Matrix Solid-phase Dispersion Research Articles

Feasibility of matrix solid-phase dispersion combined with HR-CS FAAS for determination of copper in milk-based infant foods

This study proposes, for the first time, the development of an analytical method using the matrix solid-phase dispersion (MSPD) for extraction of copper from infant formulas and milk-based foods for further determination using high resolution-continuum source flame atomic absorption spectrometry (HR-CS FAAS). MSPD parameters were investigated, and by employing a 0.25 g sample, 0.25 g of diatomaceous earth as a solid support, 1 mol/L HNO3 as the extraction solution, and 1 min of blending, higher agreements with reference values were obtained. The limit of detection of the method was 0.35 µg/g. Accuracy was assessed by comparing the results using the following methods: i) proposed method (MSPD/HR-CS FAAS); and ii) decomposition of samples by microwave-assisted digestion (MAD) and quantification by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS). The MSPD extracts were also quantified using HR-CS GFAAS. No significant difference was found between the results. The agreements ranged from 95 to 103 %, and no significant difference was observed between the results. Copper concentrations ranged from 0.40 to 3.8 μg g−1 using the proposed method, with relative standard deviations lower than 10 %. The proposed method proved to be efficient for the determination of copper in infant formulas and milk powder, offering advantages such quickness, simplicity, low cost, low energy consumption, reduced waste generation (due to the use of an aqueous extraction solution), utilization of materials from renewable sources (diatomaceous earth as a solid support), and minimized analyst exposure when compared to conventional sample preparation methods. These attributes align with the principles of Green Analytical Chemistry.

Achievements and Challenges of Matrix Solid-Phase Dispersion Usage in the Extraction of Plants and Food Samples

A review of the application of matrix solid-phase dispersion (MSPD) in the extraction of biologically active compounds and impurities from plants and food samples with a particular emphasis on conventional and new types of sorbents has been provided. An overview of MSPD applications for the isolation of organic residues from biological samples, determined using chromatographic and spectroscopic techniques, has been presented. In this study, procedural solutions that may extend MSDP applicability for the extraction such as vortex-assisted, ultrasound-assisted, microwave-assisted, and extraction with a magnetic sorbent have been discussed. Special attention has been paid to MSPD sorbents including modified silica, diatomite, magnesium silicate, alumina, carbon materials (carbon nanotubes, graphene oxide, graphene, or graphite), molecularly imprinted polymers, and cyclodextrin. An important aspect of the MSPD procedure is the use of high-purity and environmentally friendly solvents for extraction (e.g., deep eutectic solvents), with such criteria being the most important for modern analytical chemistry. Many advantages of MSPD are presented, such as high recoveries, the requirement for a smaller volume of solvent, and shorter procedure times than classical methods.

A simple and green offline-online capillary electrophoresis stacking strategy for the simultaneous determination of hydrophobic compounds in complicated samples using sodium dodecyl sulfate as the solubilizer and pseudophase

BackgroundCapillary electrophoresis is a powerful analytical method featured with high separation efficiency, minimal sample requirements, and reduced organic solvents consumption. However, its low sensitivity hinders its wide application in determination of trace analytes especially for the weakly ionized hydrophobic compounds. Offline and Online capillary electrophoresis stacking methods are more favored to enhance detection sensitivity of analytes. The determination of two sesquiterpenes and an alkaloid from the dried root of Lindera aggregata merged as an example for developing a simple, sensitive and green method for the simultaneous determination of two hydrophobic compounds in complicated matrix samples. ResultsAn offline-online capillary electrophoresis stacking strategy by integrating micro matrix solid phase dispersion with field-amplified sample stacking and micelle to cyclodextrin stacking has been developed for the simultaneous determination of dehydrocostus lactone, linderane, norisoboldine in complex matrices. The optimized parameters were set at 65 mM sodium dihydrogen phosphate, 35 % methanol, 180 s for sample injection and 210 s for cyclodextrin injection, 20 mM sodium dodecyl sulfate of sample matrix for online stacking; 1:1 sample to MCM-48, 180 s grinding time, and 1000 μL of 20 mM sodium dodecyl sulfate elution for offline procedure. Under the optimum conditions, the method showed good linearity with correlation coefficients (R2 ≥ 0.9927), low limits of detection within the range of 25–50 ng mL−1, satisfactory repeatability and reproducibility below 3.98 %, and acceptable recoveries between 94 % and 97 %. The developed method was successfully applied to two real samples, the root of L. aggregata and rat feces. SignificanceSodium dodecyl sulfate is firstly used as an eluent in micro matrix solid phase dispersion and plays a dual role throughout the analytical procedure, including extraction solvent in sample preparation and micelle pseudophase during online stacking. It brings great procedure convenience to the method. The sensitivity of this method can improve up to 1283-folds compared with the normal mode. Moreover, the overall strategy indicates satisfied green potential evaluated by greenness assessment tools.

Miniaturized matrix solid-phase dispersion assisted by deep eutectic solvent for acrylamide determination in bread samples.

Acrylamide determination is important to state its quantity in baked food preventing any potential carcinogenic effects. Matrix solid-phase dispersion (MSPD) extraction is an extraction procedure based on a homogenization phase between a solid sample and a solid dispersing material to break sample increasing analyte extraction yield, often used for acrylamide determination. The addition of a green deep eutectic solvent (DES) during the MSPD homogenization phase improves the analyte extraction, giving the possibility to reduce the amount of organic solvent used. In this work, a miniaturized MSPD extraction assisted by a DES was developed to determine acrylamide in bread, using high-performance liquid chromatography coupled with mass spectrometry detection. The optimized procedure provides 1:1 (w/w) matrix-to-dispersing material ratio, 2mL of methanol as extraction solvent, and 50 μL of choline chloride-glycerol DES added during the homogenization phase. Method validation ensured good results with minimum recoveries of 90%, high precision with a maximum intra-day error of 4%, and inter-day error of 6%. Limit of detection and limit of quantification resulted to be 16μg/kg and 35μg/kg, respectively. This miniaturized extraction procedure represents a good alternative to those reported in the literature, guaranteeing great performance and respecting green chemistry principles.

Assessment of total mercury in urban particulate matter by filter fiber assisted matrix solid-phase dispersion coupling with microplasma assisted-cold vapor generation

BackgroundThe evaluation of particle-bound mercury (PBM) exposure is a crucial aspect of assessing the global cycle of mercury (Hg) and its adverse effects on human health and ecosystems. Nevertheless, the precise and reliable measurement of PBM remains a formidable task because of the costly and cumbersome equipment required, as well as the inadequate sensitivities exhibited by current analytical techniques. In this study, we provided a unique and straightforward approach utilising filter fiber-assisted matrix solid-phase dispersion (FF-MSPD) in conjunction with single-drop solution electrode discharge-induced cold vapor generation atomic fluorescence spectrometry (SD-SEGD-CVG-AFS) for the precise quantification of PBM. The PBM contained in a small filter was efficiently extracted with 200 μL of eluent (0.2 % L-cysteine and 4 % HCOOH) by FF-MSPD and subsequently converted to Hg0 using SD-SEGD-CVG, before being subjected to examination using AFS. ResultsThe resulted limit of detection (LOD, 3σ) was 0.17 pg m−3, obtained with a sample volume of 12 m3, which was much higher than that of the techniques published in the literatures. The aforementioned technique was effectively utilised for the detection of mercury in 19 samples of PM2.5 and PM10 which were collected over a span of several months. SigniffcanceContrast to conventional methods, the proposed method offers a range of distinct advantages, including simplified operation, absence of memory effects, enhanced sensitivity, substantial reduction in reagent usage, and decreased secondary pollution. These advantages are particularly valuable for advancing research on the fate, transport, and exposure routes of environmental mercury.

Application of deep eutectic solvents on extraction of flavonoids.

Deep eutectic solvents (DESs), as a new type of eco-friendly solvent, have attracted increasing attention on the extraction and separation of flavonoid compounds from various samples, owing to their excellent properties such as biodegradability and ease of handling with very low toxicity. This article provides a status review of the applications of DESs in the extraction of flavonoids, including the introduction of flavonoid compounds, the properties and superiority of DESs, and extraction methods (ultrasonic-assisted extraction, heating reflux extraction, matrix solid-phase dispersion, and solid-phase extraction). Finally, prospects and challenges in the application of DESs on extraction and separation are extensively elucidated and critically reviewed.

Optimization of an analytical method based on miniaturized matrix solid-phase dispersion combined with gas chromatography-mass spectrometry for the determination of bisphenols in mussel samples

In this study, a new method has been optimized to determinate nine bisphenols (BPs) in mussel samples. This approach is based on miniaturized matrix solid-phase dispersion combined with gas chromatography-mass spectrometry determination after trimethylsilylation with 99% N,O-Bis-(trimethylsilyl)trifluoroacetamide + 1 % trimethylchlorosilane. The optimization process investigated the derivatization (derivatizing agent volume, time and temperature) and sample preparation (C18 co-column packed and C18 dispersant agent amounts and elution volume) parameters. A second clean-up step was performed using EMR-Lipid cartridges in order to efficiently remove lipids from mussel, the optimized parameters were Captiva EMR-Lipid sorbent amount and elution volume. The whole method was validated and very good linearity (r2 > 0.99) was obtained. The recoveries (accuracy) at two concentration levels ranged from 51.2 to 109 % and the coefficients of variation (precision) were between 0.55 and 13 %. The limits of quantification were between 0.014 μg/Kg dry weight for BPM and 4.0 μg/Kg dry weight for BPS. The analytical procedure was applied to four mussel samples from Galician Rías. Except for one of four samples whose BPAF level was below the limit of quantification, all BPs were found in concentrations that ranged from 0.39 to 301 μg/Kg dry weight.

Successful synthesis of eco-friendly Metal-Organic framework ([Ni(BDC)]n) allows efficient extraction of multiresidues pesticides and dyes from fish samples

Contaminants such as pesticides and dyes pose substantial challenges to environmental and human health, especially when found in aquatic ecosystems and ingested through the food chain. This requires the development of methods that are efficient, safe and environmentally friendly. In this scenario, this study presents the synthesis and characterization of a metal–organic framework (MOF), specifically [Ni(BDC)]n, designed as a solid adsorbent for the determination of pesticides, including atrazine, bifenthrin, chlorpyrifos, endrin, heptachlor, flutriafol and permethrin, as well as dyes such as crystal violet (CV) and Congo red (CR) in fish samples. Using Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric Analysis (TGA), X-ray Diffraction (XRD), and Brunauer-Emmett-Teller (BET), we verified the success of the MOF synthesis. BET analysis indicated MOF surface area and total pore volume of 2700 m2/g and 0.0136 cm3 g−1, respectively. The adsorption study revealed high affinity of the MOF for the target analytes, with qmax = 208.33 mg g−1 for pesticides and qmax = 4.18 mg g−1 for dyes. The kinetic study demonstrated that the adsorption mechanism follows a pseudo-second order model for all analytes. Furthermore, employing [Ni(BDC)]n, we have developed an efficient extraction method using Matrix-Solid Phase Dispersion (MSPD) combined with Gas Chromatography-Mass Spectrometry (GC–MS) and UV/Vis spectrophotometry for determination of pesticide and dyes, respectively, with pre-concentration factor ranging from 10 to 100 times for the studied analytes. The methods showed satisfactory linearity for both contaminants (pesticides and dyes), with recovery efficiency ranging from 81-103 % and precision < 13 % (n = 3) for the analytes. Linear ranges covering 10.0–500.0 μg L−1 (R2 > 0.995) for pesticides and 100.0–1000.0 μg L−1 (R2 > 0.988) for dyes. The limits of detection (LOD) and quantification (LOQ) ranged from 0.5-1.6 μg L−1 and 1.7–5.6 μg L−1 for pesticides, respectively, while for dyes, LOD and LOQ ranged from 2.0-12.0 μg L−1 and 7.6–39.6 μg L−1, respectively. These results highlight the potential of [Ni(BDC)]n as a promising material for efficient and selective extraction in the sustainable determination of pesticides and dyes in fish samples, with satisfactory reuse.

Development of magnetic matrix solid phase dispersion method for the extraction of crystal violet and rhodamine B from sediments based on magnetic ZIF-8 and a deep eutectic solvent

A magnetic matrix solid phase dispersion (MSPD) method based on magnetic ZIF-8 (SDS@MZIF-8) and a deep eutectic solvent was developed and used to the extraction of crystal violet and rhodamine B in lake sediments. SDS@MZIF-8 was prepared and used as the extraction sorbent and dispersant in MSPD. The magnetic property of MZIF-8 facilitated the recovery of the extraction sorbent after the blending step. Hydrophilic deep eutectic solvents were prepared and used as efficient green dispersing solvents in MSPD. The use of magnetic sorbent in MSPD is simple and fast, eliminating some additional steps commonly used in the classical MSPD and shortening the extraction time. The parameters influencing the extraction efficiency were investigated and optimized. Under the optimized conditions, the intra- and inter-day relative standard deviations were less than 4.9 %. The linearity ranged from 2-400 µg g−1 with coefficients of determination higher than 0.9943. The detection and quantification limits of RB and CV varied between 0.3–0.5 μg g−1 and 1.0–1.8 μg g−1, respectively. Finally, the developed method was applied to the analysis of RB and CV in the sediment samples. The recoveries ranged from 93.2 to 107.3 % and the relative standard deviations ranged from 0.8 to 4.9 %. The results suggest a high potential use of the proposed method to determine the organic pollutants in solid samples. Compared with the conventional MSPD extraction technique, the developed method considerably reduced the sample and solvent consumption, offering important environmental benefits.

Cucurbit[7]uril-mediated matrix solid phase dispersion extraction strategy combined capillary electrophoresis for detection of biogenic amines in foods

Biogenic amines (BAs) are the vital indicators of food freshness, and monitoring the change of BAs content is quite essential for food safety. Herein, we developed a matrix solid phase dispersion (MSPD) extraction technology based on cucurbit[7]uril (Q[7]) to extract BAs from pork and shrimp. Then, the extracted BAs were analyzed by capillary electrophoresis (CE) with low sample consumption and high analytical efficiency. The factors affecting MSPD extraction were optimized by Plackett-Burman and the Box-Behnken design (BBD). The limits of detection (LODs) were ranging from 0.003 to 0.019 mg kg−1, the recoveries of spiked samples were 80.15 %–110.3 %. The satisfactory accuracy and precision were attributed to the host–guest interaction between Q[7] and BAs. Furthermore, the freshness of pork and shrimp was evaluated by simultaneous determination of four BAs. For its wide linear range, high sensitivity, and cost-effectiveness, the proposed Q[7] mediated MSPD-CE-UV provides meaningful potential prospects in the rapid monitor of food freshness and safety.

Optimization of a fast and sensitive method based on matrix solid-phase dispersion-LC-ms/ms for simultaneous determination of phthalates and bisphenols in mussel samples

Bisphenols and phthalates are wide classes of endocrine disrupting chemicals (EDCs) extensively used as additives in plastic products. In this study, a fast and reliable analytical method based on matrix solid-phase dispersion (MSPD) coupled with LC-MS/MS was developed and optimized for simultaneous determination of 8 bisphenols and 7 phthalates in raw mussel extract. The LC-MS/MS method was tested for linearity (R2), inter- and intra-day repeatability, limit of detection and quantification, both for matrix-free and matrix-matched solutions. The MSPD method was optimized in terms of ratio between sample and sorbent, and the type and quantity of the eluents in order to maximize the recoveries and to minimize matrix effects. The obtained recoveries (values between 75% and 113%), limits of detection (values between 0.048 and 0.36 µg kg−1), limits of quantification (values between 0.16 and 1.28 µg kg−1), repeatability (RSD% between 1.30% and 8.41%) and linearity (R2 > 0.998) were satisfactory and suitable for the determination of target micropollutants in food samples. In addition, the low solvent consumption and fast execution make this method ideal for routinely determinations of bisphenols and phthalates in mussels.

Advancing green extraction of bioactive compounds using deep eutectic solvent-based ultrasound-assisted matrix solid-phase dispersion: Application to UHPLC-PAD analysis of alkaloids and organic acids in Coptidis rhizoma

The utilization of deep eutectic solvents (DES) in sustainable extracting and separating of phytochemicals shows promising prospect. An exceptionally fast, eco-friendly, and sustainable approach was proposed for extracting bioactive compounds from Coptidis Rhizoma based on deep eutectic solvent-based ultrasound-assisted matrix solid phase dispersion (DES-UA-MSPD). Single-factor experiments and Box-Behnken design were utilized to explore the optimal extraction conditions. The analysis indicated that the acidic DES, especially betaine-acrylic acid (Bet-Aa 1:4 mol/mol) with 50% water content, was proved to be the most effective medium for the extraction of alkaloids (magnoflorine, groenlandicine, coptisine, epiberberine, berberine and palmatine) and organic acid (chlorogenic acid). With the parameters optimized, the total maximum extraction yield of alkaloids and organic acids reached 128.83 mg g−1 applying the optimal DES, which was 1.33–5.33 folds higher than conventional extraction solvents. Additionally, through microstructure analysis using scanning electron microscopy, density functional theory , and frontier molecular orbitals theory, a deeper understanding of the extraction principle was gained, and the molecular mechanism of DES synthesis and the interactions between target compounds were systematically elucidated. The sustainable and green potential of the DES-UA-MSPD method was demonstrated through Green Analytical Procedure Indexanalysis. The overall results of this investigation revealed that the proposed technology was a highly promising and sustainable alternative for effective extraction and quantification of natural products.

Search for new green natural solid phases for sample preparation for PAHs determination in seafood samples followed by LC and GC–MS/MS analysis

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic organic pollutants found in various environments, notably aquatic ecosystems and the food chain, posing significant health risks. Traditional methods for detecting PAHs in food involve complex processes and considerable reagent usage, raising environmental concerns. This study explores eco-friendly approaches suing solid phases derived from natural sources in matrix solid phase dispersion. We aimed to develop, optimize, and validate a sample preparation technique for seafood, employing natural materials for PAH analysis. Ten natural phases were compared with a commercial reference phase. The methodology involved matrix solid phase dispersion and pressurized liquid extraction, followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Three solid phases (perlite, sweet manioc starch, and barley) showed superior performance in LC-MS/MS and were further evaluated with gas chromatography-tandem mass spectrometry (GC–MS/MS), confirming perlite as the most effective phase. Validation followed Brazilian regulatory guidelines and European Community Regulation 2021/808/EC. The resulting method offered advantages in cost-effectiveness, reduced environmental impact, cleaner extracts, and enhanced analytical performance compared to the reference solid phase and LC-MS/MS. Proficiency analysis confirmed method reliability, with over 50% alignment with green analytical chemistry principles. In conclusion, this study developed an environmentally sustainable sample preparation technique for seafood analysis using natural solid phases, particularly perlite, for PAH determination.

Vortex-blending matrix solid-phase dispersion and UPLC-Q-TOF/MS were proposed to extract and examine the urushiols from Toxicodendron vernicifluum bark

Toxicodendron vernicifluum bark has been used for many years as a component in foods and as a traditional herbal medication. Unfortunately, the presence of urushiols, which induce allergies, limits its application. This study used a vortex-blending matrix solid-phase dispersion microextraction technique to extract urushiols from Toxicodendron vernicifluum bark. HPLC was used to evaluate the amounts of the extracted urushiols (15:0, 15:1, 15:2, and 15:3). The modified magnetic adsorbent was prepared through an in situ coprecipitation method and characterized using a variety of techniques. The optimized extraction conditions are as follows: using magnetic Zeolite Socony Mobil-Five as an adsorbent, a 1:2 sample/adsorbent ratio, 2.5 min of vortex-blending time, 4 mL of 0.1% (V/V) trifluoroacetic acid-methanol as the elution solvent and 8 min of ultrasound time. There was good linearity and high repeatability in the method. Furthermore, the limits of detection for the urushiols ranged from 0.20 to 0.50 μg/mL. Under the optimized conditions, 50 compounds were identified by ultra high performance liquid chromatography and quadrupole time-of-flight mass spectrometry. These compounds included 8 phenolic acids, 9 monomeric urushiols, 11 urushiol dimers, 10 other components, and 11 flavonoids. The suggested approach, which has the advantages of few stages and high extraction efficiency over existing extraction procedures, is a potentially useful method for obtaining and evaluating urushiols in raw materials or extracts.

Multivariate optimization, in conjugation with matrix solid-phase dispersion and digital image detection, allows residual dye determination from shrimp samples

Here, we report an optimization of the extraction of crystal violet and congo red dyes from shrimp samples, employing matrix solid phase dispersion and improved multivariate optimization. Three factors were evaluated: (i) adsorbent nature (neutral alumina, silica gel and C18); (ii) eluent strength (dimethylformamide, methanol and acetonitrile); and (iii) sample-adsorbent ratio (1:1; 1:5; and 1:10, m/m). Successful extraction of dyes was achieved using dimethylformamide as eluent, neutral alumina as adsorbent and sample:adsorbent ratio of 1:5 (m/m). Adsorption and kinetic studies suggest strong interaction between dye and adsorbent. Furthermore, employing digital image colorimetric detection, the study observed limit of detection (LOD) ranging between 3.8 to 29.8 µg L−1 and limit of quantification (LOQ) ranging between 12.3 to 90.3 µg L−1 with R2 > 0.9927 for both dyes, CV and CR, respectively. Notably, recovery was greater than 86 % with a relative standard deviation (RSD) inferior to 7 % (n = 3). These findings indicate the effectiveness of the improved multivariate optimization technique in conjunction with matrix solid-phase dispersion for successful extraction and quantification of dyes from shrimp samples, showing its potential for accurate and sensitive detection in similar analyses. The proposed method was compared with the gold method (UV/Vis spectroscopy) and the statistical treatment showed that the results of both methods are comparable.

Determination of coumarins in Fructus cnidii by using deep eutectic solvent elution-based carboxymethyl chitosan matrix solid-phase dispersive extraction

Fructus cnidii has been used as a folk medicine for thousands of years. Coumarins are the active compounds behind its therapeutic effect. Thus, the determination of coumarins is necessary for quality evaluation of Fructus cnidii. However, most traditional methods for determining coumarins in natural products are time-consuming, organic solvent-consuming, and are not amenable to the analysis of volatile compounds. Herein, a novel method termed deep eutectic solvent-based carboxymethyl chitosan matrix solid-phase dispersion extraction was proposed and applied to the determination of coumarins in Fructus cnidii, including bergapten, imperatorin, and osthole. For the first time, carboxymethyl chitosan was applied as a dispersant and hexanoic acid-monoethanolamine (a deep eutectic solvent) was used as an eluting solution in the analytical procedure. The deep eutectic solvent dissolved the dispersant (CMC), thereby releasing the analytes and precluding irreversible adsorption. The analytes could be simultaneously concentrated during the elution process. The newly developed method was coupled with HPLC for the determination of coumarins in Fructus cnidii. Several critical parameters affecting the extraction performance, including the molar ratio of the sample to dispersant, grinding time, type of eluting solution, and amount of acid added were investigated. The method was validated by using HPLC. The good linearity (r ≥ 0.9998), a low detection limit, satisfactory precision (intra-day precision is less than 1.88 %, inter-day precision is less than 6.71 %) and accuracy (recovery is 91.3 %-95.0 %) were obtained. Under the optimal conditions, the proposed method had advantages including a simpler extraction process, smaller sample amount (10 mg), less organic reagent (2.4 mL), shorter extraction time (7 min), and no additional concentration process. It is also allowed the analysis of volatile compounds and is environment friendly.

Assessing Matrix Solid-Phase Dispersion Extraction Strategies for Determining Bisphenols and Phthalates in Gilthead Sea Bream Samples

Microplastics (MPs) and nanoplastics (NPs) are widely spread in the environment, generating significant concern due to their potential impact on environmental health. Marine species usually ingest plastic fragments, mistaking them for food. Many toxic compounds, such as plastic additives that are not chemically bound to the plastic matrix, can be released from MPs and NPs and reach humans via the food chain. This paper highlights the development and validation of a straightforward solid–liquid extraction clean-up procedure in combination with a matrix solid-phase dispersion method using high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS) detection, enabling facile, precise, and reliable identification and quantitation of a total of six bisphenols and phthalates in gilthead sea breams. Under the optimized conditions, the developed method showed good linearity (R2 &gt; 0.993) for all target compounds. The recoveries obtained were between 70 and 92%. The relative standard deviations (RSDs) for reproducibility (inter-day) and repeatability (intra-day) were less than 9% and 10%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) for the target compounds ranged from 0.11 to 0.68 µg/kg and from 0.37 to 2.28 µg/kg, respectively. A new, efficient extraction methodology for the determination of BPA, BPS, BPF, DBP, DEP, and DHEP in gilthead seabream has been optimized and validated.

Miniaturized centrifugation accelerated pipette-tip matrix solid-phase dispersion based on poly(deep eutectic solvents) surface imprinted graphene oxide composite adsorbent for rapid extraction of anti-adipogenesis markers from Solidago decurrens Lour

Overweight and obesity are the causes of many diseases and have become global "epidemics". Research on natural active components with anti-adipogenesis effects in plants has aroused the interest of researchers. One of the most critical problems is establishing sample preparation and analytical techniques for quickly and selectively extracting and determining the active anti-adipogenesis components in complex plant matrices for developing new anti-adipogenic drugs. In this study, a new poly(deep eutectic solvents) surface imprinted graphene oxide composite (PDESs-MIP/GO) with high selectivity for phenolic acids was prepared using deep eutectic solvents as monomers and crosslinkers. A miniaturized centrifugation-accelerated pipette-tip matrix solid-phase dispersion method (CPT-MSPD) with PDESs-MIP/GO as adsorbent, coupled with high-performance liquid chromatography, was further developed for the rapid determination of anti-adipogenesis markers in Solidago decurrens Lour. (SDL). The established method was successfully used to determination anti-adipogenesis markers in SDL from different regions, with the advantages of accuracy (recoveries: 94.4-115.9%, RSDs≤9.8%), speed (CPT-MSPD time: 11min), selectivity (imprinting factor: ∼2.0), and economy (2mg of adsorbent and 1mL of solvents), which is in line with the current advanced principle of "3S+2A" in analytical chemistry.

Matrix solid-phase dispersion extraction of organophosphorus flame retardants in soil based on response surface methodology

Organophosphorus flame retardants (OPFRs) are widely used in commercial products owing to their exceptional flame-retarding and plasticizing properties. However, OPFRs are also well recognized as emerging persistent organic pollutants (POPs) because of their environmental persistence, biological concentration, and potential toxicity. Thus, the accurate detection of OPFRs in environmental media is critical for analyzing their fate, transport, and ecological risk. However, very few OPFR detection methods are currently available, and the types of OPFRs detected may vary from site to site. In this study, matrix solid-phase dispersion extraction (MSPD), a simple, rapid, and versatile technique for preparing solid, semisolid, liquid, and viscous samples, was combined for the first time with gas chromatography-tandem mass spectrometry (GC-MS/MS) to analyze 10 OPFRs in soil, namely, tripropyl phosphate (TPrP), tri-n-butyl phosphate (TnBP), tri-iso-butyl phosphate (TiBP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(2-chloroethyl) phosphate (TCEP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), triphenylphosphine oxide (TPPO), and trimethylphenyl phosphate (TCP). The GC-MS/MS system was equipped with a Bruker-5MS capillary column coupled with a triple quadrupole mass spectrometer operated in multiple reaction monitoring (MRM) mode. Prior to detection, a mixed standard solution was fortified with 10 ng of13C-PCB208 as an internal standard. The optimal conditions under which MSPD could achieve high selectivity for OPFRs were determined. In addition, single-factor analysis was used to examine the influence of the sorbent (i. e., C18, PSA, Florisil, GCB, and multiwalled carbon nanotubes (MWCNTs)) as well as the dosage, type, and volume of the eluent on the extraction efficiency of the method for the 10 OPFRs. When GCB and ethyl acetate were used as the adsorbent and solvent, respectively, during elution, high extraction recoveries for the OPFRs were achieved. Optimization via response surface methodology (RSM) was adopted to further analyze the impact of three key factors, namely, the adsorbent dosage, eluent volume, and grinding time, as well as their interactions, on OPFR recoveries. Under the optimal conditions of 0.3 g of GCB as the adsorbent, 10 mL of ethyl acetate as the eluent, and 5 min of grinding time, the relative average recovery of the OPFRs was 87.5%. Furthermore, the 10 OPFRs showed good linear relationships under five concentration gradients, with correlation coefficients greater than 0.998. The limits of detection (LODs) and quantification (LOQs) were calculated as signal-to-noise ratios (S/N) of 3 and 10, respectively, and found to be in the ranges of 0.006-0.161 and 0.020-0.531 ng/g, respectively. The performance of the proposed method was verified by determining the recoveries and relative standard deviations (RSDs) of the OPFRs in soils spiked at low, medium, and high levels (10, 20, and 100 ng/g, respectively). The recoveries of the OPFRs ranged from 70.4% to 115.4%, with RSDs ranging from 0.7% to 6.7%. Compared with the conventional accelerated solvent extraction (ASE) method, MSPD presents higher efficiency, simpler operation, and less solvent requirements. The developed method was applied to determine OPFRs in soil samples collected from different sites in Suzhou, including an electronics factory, an auto-repair factory, a paddy field, and a school field. The results revealed that the contents of OPFRs in the soils from the electronics and auto-repair factories were significantly higher than those in the soils from the paddy and school fields. The main pollutants in the soil samples collected from the electronics and auto-repair factories were TCIPP, TPPO, TCEP, and TDCPP. Moreover, the contents of these compounds were 5.30, 4.44, 4.54, and 4.20 ng/g, in soils from the electronics factory and 2.70, 3.93, 7.60, and 5.04 ng/g, in soils from the auto-repair factory. To the best of our knowledge, this study is the first to determine high concentrations of TPPO in industrial soils. Thus, the combination of MSPD and GC-MS/MS adopted in this study can provide useful insights into the detection of the 10 OPFRs in soil.

Optimization of the Extraction of Bioactive Compounds from Cabernet Sauvignon Grape Pomace from Querétaro, Mexico, Using MSPD

Red wine contains polyphenols which are extracted during the winemaking process. However, winemaking is not an extraction; therefore, the resulting byproducts still have a substantial polyphenol content. The aim of this study was to compare two methods for the extraction of phenolic compounds: maceration and matrix solid-phase dispersion (MSPD). Grape pomace (Vitis vinifera var. Cabernet Sauvignon) from a winery in Querétaro, Mexico was used. The optimal conditions for both methods were identified. Phenolic compounds and antioxidant activity were the response variables. A central composite design was used (Minitab 17) for the extraction by maceration. The maceration time (1, 4, 12, 20, and 24 h) and the ratio of ethanol (50 to 80%) acidified with 1% HCl were the two factors studied. For the MSPD extraction, sea sand was used as a dispersant, and a 22 factorial design was employed for the evaluation, with the elution volume and the ratio of sample/dispersant being the two factors analyzed. The optimal extraction method was MSPD with 96 mL (acidified ethanol) as the elution volume and a 1:2 ratio of sample/dispersant. Using these conditions, 14.01 ± 0.19 mMol TEAC/100 g db (Trolox equivalent of antioxidant capacity) of grape pomace was obtained, whereas the total phenolic content was 2836.73 ± 41.90 mg GAE/100 g db. These values are greater than those obtained by maceration. These conditions are close to those predicted by the model (analysis of variance (ANOVA) with a level of significance of 5% (p &lt; 0.05) and a Tukey comparison test for determining significant differences in the comparison of results).