Matrix Solid-phase Dispersion Extraction Research Articles

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.

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.

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.

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 < 0.05) and a Tukey comparison test for determining significant differences in the comparison of results).

Valorization of Defatted Cherry Seed Residues from Liquor Processing by Matrix Solid-Phase Dispersion Extraction: A Sustainable Strategy for Production of Phenolic-Rich Extracts with Antioxidant Potential.

The integrated valorization of food chain waste is one of the most promising alternatives in the transition to a sustainable bioeconomy. Thus, an efficient solid-phase matrix dispersion extraction method, using experimental factorial design and response surface methodology, has been developed and optimized for the recovery of polyphenols from defatted cherry seeds obtained after cherry liquor manufacture and subsequent fatty acid extraction, evaluating the effect of each processing step on the composition and phenolic content of sweet cherry residues. The phenolic extracts before fermentation showed the highest content of total polyphenols (TPC) and flavonoids (TFC) (3 ± 1 mg QE·g-1 and 1.37 ± 0.08 mg GAE·g-1, respectively), while the highest antioxidant capacity was obtained in the defatted seed extracts after both fermentation and distillation. In addition, high-performance liquid chromatography coupled to a quadrupole time-of-flight mass spectrometer (HPLC-ESI-QTOF-MS) was used to determine the phenolic profile. Dihydroxybenzoic acid, neochlorogenic acid, caffeic acid, and quercetin were the main phenolics found, showing differences in concentration between the stages of liquor production. The results underline the prospective of cherry by-products for obtaining phenol-rich bioactive extracts for possible use in different industrial sectors, offering a feasible solution for the cascade valorization of cherry agri-food waste.

A rapid and eco-friendly method for determination of dictamnine, obacunone, and fraxinellone in Cortex Dictamni by LC–MS and matrix solid-phase dispersion extraction

This study develops a rapid and eco-friendly liquid chromatography–mass spectrometry method for determining dictamnine, obacunone, and fraxinellone in Cortex Dictamni. The samples were extracted by matrix solid-phase dispersion extraction with ethanol. The liquid chromatography separation was operated on an Agilent InfinityLab Poroshell 120 EC-C18 column (2.1 mm × 30 mm, 2.7 μm) using 45% ethanol at a 0.3 mL/min flow rate. Mass spectrometry detection was set at positive ion mode, and the selected ion monitoring mode was used to record the target compounds: dictamnine (mass-to-charge ratio 200), obacunone (mass-to-charge ratio 455), and fraxinellone (mass-to-charge ratio 233). The calibration curves exhibited good linearity (R > 0.9994) within the test range. The intra-day precision was 0.601% for dictamnine, 1.03% for obacunone, and 0.898% for fraxinellone. The recoveries were 100% for dictamnine, 101% for obacunone, and 96.2% for fraxinellone. Six samples were analyzed, and they all conformed to the content requirements of the Chinese Pharmacopeia. Notably, the developed method only requires 6.07 mL ethanol and costs 12 min. This study presents a rapid and eco-friendly analytical method for determining three components in Cortex Dictamni, which will help improve the quality evaluation technology of Cortex Dictamni.

Simultaneous Extraction and Determination of Lignans from Schisandra chinensis (Turcz.) Baill. via Diol-Based Matrix Solid-Phase Dispersion with High-Performance Liquid Chromatography.

The quality of Schisandra chinensis (Turcz.) Baill. (S. chinensis) is principally attributed to lignan compounds. In this paper, a simple and rapid strategy for simultaneous extraction and determination of 10 lignans from S. chinensis was established through matrix solid-phase dispersion (MSPD) assisted by diol-functionalized silica (Diol). The experimental parameters for MSPD extraction were screened using the response surface methodology (RSM). Diol (800 mg) was used as a dispersant and methanol (MeOH, 85%, v/v) as an eluting solvent (10 mL), resulting in a high extraction efficiency. MSPD extraction facilitated the combination of extraction and purification in a single step, which was less time-consuming than and avoided the thermal treatment involved in traditional methods. The simultaneous qualification and quantification of 10 lignans was achieved by combining MSPD and high-performance liquid chromatography (HPLC). The proposed method offered good linearity and a low limit of detection starting from 0.04 (schisandrin C) to 0.43 μg/mL (schisantherin B) for lignans, and the relative standard deviation (RSD, %) values of precision were acceptable, with a maximum value of 1.15% (schisantherin B and schisanhenol). The methodology was successfully utilized to analyze 13 batches of S. chinensis from different cultivated areas of China, which proved its accuracy and practicability in the quantitative analysis of the quality control of S. chinensis.

Investigation of the spatial distribution of airborne polycyclic aromatic hydrocarbons using Rhytidiadelphus squarrosus in Tórshavn, Faroe Islands.

Due to adverse effects of Polycyclic Aromatic Hydrocarbons (PAHs) on human health, it is important to understand how airborne PAHs, are spatially distributed within urban areas. Moss has been shown to be a suitable material for biomonitoring of airborne PAH pollution. In this study, the moss Rhytidiadelphus squarrosus was sampled throughout Tórshavn, Faroe Islands. 53 Rhytidiadelphus squarrosus samples were extracted using a matrix solid-phase dispersive extraction method and analysed for 19 parent PAHs and six groups of alkylated PAHs using gas chromatography mass-spectrometry. All PAHs were quantified in at least one Rhytidiadelphus squarrosus sample, and the sum of the EPA 16 PAHs (ƩPAHEPA16) ranged from 0.90 to 344µgkg-1 dry weight. Higher concentrations were found close to the harbour and the main roads. The spatial correlation was investigated for the ƩPAHEPA16, pyrene, fluoranthene, chrysene, benzo(e)pyrene, benzo(g,h,i)perylene, C1-phenanthrenes/C1-anthracenes, and C2-phenanthrenes/C2-anthracenes using variograms. The effective range of the spatial correlation was between 500 to 700m of all PAHs. The evaluation of diagnostic ratios of fluoranthene to pyrene, and benzo(a)anthracene to chrysene suggest that different pollution sources affect urban areas of different types. To the best of our knowledge, this is the first time airborne PAH pollution patterns were mapped in an Arctic town, and the first time, Rhytidiadelphus squarrosus was used for tracing PAH pollution sources. Rhytidiadelphus squarrosus is suitable for biomonitoring and mapping PAH pollution within urban areas since it is widespread, and suitable for mapping PAHs.

A novel strategy by combining “magnified” matrix solid phase dispersion extraction with high-speed countercurrent chromatography for the rapid and efficient isolation of flavonoids isomers with anti-inflammatory effect from Lindera aggregata (Sims) Kosterm Leaves

A rapid and efficient isolation strategy by combining matrix solid phase dispersion extraction (MSPD) with high-speed countercurrent chromatography (HSCCC) had been proposed in this study for the separation of four flavonoids with anti-inflammatory effect in high edible value plant food, leaves of Lindera aggregata (Sims) Kosterm (L.aggregata-L). MSPD was firstly developed as an efficient extraction methodology to obtain a “clean” extract for the purpose of further isolation of target compounds. Then, two runs of HSCCC isolation were consecutively performed on MSPD extract to purify the target compounds, in which an environmental-friendly biphasic solvent system composed of ethyl acetate-n-butanol-0.05 mol/L of phosphate buffer (pH 3.16) containing 0.05 mol/L of hydroxypropyl-β-cyclodextrin (HP-β-CD) was established for the successful separation of the flavonoids isomers, for the first time. As a result, 21.3 mg of quercetin-3-O-rhamnopyranoside (purity of 96%), 18.7 mg of kaempferol-7-O-α-l-rhamnopyranoside (purity of 89%), 5.5 mg of quercetin-3-O-β-D-glucoside (purity of 90.3%) and 6.4 mg of quercetin-5-O-β-D-glucoside (purity of 86.4%) were obtained from 5 g plant materials. Further cellular assays (RAW264.7 mouse macrophage cells) revealed that the isomers demonstrated good anti-inflammatory activities, of which quercetin-5-O-β-D-glucoside exhibited better anti-inflammatory effect (330% higher than quercetin-3-O-β-D-glucoside at the concentration of 25 μM) but lower cytotoxicity (50% lower than quercetin-3-O-β-D-glucoside at the concentration of 400 μM). In summary, this research indicated a promising isolation strategy of natural compounds which would provide a solid surport for the subsequent further study and development of L. aggregata-L.

Simultaneous determination of five lignans from Schisandra chinensis by matrix solid-phase dispersion extraction-high performance liquid chromatography

The kidney-shaped, red-colord fruit from the plant, Schisandra chinensis (Turcz.) Baill, which belongs to the Schisandraceae family, is among the most popular remedies used in traditional Chinese medicine. The English name of the plant is "Chinese magnolia vine". It has been used in Asia since ancient times to treat a variety of ailments, including chronic cough and dyspnea, frequent urination, diarrhea, and diabetes. This is because of the wide range of bioactive constituents, such as lignans, essential oils, triterpenoids, organic acids, polysaccharides, and sterols. In some cases, these constituents affects the pharmacological efficacy of the plant. Lignans with a dibenzocyclooctadiene-type skeleton are considered to be the major constituents and main bioactive ingredients of Schisandra chinensis. However, because of the complex composition of Schisandra chinensis, the extraction yields of lignans are low. Thus, it is particularly important to study pretreatment methods used during sample preparation for the quality control of traditional Chinese medicine. Matrix solid-phase dispersion extraction (MSPD) is a comprehensive process involving destruction, extraction, fractionation, and purification. The MSPD method is simple, it requires only a small number of samples and solvents, it does not require any special experimental equipments or instruments, and it can be used to prepare liquid, viscous, semi-solid, solid samples. In this study, a method combining matrix solid-phase dispersion extraction with high performance liquid chromatography (MSPD-HPLC) was established for the simultaneous determination of five lignans (schisandrol A, schisandrol B, deoxyschizandrin, schizandrin B, and schizandrin C) in Schisandra chinensis. The target compounds were separated on a C18 column with a gradient elution of 0.1% (v/v) formic acid aqueous solution and acetonitrile as the mobile phases, and detection was performed at a wavelength of 250 nm. First, the effects of 12 adsorbents, including silica gel, acidic alumina, neutral alumina, alkaline alumina, Florisil, Diol, XAmide, Xion, and the inverse adsorbents, C18, C18-ME, C18-G1, and C18-HC, on the extraction yields of lignans were investigated. Second, effects of the mass of the adsorbent, the type of eluent, and volume of eluent on the extraction yields of lignans were investigated. Xion was chosen as an adsorbent for MSPD-HPLC analysis of lignans from Schisandra chinensis. Optimization of the extraction parameters showed that the MSPD method had a high lignan extraction yield with Schisandra chinensis powder (0.25 g) as a fixed value, Xion as the adsorbent (0.75 g), and methanol as the elution solvent (15 mL). Analytical methods were developed for five lignans from Schisandra chinensis and these methods showed good linearity (correlation coefficients (R2)≥ 0.9999) for each target analyte. The limits of detection and quantification ranged from 0.0089 to 0.0294 μg/mL and 0.0267 to 0.0882 μg/mL, respectively. Lignans were tested at low, medium, and high levels. The average recovery rates were 92.2% to 111.2%, and the relative standard deviations were 0.23% to 3.54%. Both intra-day and inter-day precisions were less than 3.6%. Compared with hot reflux extraction and ultrasonic extraction methods, MSPD has the advantages of combined extraction and purification, being less time-consuming, and requiring lower solvent volumes. Finally, the optimized method was successfully applied to analyze five lignans from Schisandra chinensis samples from 17 cultivation areas.

Simultaneous extraction and determination of alkaloids and organic acids in Uncariae Ramulas Cum Unicis by vortex-assisted matrix solid phase dispersion extraction coupled with UHPLC-MS/MS.

A simple and efficient vortex-assisted matrix solid phase dispersion with a ultra-high-performance liquid chromatography-triple quadrupole mass spectrometer (VA-MSPD-UHPLC-MS/MS) was applied for simultaneous extraction and determination of seven alkaloids and three organic acids from Uncariae Ramulas Cum Unicis. The optimal extraction conditions of the target components were obtained by Box-Behnken design (BBD) combined with response surface methodology (RSM). The results of the method validation showed that this analytical method displayed good linearity with a correlation coefficient (r) no lower than 0.9990. The recoveries of ten active ingredients from Uncariae Ramulas Cum Unicis ranged from 95.9% to 103% (RSD ≤ 2.77%). The RSDs of intra-day and inter-day precisions were all below 2.97%. The present method exhibited not only lower solvent and sample usage, but also shorter sample processing and analysis time. Consequently, the developed VA-MSPD-UHPLC-MS/MS method could be successfully and effectively used for the extraction and analysis of ten active components from Uncariae Ramulas Cum Unicis.

An integrated strategy for characterization of chemical constituents in Stephania tetrandra using LC–QTOF–MS/MS and the target isolation of two new biflavonoids

LC–MS has been a widely used analytical technique for identification of natural compounds. However, sophisticated and laborious data analysis is required to identify chemical components, especially new compounds, from a large LC–MS dataset. The aim of this study is to develop an integrated data-mining strategy that combines molecular networking (MN), in-house polygonal mass defect filtering (MDF), and diagnostic fragment ion filtering (DFIF) to identify phytochemicals in Stephania tetrandra based on LC–MS data. S. tetrandra samples were prepared by matrix solid-phase dispersion extraction methods and then raw MS spectra were acquired using LC–QTOF–MS/MS. MN and in-house polygonal MDF classified the compounds roughly. Modified DFIF were then used in succession to place each spectrum into a specific class. Finally, the exact structures were deduced by fragmentation pathways and related botanical biogenesis, with the help of the narrowed classification from MN and MDF. The total workflow was a combination of data filtering and identification methods for rapid characterization of known compounds (dereplication) and discovery of new compounds. Consequently, 144 compounds were identified or tentatively identified in the aerial parts and roots of S. tetrandra, including 11 potentially new compounds and 63 compounds first identified in this species. Among 144 compounds, 61 were from the aerial parts exclusively, 8 were from the roots exclusively, and 75 were found in both parts. Furthermore, two new biflavonoids were isolated with the guide of LC–MS analysis and structurally elucidated by spectroscopic methods. In conclusion, the proposed data-mining strategy based on LC–MS can be used to profile chemical constituents with high efficiency and guide the isolation of new compounds from medicinal plants. The comparison of the components of the aerial parts and roots of S. tetrandra would be helpful for the rational utilization of the medicinal plant.

Recent Advances in Molecularly Imprinted Polymers for Antibiotic Analysis.

The abuse and residues of antibiotics have a great impact on the environment and organisms, and their determination has become very important. Due to their low contents, varieties and complex matrices, effective recognition, separation and enrichment are usually required prior to determination. Molecularly imprinted polymers (MIPs), a kind of highly selective polymer prepared via molecular imprinting technology (MIT), are used widely in the analytical detection of antibiotics, as adsorbents of solid-phase extraction (SPE) and as recognition elements of sensors. Herein, recent advances in MIPs for antibiotic residue analysis are reviewed. Firstly, several new preparation techniques of MIPs for detecting antibiotics are briefly introduced, including surface imprinting, nanoimprinting, living/controlled radical polymerization, and multi-template imprinting, multi-functional monomer imprinting and dummy template imprinting. Secondly, several SPE modes based on MIPs are summarized, namely packed SPE, magnetic SPE, dispersive SPE, matrix solid-phase dispersive extraction, solid-phase microextraction, stir-bar sorptive extraction and pipette-tip SPE. Thirdly, the basic principles of MIP-based sensors and three sensing modes, including electrochemical sensing, optical sensing and mass sensing, are also outlined. Fourthly, the research progress on molecularly imprinted SPEs (MISPEs) and MIP-based electrochemical/optical/mass sensors for the detection of various antibiotic residues in environmental and food samples since 2018 are comprehensively reviewed, including sulfonamides, quinolones, β-lactams and so on. Finally, the preparation and application prospects of MIPs for detecting antibiotics are outlined.

Natural Deep Eutectic Solvent-Based Matrix Solid Phase Dispersion (MSPD) Extraction for Determination of Bioactive Compounds from Sandy Everlasting (Helichrysum arenarium L.): A Case of Stability Study.

In the present study, vortex-assisted matrix solid-phase dispersion (VA-MSPD) extraction was used to isolate the major bioactive compounds from H. arenarium. To reduce the negative environmental impact of the conventionally used organic solvents, four different choline chloride-based natural deep eutectic solvents (NADES) were investigated as possible eluents. The most influential VA-MSPD extraction parameters: stationary phase (adsorbent), adsorbent/sample ratio, vortex time, and volume of extraction solvent were systematically optimized. Ultrasound-assisted extraction with 80% MeOH was used as the standard method for the comparison of results. The stability of the obtained extracts was studied over a period of 0 to 60 days at three different temperatures (-18 °C, 4 °C, and 25 °C). All extracts were evaluated both spectrophotometrically (determination of total phenolic content (TPC) and antioxidant activity by ABTS and FRAP assay) and chromatographically (HPLC-UV). NADES based on choline chloride and lactic acid (ChCl-LA) was selected as the most effective extractant, with a determined TPC value of its extract of 38.34 ± 0.09 mg GA/g DW (27% higher than the methanolic VA-MSPD extract) and high antioxidant activity. The content of individual phenolic compounds (chlorogenic acid, dicaffeoylquinic acid isomers, naringenin isomers, and chalcones) in the ChCl-LA extract, determined by HPLC-UV, was comparable to that of the conventionally obtained one. Moreover, the stabilization effect of ChCl-LA was confirmed for the studied compounds: chlorogenic acid, naringenin-4'-O-glucoside, tomoroside A, naringenin-5-O-glucoside, isosalipurposide, and naringenin. The optimum VA-MSPD conditions for the extraction of H. arenarium polyphenols were: florisil/sample ratio of 0.5/1, a vortex time of 2 min, and an elution volume of ChCl-LA of 10 mL.

An ultra-rapid and eco-friendly method for determination of loganic acid and gentiopicroside from Gentianae Macrophyllae Radix by vortex-assisted matrix solid-phase dispersion extraction and LC-MS

An ultra-rapid and eco-friendly method for the determination of loganic acid and gentiopicroside in Gentianae Macrophyllae Radix (GMR) was developed by vortex-assisted matrix solid-phase dispersion extraction (VAMSPD) and liquid chromatography with mass spectrometry (LC-MS). The optimized VAMSPD parameters are as follow: sample-dispersant (diatomaceous earth) ratio is 1:5, grinding for 0.5 min and whirling with 0.5 mL 15 % ethanol for 0.5 min. The LC separation is performed on a Poroshell 120 EC-C18 column (30 ×2.1 mm, 2.7 µm) and eluted by an eco-friendly mobile phase (14 % ethanol containing 0.1 % formic acid) at a flow rate of 0.5 mL min−1 in isocratic mode, and detected by mass spectrometry (MS). The developed method exhibits a good linearity for the analytes (r > 0.9990). The RSDs of precision and repeatability are less than 4.0 %, the recoveries for loganic acid and gentiopicroside are 106.5 % (RSD=3.6 %) and 95.7 % (RSD=8.0 %), respectively. The developed method was successfully applied in the analysis of loganic acid and gentiopicroside in GMR samples. The total analysis time is 2 min, including 1 min for sample extraction and 1 min for LC-MS analysis. In addition, the method only requires 0.3 mL of ethanol.

Screening the extraction process of phenolic compounds from pressed grape seed residue: Towards an integrated and sustainable management of viticultural waste

The integrated valorisation of waste from the food chain to obtain value-added compounds with biological functionality will facilitate the transition to the era of a sustainable bioeconomy. To this end, an efficient matrix solid-phase dispersion (MSPD) extraction method was developed and optimized, using experimental factorial design and response surface methodology, for polyphenols recovery from pressed grape seeds obtained after the extraction of essential oils by cold pressing. Gallic, dihydroxybenzoic, p-coumaric and trans-ferulic acid, naringin, resveratrol, quercetin and kaempferol were quantified at 2.1–295 μg g−1 by capillary liquid chromatography coupled to a diode array detector and a mass analyser (cLC-DAD-MS). Furthermore, total antioxidant activity, free radical scavenging and lipid peroxidation suppression, together with the inhibition of beta-amyloid (Αβ42) protein aggregation, considered one of the main pathological effects of Alzheimer's disease, were evaluated. Potent lipid peroxidation inhibition (IC50 0.238 ± 0.003 ng g−1) was observed, along with the reduction of Αβ42 fibril width (9.4–54.8%) and aggregation. The results presented proved that the MSPD extraction method could be considered as an efficient and sustainable methodology to produce phenolic-rich extracts that may serve as an alternative antioxidant and neuroprotective ingredient for the food or pharmaceutical formulations, leading to the cascade valorisation of winery by-products.

Optimization of Microwave-Assisted Extraction and Matrix Solid-Phase Dispersion for the Extraction of Polyphenolic Compounds from Grape Skin

Polyphenols are organic compounds that can be found in food, especially in fruits, vegetables, and their products. It was shown that their presence significantly affects the properties of food products and that the consumption of food rich in phenolic compounds has a beneficial effect on human health. The subjects of this research were polyphenols: anthocyanins, flavonols, and flavan-3-ols in the skin of grapevine variety Regent. Polyphenols from grape skins were extracted via microwave-assisted extraction (MAE) and matrix solid-phase dispersion (MSPD) as unconventional and green techniques. Therefore, the main aim of this work was to optimize the conditions for the extraction of polyphenolic compounds from grape skin using MAE and MSPD. The extracts were analyzed using high-performance liquid chromatography with a diode array detector and fluorescence detector. Analyses showed that MAE was a very effective method for extracting polyphenolic compounds from grape skin with 10 mL of 60% ethanol for 5 min at 40 °C. The best results for the MSPD extraction of polyphenolic compounds from grape skin were obtained with phenyl as an MSPD sorbent with 10 mL of acetonitrile:water 50:50 v/v as an elution solvent. This scientific research can be used for the better use of grapes as a basis for obtaining flavonoids for commercial purposes.

Chitosan-based matrix solid-phase dispersion extraction assisted cell membrane magnetic bead ligand-affinity assay for screening active compounds from Fructus Cnidii.

Cell membrane ligand-affinity assay is a useful tool for screening the active compounds from natural products. However, in traditional cell membrane ligand-affinity assays, natural products need to be refluxed, before being analyzed. This process consumes considerable time and energy and cannot be used for screening natural products that contain thermally unstable compounds. Therefore, an efficient analytical method is required. In this study, chitosan-based matrix solid-phase dispersion extraction was combined with cell membrane magnetic bead ligand-affinity assay to form a novel method for identifying the active compounds in Fructus Cnidii such as osthole and imperatorin. When compared with traditional cell membrane ligand-affinity assays, this assay requires less energy, extraction time (7min), solvent volume (1.2mL), and fewer natural products (40mg). This indicates that the chitosan-based matrix solid-phase dispersion extraction assisted cell membrane magnetic beads ligand-affinity assay is an alternative analytical method for studying natural products.

Determination of multiclass pesticides in river sediments via matrix solid-phase dispersion extraction and gas chromatography-tandem mass spectrometry.

A fast and environment-friendly analytical method was implemented to determine multiclass pesticides in river sediments. Twenty-three pesticides-organochlorine pesticides, organophosphorus pesticides, and triazines-were extracted via matrix solid-phase dispersion (MSPD) and analyzed by gas chromatography-tandem mass spectrometry (GC-MS/MS). Florisil demonstrated excellent analytes uptake capability as the extractant phase, with suitable selectivity for treating complex sediment samples. Under defined extraction conditions, the MSPD-GC-MS/MS method demonstrated robustness in the n inter-day analysis of sediments from different sources, providing limit of quantifications (LOQs) between 5 and 15ng/g, linear responses in the range between LOQs and 150ng/g, extraction recoveries of 71%-106%, and precision, assessed as relative standard deviation below 20%. The MSPD significantly reduced samples and solvents' consumption, providing critical environmental gains compared to traditional extraction methods like Soxhlet. Finally, the method was applied to analyze sediment samples from three different collection areas of the Subachoque River (Cundinamarca, Colombia), demonstrating a fast, efficient, confident, and profitable analytical tool for pollution control and monitoring in environmental samples. The method allowed us to determine the current use in Colombia of banned pesticides under the 2001 Stockholm Convention.