method for selective enrichment of pharmaceutical contaminants including tetracycline, chlortetracycline, methacycline and oxytetracycline in the environment and food samples was proposed by combining with high performance liquid chromatography (HPLC). To understand the adsorption mechanism, selectivity test and molecular dynamics (MD) simulated calculation were both carried out. The experimental and in-silico results demonstrated that the COFs-aerogel possessed high selectivity for contaminants with H bond acceptors/donors and good efficiency with maximum adsorption capacity up to 294.1 mg/g. The SPE-based HPLC method worked well in the range of 8–1000 ng/mL, with the need of little dose of adsorbent and sample volume while no need of spectrometer, outgoing the reported adsorbents. Under the optimized conditions, the intra-day and inter-day relative standard deviations (RSD) of repeatability were within 2.78–6.29 % and 2.44–8.42 % (n = 5). The results meet the current detection requirement for practical applications, and could be extended for further design of promising adsorbents.

Preparation of ionic porous polymers for extraction of four phenolic endocrine disrupting chemicals from fish and water samples

In this paper, series of ionic polymers were synthesized by crosslinking alkyl quaternary ammonium salts with 1,4-bis(chloromethyl)benzene. Among them, hyper-crosslinked polymer fabricated with dodecyl dimethyl benzyl ammonium chloride (HCP-DD) as monomer delivered superior adsorption performance for endocrine disrupting chemicals (EDCs). The adsorption mechanism mainly includes π-π stacking, hydrophobic and electrostatic interaction. With HCP-DD as solid phase extraction sorbent, a high performance liquid chromatography-diode array detection method was developed for the detection of four phenolic EDCs in water and fish samples. The detection limits of the method were 0.005–0.02 ng mL−1 for water samples and 3–30 ng g−1 for fish samples. The recoveries of EDCs in water samples and fish samples were 80–119% and 81.3–117% (relative standard deviations <4.4%), respectively. The study not only provides a route for preparation ionic porous polymers, but also highlights the applications of ionic polymers as efficient adsorbent to enrich organic pollutants.

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.

The potential of polyaniline-coated stationary phase in hydrophilic interaction liquid chromatography-based solid-phase extraction for glycopeptide enrichment

Glycopeptide enrichment is a crucial step in glycoproteomic analysis, often achieved through solid-phase extraction (SPE) on polar stationary phases in hydrophilic interaction liquid chromatography (HILIC). This study explores the potential of polyaniline (PANI)-coated silica gel for enriching human immunoglobulin G (IgG). Experimental conditions were varied to assess their impact on glycopeptide enrichment efficiency, comparing PANI-cotton wool SPE with conventional cotton wool as SPE sorbents. Two formic acid concentrations (0.1% and 1%) in elution solvent were tested, revealing that higher concentrations led to earlier elution of studied glycopeptides, especially for sialylated glycopeptides. Substituting formic acid with acetic acid increased the interaction of neutral glycopeptides with the PANI-modified sorbent, while sialylated glycopeptides showed no significant change in enrichment efficiency. Acetonitrile concentration in the elution solvent (5%, 10%, and 20%) affected the enrichment efficiency with most glycopeptides eluting at the lowest acetonitrile concentration. The acetonitrile concentration in conditioning and washing solutions (65%, 75%, and 85%) played a crucial role; at 65% acetonitrile, glycopeptides were least retained on the stationary phase, and neutral glycopeptides were even detected in the flow-through fraction. This study shows the potential of in-house-prepared PANI-modified sorbents for SPE-HILIC glycopeptide enrichment, highlighting the crucial role of tuning experimental conditions in sample preparation to enhance enrichment efficiency and selectivity.

Rapid, efficient, and accurate determination of aflatoxins and capsaicinoids in vegetable oils by immunomagnetic sorbents coupled with UHPLC–MS/MS

AbstractA fast, simple, and sensitive analytic method was proposed for the simultaneous quantification of aflatoxins (AFTs) and capsaicinoids in vegetable oils by immunomagnetic sorbent coupled with ultra‐performance liquid chromatography coupled with tandem mass spectrometry. The immunomagnetic solid phase extraction (IMSPE) sorbents were synthesized with the monoclonal antibodies via cyanogen bromide magnetic sorbents, which could modify the surface magnetic sorbents under mild synthetic condition. The IMSPE procedure had the following aspects such as ease manipulation, easy disperse, quick isolation, eco‐friendly, and cost‐effective. The major conditions of IMSPE procedure were systemically studied, and the optimized pretreatment was accomplished in 15 min avoding complicated condition or sophisticated equipment. Excellent linearities were achieved by the correlation (R2) more than 0.9983. The limits of quantifications of all analytes ranged from 0.03 to 0.20 µg kg−1, and the recoveries were satisfactory ranging from 75.7% to 124.0% with the intra‐day and inter‐day precisions less than 10.1%. Additionally, the proposed method was used to analyze AFTs and capsaicinoids in retail oil samples. Overall, 25% of soybean and peanut oils and 12.5% of corn and blended oil were detected with AFTs, and no capsaicinoid was found. The content of AFTs was under the MRLs set by EU and China regulation for food quality and safety. The validated results indicated that this method could be utilized for a rapid, efficient, and accurate quantification of AFTs and capsaicinoids in complex lipid‐based matrix.