Solid-phase Extraction Material Research Articles

Core-Shell Magnetic Imprinted Polymers for the Recognition of FLAG-Tagpeptide

FLAG® tag (DYKDDDDK) is a small epitope peptide employed for the purification of recombinant proteins such as immunoglobulins, cytokines, and gene regulatory proteins. It provides superior purity and recoveries of fused target proteins when compared to the commonly used His-tag. Nevertheless, the immunoaffinity-based adsorbents required for their isolation are far more expensive than the ligand-based affinity resin used in combination with the His-tag. In order to overcome this limitation we report herein the development of molecularly imprinted polymers (MIPs) selective to the FLAG® tag. The polymers were prepared by the epitope imprinting approach using a four amino acids peptide, DYKD, including part of the FLAG® sequence as template molecule. Different kinds of magnetic polymers were synthesised in aqueous and organic media also using different sizes of magnetite core nanoparticles. The synthesised polymers were used as solid phase extraction materials with excellent recoveries and high specificity for both peptides. The magnetic properties of the polymers confer a new, effective, simple, and fast method in the purification using FLAG® tag.

Single-vial preconcentration and cold vapor generation for the determination of Hg(II) in water samples of different salinities.

In this work, a single-vial methodology for the extraction and cold vapor generation of mercury(II) was developed, followed by the determination of the analyte by atomic absorption spectrometry, with application in water samples of different salinities. L-cystine-modified Fe3O4 nanoparticles (2LcysMNP) were used as sorbent material in the magnetic solid phase extraction (MSPE) in the same flask in which the mercury vapor generation step was performed using a handmade gas-liquid separator developed in our laboratory. The main conditions for extraction, pre-concentration, and cold vapor generation of mercury were optimized. Under the optimized conditions, detection and quantification limits of 0.04 and 0.12 μg L-1, respectively, were achieved with a relative standard deviation of 7.5%. The single-vial system allowed for a preconcentration factor of 30 and an enrichment factor of 24. The accuracy of the method was evaluated by applying it to certified reference materials, and the obtained values were not significantly different from the expected values according to the Student's t-test. Verification of non-specific interferences was assessed by recovery tests, resulting in recoveries ranging from 81 to 111% for water samples of different salinities.

A high-capacity malleable cellulose aerogel with layered double hydroxide decorating ZIF-8 for efficient adsorption of ciprofloxacin

The misuse of ciprofloxacin (CIP) poses significant risks to our ecosystems by causing serious environmental pollution and the development of antibiotic-resistant bacteria, which requires effective remediation technologies. Herein, we developed a composite material (CMC/CoNiFe-LDH/ZIF-8, abbreviated as CLZ) of loading layered double hydroxide (CoNiFe-LDH) decorating zeolitic imidazolate framework (ZIF-8) on the carboxymethylcellulose sodium (CMC) aerogel as an adsorbent for CIP removal. The CMC aerogel in the composite provided a porous structure as the growth template of CoNiFe-LDH, while CoNiFe-LDH provided growing points for ZIF-8, and ZIF-8 could be used as a carrier for loading CIP, resulting in a high adsorption property of CLZ with optimized mass ratios of CMC/CoNiFe-LDH aerogels and ZIF-8 at 5:1 (denoted as CLZ-1). The adsorption process of CLZ-1 followed the pseudo-second-order kinetic model and Langmuir isotherm model, and the maximum capacity of CLZ-1 to adsorb CIP was 1397.5 mg·g−1. The results of characterization, data fitting and parameter revealed that strong hydrogen bonding, complexation of unsaturated metals, electrostatic interaction, and π–π stacking between CLZ-1 and CIP were the main mechanisms for CIP adsorption. In addition, the CLZ-1 was successfully used as a solid phase extraction material combined with high performance liquid chromatography (HPLC) for the detection of CIP. Meanwhile, the CLZ-1 adsorbed CIP showed excellent antibacterial activity. Hence, CLZ-1 demonstrated great potential and promising practicability in separation and removal of antibiotic contaminants.

Immunoaffinity extraction followed by enzymatic digestion for the isolation and identification of proteins employing automated μSPE reactors and mass spectrometry

This work describes a novel automated and rapid method for bottom-up proteomics combining protein isolation with a micro-immobilised enzyme reactor (IMER). Crosslinking chemistry based on 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling was exploited to immobilise trypsin and antibodies onto customisable silica particles coated with carboxymethylated dextran (CMD). This novel silica–CMD solid-phase extraction material was characterised using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), conductometric titrations and enzymatic colorimetric assays. Micro-solid-phase extraction (μSPE) cartridges equipped with the modified CMD material were employed and integrated into an automated and repeatable workflow using a sample preparation workstation to achieve rapid and repeatable protein isolation and pre-concentration, followed by tryptic digestion producing peptide fragments that were identified by liquid chromatography mass spectrometry (LC-MS).Graphical abstract

Three-dimensional flower-like SnS2 materials for dispersive solid-phase extraction of endocrine-disrupting phenols.

In this study, three-dimensional flower-like tin disulfide materials were prepared, and a highly efficient dispersive solid-phase extraction method was developed using the obtained three-dimensional tin disulfide adsorbents for the preconcentration and determination of six endocrine-disrupting phenols in combination with high-performance liquid chromatography-ultraviolet detection. Several important experimental parameters influencing extraction efficiency were investigated, including the amount of adsorbent, ultrasound time, sample solution pH, sample volume, type of elution solvent, desorption time, and the number of desorption times. Under the optimized experimental conditions, the developed method showed good linearity with the determination coefficients of 0.993-0.998 in the linear range of 0.5-400ng/ml and low limits of detection in the range of 0.15-1.0ng/ml, as well as satisfactory intra-day and inter-day precisions with relative standard deviations of 0.1-9.8%. Finally, the proposed method was successfully applied for the enrichment and determination of trace endocrine-disrupting phenols in milk, tea beverage, and plastic bottled water samples, and acceptable recoveries were obtained from 70.1% to 119.1% under four different spiked concentration levels. The results showed that the three-dimensional tin disulfide materials had great potential for the extraction of endocrine-disrupting phenols contaminants in environmental and food samples.

Designing and preparing metal mediated magnetic imprinted polymer for recognition of tetracycline

Recently, metal mediated molecularly imprinted polymers (MMIPs) raise extensive attention due to their special adsorption/desorption mechanism. And the metal ion plays a key role both for MMIPs preparation and molecular recognition. But it is still a big question to select one suitable metal ion. To overcome above problem, one computational approach was proposed by calculating interaction energy (ΔE) of ternary complexes (monomer-M2+-template) with GAMESS software at the PBE0 level. Finally Cu(II) was screened from four doubly charged metal ions with different radii. Then Cu mediated MIP was prepared via surface imprinting technique with Fe3O4 as the core in a water system. Subsequently, the adsorption behavior of the MMIP immobilized Cu(II) was investigated in detail. The results indicated the microspheres own excellent specificity and selectivity towards tetracycline (TC), as well as long-term stability and good reproducibility. The apparent maximum binding capacity and the imprinting factor were as high as 163.5 mg g− 1 and 19, respectively. Coupled with HPLC-PDA, the microspheres was successfully used as a dispersed solid phase extraction material to extract trace TC in chicken liver. At three spiking levels, mean recoveries ranged from 89.3% to 97.1% with relative standard deviations less than 4.0% (n = 3). Limits of detection and quantitation were 0.0073 mg kg− 1 and 0.024 mg kg− 1, respectively, which can meet the strict requirement of the regulations stipulated by EU. Moreover, preliminary studies showed the radius of the metal ion and ΔE of the complexes all affect the adsorption capacity, specificity and mass transfer rate of the MMIP.

Novel approach for strontium preconcentration from seawater and rapid determination of 89,90Sr in emergency situations

A novel approach for rapid 89,90Sr determination in seawater samples is developed. For the first time in the radioanalytical application, the features of the synthetic zeolite Z4A and a highly selective material for Sr separation were synergically employed. Seawater composition significantly reduces Sr yield on highly selective solid-phase extraction materials, making the preconcentration step essentially important but laborious and time-consuming. To address this issue, the ability of zeolite 4A to concentrate the Sr from the seawater matrix was employed. With the proposed method, two important goals were achieved: (i) simple preconcentration of Sr that can be conducted directly at the sampling site, enabling a rapid procedure for 89,90Sr determination in emergencies, and (ii) high and stable Sr recoveries (89 ± 4%) necessary for lowering detection limits. Strontium is effectively separated from 1 L of seawater in less than 1.5 h, which is especially important in emergency situations, such as the Fukushima Daiichi Nuclear Power Plant accident. Minimum detectable activities achieved for 89Sr:90Sr activity ratio ∼10:1 were 0.74 Bq/L for 89Sr, and 1.47 Bq/L for 90Sr, detected by Cherenkov counting, 36–38 h after separation, and 30 min counting time.

Cationic microcrystalline cellulose - Montmorillonite composite aerogel for preconcentration of inorganic anions from dairy wastewater.

Development of efficient adsorbents to inorganic anions as a solid phase extraction (SPE) material is highly desirable for chromatographic analysis and pollution control. In this work we developed a new hybrid cationic microcrystalline cellulose aerogel composite. Cationic cetylpyridinium imbedded montmorillonite (CPC-MT) was uniformly entrapped in microcrystalline cellulose (MCC) to enhance anionic adsorption efficiency and mechanical stability. The developed CPC-MT@MCC aerogel was used as an SPE adsorbent for anions from dairy wastewater by coupling with ion-column chromatography. Further quaternized CPC-MT@MCC aerogel (CPC-MT@QMCC) showed unique low density (10.6mgcm-3), large specific surface area (320m2g-1), porosity 70%, 800mgg-1 nitrate adsorption capacity within 60min and ease of elution in alkaline solutions. The CPC-MT@QMCC aerogel showed efficient regeneration and reuse performances for up to 10 cycles. More importantly, a dynamic binding efficiency of 710mgg-1 highlights its excellent performance for practical applications. 96% of nitrate anion from environmental manure wastewater samples were adsorbed with 98.7% recovery. A good linear relationship was obtained in the range of 0.01-10mgL-1 and the limits of detection was 0.5mgL-1 using CPC-MT@QMCC aerogel as a preconcentration column. The successful synthesis of such intriguing and economic CPC-MT@QMCC aerogel may provide a promising matrix for high-performance and high efficiency chromatographic media.

Assessment of automated off-line solid-phase extraction LC-MS/MS to monitor EPA priority endocrine disruptors in tap water, surface water, and wastewater.

EPA method 539.1 recently introduced an expanded list of priority endocrine-disrupting compounds (EDCs), some of which were also included in the Unregulated Contaminant Monitoring Rule 3 (UCMR3). Though standardized methods are available for drinking water, analysis of steroid hormones and bisphenol A (BPA) at the ultra-trace level remains challenging. This study set out to evaluate the suitability of automated off-line solid-phase extraction (SPE) liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) for the determination of EPA-priority EDCs in environmental water matrixes (tap water, surface water, and wastewater influents and effluents). The target molecules included 14 steroid hormones (altrenogest, androstenedione, equilenin, equilin, α-estradiol, β-estradiol, estriol, estrone, ethinylestradiol, levonorgestrel, medroxyprogesterone, norethindrone, progesterone, testosterone) and BPA. Factors that may influence the analytical performance were assessed. This involved, for instance, testing combinations of SPE materials from different brands and protocol variations. Several materials presented absolute extraction efficiencies in acceptable ranges. Initial sample pH, nature of reconstitution medium, and mobile phase salt concentration were among the potential factors affecting analyte signal. Storage conditions (different preservative agents) possibly exerted the strongest influence, in agreement with the literature. Limits of detection were in the range of 0.03-0.5ng/L in drinking water, 0.1-0.5ng/L in surface water, and 0.16-1ng/L in wastewater. Method validation also involved testing linearity, accuracy, and precision in reagent water and matrix-matched extracted calibrants. The method was applied to field-collected water samples in Eastern Canada. Summed EDC concentrations remained low in tap water (<LOQ-0.92ng/L), while higher detection frequencies and contamination levels were reported in riverine surface waters (2.6-37ng/L) and municipal wastewaters (10-424ng/L).

Solid phase extraction materials as a key for improving the accuracy of silver nanoparticle characterization with single-particle inductively coupled plasma mass spectrometry in natural waters through dissolved silver removal

The accurate characterization of silver nanoparticles (Ag NPs) in environmental samples is crucial for understanding the potential impact of these materials on the environment and human health. Single-particle inductively coupled plasma mass spectrometry (spICP-MS) is one of the few techniques available for quantifying NPs at environmentally relevant concentrations. However, the spICP-MS detection of Ag NPs can be interfered with coexisting dissolved analyte causing high background signals, which mask NP signals leading to a significant bias in NP characterization. In this paper, a simple sample pre-treatment procedure for efficient removal of dissolved silver in natural waters is proposed using solid phase extraction (SPE) materials, allowing more accurate characterization of NPs in environmental water matrices. The applicability of eight commercially available SPE materials was evaluated based on their effects on sample Ag NP properties and dissolved silver extraction efficiency in environmental waters, which were shown to depend on sample matrix. The SPE materials found most efficient in dissolved silver extraction were further studied for improving the characterization of 30 nm Ag NPs in colorless and dark-colored waters. Whereas dissolved silver concentrations of ≤1 μg kg−1 were shown to lead to a significant bias in NP characterization (up to +58% increase in NP size and − 90% decrease in particle concentration), pre-treatment of the samples with SPE materials ‘SiliaMetS Thiol’ and ‘Purolite C115HMR’ minimized the effect of dissolved silver interference. As a result, highly more accurate NP sizing (28 ± 2 nm) and relatively stable particle concentration was obtained for 30 nm Ag NPs in environmental waters.

Three-Dimensional Ordered Macroporous Magnetic Inverse Photonic Crystal Microsphere-Based Molecularly Imprinted Polymer for Selective Capture of Aflatoxin B1.

Development of an efficient detection method to monitor residual mycotoxins in food is very important to ensure food safety, but the complex food matrix seriously affects the detection sensitivity and accuracy. Here, using a three-dimensional ordered macroporous magnetic inverse photonic crystal microsphere (MPCM) as the supporting material, a molecularly imprinted polymer (MIP) that can selectively recognize aflatoxin B1 (AFB1) was synthesized through the dummy template imprinting strategy. The MPCM@MIP prepared by employing 5,7-dimethoxycoumarin as the template and methacrylic acid as the functional monomer displayed selectivity toward AFB1 (imprinting factor of 1.5) and could be used as a solid-phase extraction material. By coupling with high-performance liquid chromatography, an analytical method targeting AFB1 was established and displayed a wide linear range of 5-1000 ng/mL with a low detection limit of 0.4 ng/mL. The method showed a good recovery rate of 73-92% in AFB1-spiked soy sauce and vinegar samples. Moreover, the MPCM@MIP could be separated from the sample solution easily because of its magnetic performance, displaying a promising future not only in the enrichment of AFB1 to improve the detection sensitivity and accuracy but also in the removal of AFB1 from food and environmental samples.

Multiresidue pesticide analysis in green chilli using GC–MS/MS using modified QuEChERS method with highly efficient Fe3O4@CFR@GO nanocomposite

• Fe 3 O 4 @CFR@GO was tested for the elimination of pigments in pesticide analysis. • Fe 3 O 4 @CFR@GO showed an excellent clean-up efficiency. • Satisfactory purification and recovery effects were achieved in chilli matrices. The presence of pesticide residues in food and vegetables is a growing concern for consumers. In order to monitor these residues reliably, a selective and sensitive, multi-residue system has been developed and validated in green chilli by gas chromatography-tandem mass spectrometry (GC–MS/MS). Fe 3 O 4 @CFR@GO (Fe 3 O 4 @Catechol Formaldehyde Resin@Graphene Oxide) magnetic nanocomposite is used as reversed dispersive solid phase extraction (r-DSPE) materials. Fe 3 O 4 @CFR@GO magnetic nanocomposite is synthesized, characterised by XRD, FTIR and SEM. Comparative investigations have shown that Fe 3 O 4 @CFR@GO magnetic nanocomposite not only has high pigment removal efficiency, but also has more clean-up than typical graphitized carbon black (GCB). The processing of two multiple reaction monitoring (MRM) transformations for each analyte is done by GC–MS/MS in electron impact (EI) mode. Precision and accuracy were tested by recovery studies. The technique proved to be reliable and sensitive in green chilli samples for the routine testing of 35 pesticides.

3DG Functionalized Magnetic Solid Phase Extraction Materials for the Efficient Enrichment of Hexamethylenetetramine in Vermicelli.

Solid phase extraction (SPE) is regarded as the most effective purification method for complex matrix samples owing to its simplicity of operator, time-saving, high accuracy, and environmental friendliness. SPE technology is still affected by the high cost of commercial SPE columns and poor adsorption selectivity. Hence, the development of low-cost and highly selective adsorbents is quite challenging and demanding in SPE. In this study, a novel 3DG functionalized magnetic solid phase extraction materials was prepared based on “thiol-ene” click chemistry. The structure, morphology, thermal stability, and magnetic properties of the magnetic composites were studied by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). Then the adsorption performance of composite was determined by static adsorption experiments, which showed fast binding kinetics (100 min) and good adsorption performance (Qe = 65.34 mg/g). Moreover, these magnetic nanoparticles were used as adsorbents for magnetic solid phase extraction (MSPE) and coupled with high-performance liquid chromatography (HPLC) for separation and detection of illegally added hexamethylenetetramine in vermicelli. As for practical application, the recoveries for the spiked samples in the concentration range of 8–40 μg/g were between 83.24–92.69%, and the RSD was between 0.20–2.07%.

Copper mediated molecularly imprinted polymers for fast recognizing tylosin

As one kind of artificial antibody, molecularly imprinted polymers (MIPs) has been widely used to separate/enrich target molecules from samples with the complex matrix prior to instrumental analysis. In this work, one novel copper mediated magnetic MIPs was developed towards anti-bacteria macrolide antibiotic tylosin (TYL). The obtained microspheres had a lot of convexities distributed evenly on the surface. And it exhibited high hydrophilicity and superparamagnetic ability, as well as excellent selectivity and specificity. Notably, it only took 5 min to reach the absorption equilibrium for TYL, which made it highly feasible for high-throughput analysis. Furthermore, the microspheres was applied as the magnetic dispersed solid phase extraction material to enrich trace TYL residue in (spiked) human urine. At three spiking levels, mean recoveries are in the range of 76.42–93.72% with relative standard deviations of 2.75–8.24% (n = 3) with HPLC/UV-Vis. The work provided one promising reference to prepare novel solid phase extraction materials for enriching/separating trace component in complex matrix.

Selective enrichment of microbiota-derived tryptophan metabolites in mouse faeces based on molecularly imprinted solid-phase extraction for HPLC analysis

Gut microbiota-derived tryptophan (TRP) metabolites, especially the indole derivatives, function as critical modulators of intestinal immune function and integrity via modulating the aryl hydrocarbon receptor pathway. Selective enrichment of these indole metabolites in biological samples is important for quantitative determination by routine methods such as HPLC. Here, we report a molecularly imprinted polymer (MIP) for solid-phase extraction (SPE) of TRP-derived indole metabolites from faeces of mice. The MIP was synthesized by surface polymerization by using indole-3-acetic acid (IAA) and acrylamide after cross-linking by ethylene glycol dimethacrylate (EGDMA) and initialed by 2′,2-azobisisobutyronitrile (AIBN). The MIPs were then characterized by transmission electron microscope (TEM) and fourier transform infrared spectroscopy (FTIR), and the adsorption capacity, selectivity and reusability of MIPs were systematically evaluated. Results showed that IAA-MIPs showed a uniformly distributed nanoshell layer with a thin shell thickness of 26 nm. The IAA-MIPs could selectively adsorb IAA, indole-3-propionic acid (IPA), and indole-3-lactic acid (ILA) in a mixed solution that also contains TRP and tyrosine. The adsorption capacity of IAA-MIPs only slightly decreased with the increase of recycling use. As purification material for SPE, the IAA-imprinted polymers (IAA-MIPs) were successfully applied to extract IAA, IPA, and ILA from normal and colitis mice for HPLC determination. Collectively, these surface molecularly imprinted polymers could find extensive use to selective enrichment of microbiota-derived indole metabolites in biological samples.

An Overview of Modified Chitosan Adsorbents for the Removal of Precious Metals Species from Aqueous Media.

This mini-review provides coverage of chitosan-based adsorbents and their modified forms as sustainable solid-phase extraction (SPE) materials for precious metal ions, such as gold species, and their complexes in aqueous media. Modified forms of chitosan-based adsorbents range from surface-functionalized systems to biomaterial composites that contain inorganic or other nanomaterial components. An overview of the SPE conditions such as pH, temperature, contact time, and adsorbent dosage was carried out to outline how these factors affect the efficiency of the sorption process, with an emphasis on gold species. This review provides insight into the structure-property relationships for chitinaceous adsorbents and their metal-ion removal mechanism in aqueous media. Cross-linked chitosan sorbents showed a maximum for Au(III) uptake capacity (600 mg/g), while S-containing cross-linked chitosan display favourable selectivity and uptake capacity with Au(III) species. Compared to industrial adsorbents such as activated carbon, modified chitosan sorbents display favourable uptake of Au(III) species, especially in aqueous media at low pH. In turn, this contribution is intended to catalyze further research directed at the rational design of tailored SPE materials that employ biopolymer scaffolds to yield improved uptake properties of precious metal species in aqueous systems. The controlled removal of gold and precious metal species from aqueous media is highly relevant to sustainable industrial processes and environmental remediation.

Sulfonated halloysite nanotubes as a novel cation exchange material for solid phase extraction of toxic pyrrolizidine alkaloids.

Pyrrolizidine alkaloids are phytochemicals, which present a highly toxic class of compounds in multiple food resources and are therefore a late-breaking topic in food safety. This study describes the first use of modified halloysite nanotubes as a novel solid material for solid phase extraction. As a result of a fast one-pot sulfonation of the cheap and non-toxic halloysite nanotubes, an efficient cation exchange phase has been prepared. After optimization of the solid phase extraction protocol, high extraction efficiencies and overall recoveries were obtained for a mixture of four pyrrolizidine alkaloid structures through UHPLC-MS/MS analysis with caffeine as the internal standard. Furthermore, the novel solid phase was used for the selective binding of the toxic pyrrolizidine alkaloids in a real-life honey sample, which itself is often contaminated with these compounds. In-house validation showed great extraction efficiencies up to 99.9% for senecionine with a lower limit for lycopsamine with 59.3%, which indicated high selectivity even in the presence of potential interfering compounds. Subsequently, overall recoveries up to 91.5% could be obtained for senecionine while the lowest value was reached for lycopsamine with 55.1%. Comparison with a commercial strong cation exchange tube procedure showed the high competitiveness of the novel solid phase with respect to overall performance. Only slight disadvantages regarding precision and repeatability with values under 5.7% and 11.6% could be observed. Therefore, sulfonated halloysite nanotubes present themselves as an easy to prepare, cheap and highly efficient novel cation exchange material for the selective solid phase extraction of toxic pyrrolizidine alkaloids in frequently contaminated real-life samples like honey.

TiO2@MOF-919(Fe-Cu) as a sorbent for the extraction of benzoylurea pesticides from irrigation water and fruit juices.

The TiO2@MOF-919(Fe-Cu) solid-phase extraction material was prepared by growing MOF-919(Fe-Cu) in situ on three-dimensional radial TiO2 microspheres by a simple solvothermal method. This combination drew on both the resources of good single dispersion and extraction rate, which made it a better extraction material. It was accompanied with high-performance liquid chromatography (SPE-HPLC) for the separation and determination of four benzoylurea pesticides (triflumuron, chlorbenzuron, teflubenzuron and diflubenzuron) in afforestation irrigation water and juice samples (grape, peach and apple juices). Under the optimal conditions, the linearity of the method ranged from 1 to 400 μg L-1 with a correlation coefficient (R2) ≥ 0.9994, while the detection limit was in the range of 0.40-0.56 μg L-1 for the four pesticides. The adopted material showed good reusability and can be used no less than 10 times. The intra-day and inter-day precision were in the range of 1.78-3.24% and 4.06-5.08%, respectively. The proposed method was then successfully applied for the detection of benzoylurea pesticides in the spiked samples with good recoveries (72.3-108.4%) and good precision (5.15%) due to π-π and hydrophobic interactions between the analytes and adsorbent. The results show that the composite had the potential to be used as a SPE adsorbent for the enrichment and extraction of benzene ring structures containing imide groups in actual samples.

A new core-shell magnetic mesoporous surface molecularly imprinted composite and its application as an MSPE sorbent for determination of phthalate esters.

In this study, a new core–shell magnetic mesoporous surface molecularly imprinted polymer (Fe3O4@SiO2@mSiO2-MIPs) which has specific adsorption and rapid adsorption rate for phthalate esters (PAEs) was prepared by a convenient method. Based on this composite as a magnetic solid phase extraction (MSPE) material, a rapid, efficient and sensitive matrix dispersion magnetic solid-phase extraction gas chromatography-mass spectrometry method (DMSPE-GC/MS) was developed for the determination of PAEs in multiple liquid samples. It is the first time that Fe3O4@SiO2@mSiO2-MIPs have been prepared by bonding amino groups on the surface of a double layer silicon substrate with diisononyl phthalate (DINP) as virtual template and 3-(2-aminoethyl)-aminopropyl trimethoxymethylsilane (TSD) as functional monomer. FT-IR, TEM, EDS, SEM, XRD, BET and VSM were used to characterize the composite. The adsorption isotherm and kinetics of Fe3O4@SiO2@mSiO2-MIPs showed that it possessed fast adsorption rates (approximately 5 min to reach equilibrium), high adsorption capacities (523.9 mg g−1) and good recognition of PAEs. The real samples were preconcentrated by Fe3O4@SiO2@mSiO2-MIPs, under the optimum DMSPE-GC/MS conditions. Validation experiments showed that the method presented good linearity (R2 > 0.9971), satisfactory precision (RSD < 5.7%) and high recovery (92.1–105.8%), and the limits of detection ranged from 1.17 ng L−1 to 3.03 ng L−1. The results indicated that the novel method had good sensitivity, high efficiency and wide sample application and was suitable for the determination of PAEs in liquid drink samples such as water, alcohol, beverages and so on.

Multiresidue pesticide analysis in tomato using GC-MS/MS using modified QuEChERS method with titanium-coated graphite with CNT-ABS nanocomposite as dispersive solid-phase extraction materials

Abstract The presence of pesticide residues in food and vegetables is a growing concern for consumers. To monitor these residues reliably, a selective and sensitive multiresidue system has been developed and validated in tomato by gas chromatography–tandem mass spectrometry (GC-MS/MS). Titanium-coated graphite with carbon nanotube (CNT) in acrylonitrile–butadiene–styrene (ABS) used as reversed-dispersive solid-phase (extraction materials with modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method. Titanium-coated graphite with CNT-ABS is synthesized, characterized by X-ray diffraction and scanning electron microscopy. The clean-up performance of titanium-coated graphite with CNT-ABS was demonstrated to be better to primary secondary amine and graphitized carbon black cartridges. The processing of two multiple reaction monitoring transformations for each analyte is done using GC-MS/MS in electron impact mode. Satisfactory purification and recovery effects (74%–100%) of 35 pesticides were achieved in tomato matrices when using 5 mg of titanium-coated graphite ABS-CNT nanocomposite. It was observed that quinolphos and deltamethrin are present above the maximum residue limit. The technique proved to be reliable and sensitive in tomato samples for the routine testing of 35 pesticides.