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Matrix solid phase dispersion (MSPD) is a rapid and flexible sample pretreatment method that accomplishes sample disruption, extraction, filtering and purification in one step and is especially suitable for solid, semisolid and viscous samples. More than 30 years have elapsed since it was first proposed, and there are many published reviews. However, there is no review on the use of MSPD to extract active compounds from natural products. In this review, the latest developments from 2015–2021 in MSPD microextraction techniques, including sorbents, elution solvents and assisted MSPD extraction, along with their applications in natural products, are systematically discussed and classified according to the structure of the active constituents, which mainly refer to phenolic acids, flavonoids, alkaloids, anthraquinones and terpenes. [ABSTRACT FROM AUTHOR]

The mixed enzymes-assisted mechanical bio-extraction method was first used to extract polysaccharides from Dendrobium officinale. Different parameters including the ratio of enzyme, the amount of enzyme, the grinding time, the extraction time and the solid/liquid ratio were investigated by single factor experiments and multifactorial experiments. Through the response surface methodology the optimal extraction conditions were obtained with the ratio of cellulase to pectinase was 2: 1 and total amount of enzyme was 0.23 mg, the grinding time of 11.48 min, the extraction time of 5.99 min. The obtained polysaccharide extracts were hydrolyzed and derivatized and then injected into high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC-Q-TOF/MS) for monosaccharide composition analysis. After optimization of the chromatographic conditions (including mobile phase and column), twelve monosaccharides were successfully determined within 20 min. The proposed method provided satisfactory linearity with the correlation coefficients higher than 0.99, suitable recoveries (81.46–114.92 %), acceptable reproducibility ranging from 0.06 % to 4.77 %, low limits of detection (0.70–45.45 ng/mL). Compared with other methods, this method makes the extraction efficiency much higher and has the advantages of simple operation, environmental friendliness and mild extraction conditions. Therefore, this method can be used for the extraction of polysaccharides from plants and the determination of monosaccharides and has the potential to be used in more areas. [ABSTRACT FROM AUTHOR]

[Display omitted] • On-line sandwich derivatization and stacking by CE were developed. • Multi-amino acids were simultaneously preconcentrated. • Application to soybean and Dendrobium officinale with good recovery. • The enrichment factors of nine amino acids increased 8 to 62-fold. An online sandwich derivatization and stacking strategy using capillary electrophoresis was developed and successfully applied to the preconcentration of multi-amino acids in two functional food samples. Amino acids were derived with 4-Chloro-7-nitro-1, 2, 3-benzoxadiazole (NBD-Cl) to make the new compounds with chromophore in the stacking process, then the derivatives were stacked by on-column sample preconcentration and detected at 475 nm UV wavelength. The novel sandwich injection sequence was amino acids, NBD-Cl, and amino acids separately. Additionally, the running buffer was 40 mM borax buffer (pH = 9.0). A succession of derivatization and stacking conditions were optimized, including buffer concentration, pressure, NBD-Cl injection time, waiting time, matrix concentration, and sample injection time. In the appropriate range, good linearity values (R2) were obtained for nine amino acids at 0.996–0.999. Intra-day and inter-day precision with a relative standard deviation < 6.23 % (n = 5), the limit of detection in the range of 2.8–25.2 μM, and recovery ranging from 83.2 to 108.2 % were obtained. Besides, the enrichment factors were in range of 8–62 for nine AAs. The stacking approach was successfully applied to soybean and Dendrobium officinale samples, which shows great potential in the determination of free amino acids in samples containing complex matrices. [ABSTRACT FROM AUTHOR]

• A mechanically assisted coamorphous dispersion extraction method was developed. • This method successfully extracted hydrophobic compounds from plant tea with water. • Environmental protection and higher extraction efficiency were achieved. This study aimed to establish a novel mechanically assisted coamorphous dispersion extraction (MADE) method for the extraction of hydrophobic compounds (hesperidin, nobiletin and tangeretin) from Citri Reticulatae Pericarpium using water. The surface morphology, particle size distributions, phase states and functional groups of the coground product surface were characterized by Scanning Electron Microscopy, X-ray diffraction and Fourier transform infrared spectroscopy. The parameters affecting the efficiency of extraction method were optimized by single-factor experiments and response surface methodology. The method showed good linear relationships in the range of 1–500 μg/mL with correlation coefficients (R2) ≥ 0.9990, low limits of detection ranging from 3.0 to 28.3 ng/mL, and acceptable recoveries ranging from 87.0 to 91.0%. Therefore, the proposed MADE method is a promising, efficient and organic solvent-free method for the extraction of hydrophobic compounds from plant tea. [ABSTRACT FROM AUTHOR]

Dendrobium has great medicinal value, and their active components vary across different species of Dendrobium. In this study, a two-dimensional ion mobility mass spectrometry point image based on retention time and drift time was first proposed, and the collision cross-section values of Dendrobium metabolites were calculated by the IM browser, which can identify the targeted compounds more accurately, especially for isomeric compounds. During the experimental process, a total of 74 batches of Dendrobium samples containing nine species of Dendrobium were analyzed by ultrahigh-performance liquid chromatography coupled with ion mobility quadrupole-time-of-flight mass spectrometry. Nontargeted plant metabonomics combined with multivariate statistical analysis was used to realize the clustering of different species of Dendrobium , which made the identification more scientific. Therefore, this method can realize the analysis of multiple active components in Dendrobium , can be used for the identification of Dendrobium teas and can provide a reference for the quality control of Dendrobium. • Two-dimensional IM-MS point image technology was first proposed. • UHPLC-IM-Q-TOF MS was first used for the determination of plant teas. • Nontargeted metabonomics was used for the identification of Dendrobium species. [ABSTRACT FROM AUTHOR]

A novel, green and efficient in-situ cloud point-reinforced ionic liquid-assisted mechanochemical extraction (IS-CPR-IL-MCE) technique coupled with ultrahigh performance liquid chromatography was established to simultaneously extract, concentrate and separate five alkaloids (including liensinine, isoliensinine, neferine, O-demethyl nuciferine and nuciferine) from lotus leaf. The parameters affecting the extraction efficiency of target analytes, such as the amount of IL, surfactant and salt, grinding time, pH, enrichment temperature and time were systematically studied and optimized by single-factor and multifactor experiments. The highest extraction yield of alkaloids was obtained by IS-CPR-IL-MCE under the following conditions: 0.23 g of 1-dodecyl-3-methylimidazolium bromide, 0.37 g of Triton X-100, 7.73 of pH, 5 min of milling time, 2.5 g of (NH 4) 2 SO 4 , 60 ℃ and 20 min of enrichment temperature and time. The developed method exhibited a good linearity in the range of 0.5–100.0 μg/mL with the coefficients of correction more than 0.9992, low limit of detection of 8.0–11.2 ng/mL, acceptable reproducibility below 4.45%, and satisfactory recovery in the range of 80.4–93.7% The results demonstrated that the proposed method was successfully applied to the extraction of alkaloids from lotus leaf. • An ionic liquid assisted mechanochemical extraction was developed. • This method was reinforced by in-situ cloud point extraction. • This method was suitable for simultaneous extraction and enrichment of alkaloids. • Environmental protection, efficient extraction and good repeatability were achieved. [ABSTRACT FROM AUTHOR]

• A biosurfactant-assisted mechanical amorphous dispersion extraction was developed. • Salvia miltiorrhiza samples were mechanically ground with sodium chenodeoxycholate. • Simultaneous extraction of hydrophilic and hydrophobic analytes was achieved. • The method obtained high extraction efficiency under organic solvent-free conditions. A biosurfactant-assisted mechanical amorphous dispersion extraction (BA-MADE) procedure was established for the simultaneous capture of hydrophilic phenolic acids and hydrophobic tanshinones from Salvia miltiorrhiza. Single-factor experiments and the response surface methodology were used to optimize and analyze the crucial parameters for the method, such as the type and amount of amorphous-dispersion extractants, grinding time, extraction time and solid-to-liquid ratio. The optimized parameter values for the BA-MADE process were 407.02 mg of sodium chenodeoxycholate, a grinding time of 4.87 min, an extraction time of 4.92 min, and a solid-to-liquid ratio of 0.5:10 g/mL. The calibration curves of danshensu, rosmarinic acid, lithospermic acid, salvianolic acid B, salvianolic acid A, dihydrotanshinone I, cryptotanshinone, tanshinone I, and tanshinone II A exhibited good linearity in the range of 1–500 μg/mL (R2 ≥ 0.9990). The limits of detection of nine analytes ranged from 5.46 to 130 ng/mL, the relative standard deviations (RSDs) of intraday and interday precision were less than 1.95 and 3.56%, respectively, and the recoveries of the real sample were in the range of 85–113%, with RSD% below 3.21%. The BA-MADE method was compared with previously reported methods, such as heating reflux extraction, ultrasonic extraction and microwave-assisted micellar extraction, and the results demonstrated that the developed method has significant advantages in the simultaneous extraction of hydrophilic and hydrophobic active components from Salvia miltiorrhiza. [ABSTRACT FROM AUTHOR]

[Display omitted] • An in-situ formation of ion pair assisted LLME method was developed. • This method was suitable for the separation of highly ionized basic compounds. • The proposed method was optimized by single-factor and multi-factor experiments. • Higher extraction efficiency, better reproducibility and environmental protection were achieved. A simple and rapid method for the determination of microsacle natural alkaloids, being based on the reaction of in-situ formation of ion pair assisted liquid–liquid microextraction (LLME) was established. Microsacle alkaloids and acid dyes formed ion pairs online, which were easily extracted by bonding reagent at an appropriate pH, so as to realize the enrichment and determination of alkaloids. The experimental parameters such as pH value, vortex time, dye types, amount of dye and solvent types were investigated and optimized. Under the optimum conditions, good linear relationships (R2 ≥ 0.9995) were obtained, the detection limits of the proposed method were between 8.9 and 16.7 ng/mL, and the average recoveries of four alkaloids ranged from 87.20 to 102.50%. These results demonstrated that the LLME procedure was a potential method for the separation and determination of alkaloids from natural medicinal materials. [ABSTRACT FROM AUTHOR]

In this study, a simple, high-efficiency and eco-friendly enrichment method using an ionic liquid (IL)-assisted aqueous two-phase system was proposed for the enrichment of multiple monosaccharides. The parameters affecting the enrichment effect were the type of IL, the mass of the IL, the amount of salt, the vortex time, and the pH value of the solution. All of these parameters were optimized using single-factor tests or multifactor experiments. The optimal conditions were as follows: [C 4 min]Br was 313.49 mg, the mass of K 2 HPO 4 was 4.6 g, the vortex time was 3.18 min, and the pH value was 9. In addition, the established method was verified to have good linearity (r2 ≥ 0.9991) and high sensitivity, with limits of detection ranging from 6.1 to 34.09 ng/mL and limits of quantification ranging from 20.57 ng/mL to 113.63 ng/mL. Spiked samples had recoveries ranging from 85.68 % to 104.83 %. The present work demonstrated that this established method can be successfully used for the extraction and enrichment of various monosaccharides from jujube. [Display omitted] • An ionic liquid-assisted aqueous two-phase system enrichment method was established. • Ultrasonic extraction combined with aqueous two-phase system was used. • This method was suitable for the enrichment of multiple monosaccharides from jujube. • Environmental protection, efficient extraction and good repeatability were achieved. [ABSTRACT FROM AUTHOR]

[Display omitted] • A carbon black-assisted miniaturized solid phase extraction method was established. • Carbamate residues were determined by SFC-IM-Q-TOF/MS. • The CCS values of carbamate pesticides were accurately measured for identification. • This method was highly efficient, highly sensitive and environmentally friendly. In this study, the qualitative and quantitative analysis of carbamate pesticide residues was achieved by a miniaturized solid phase extraction (SPE) method and supercritical fluid chromatography (SFC) combined with ion mobility quadrupole time-of-flight mass spectrometry (IM-Q-TOF/MS). The target compounds in real samples were enriched using the miniaturized SPE method, and the parameters affecting enrichment efficiency were evaluated with the optimal enrichment conditions as follows: carbon black (20 mg) and methanol used as the elution solvent with a volume of 200 µL. Meanwhile, the back temperature, back pressure and make-up solvent in SFC were investigated, and the corresponding optimal conditions were 60 °C, 140 bar and methanol with 0.1% formic acid, respectively. Subsequently, accurate mass values of nine carbamate pesticides were identified by IM-Q-TOF/MS. Through method validation and sample analysis, the results indicated that satisfactory validation parameters, such as linearity (R2 > 0.99), limit of detection (<7.01 ng/mL), limit of quantitation (<23.36 ng/mL), precision (0.21–3.91%) and reproducibility (0.08–4.76%), were obtained. Finally, this method was successfully applied to the enrichment and detection of carbamate residues in real samples of ginger. [ABSTRACT FROM AUTHOR]

• Electrokinetic sampling-assisted MSS in coated tubing for CE was developed. • Zwitterionic surfactant served as a micellar solution in the MSS. • The enrichment factors of compounds increased 840- to 3820-fold. • A highly sensitive technique for As detection in kelp and rice samples is proposed. An effective and sensitive two-step stacking of arsenic species by electrokinetic injection and micelle-to-solvent stacking (MSS) using zwitterionic surfactant 3-(N,N-dimethylpalmitylammonio) propane sulfonate was successfully developed in a co-electro-osmotic flow (co-EOF) capillary zone electrophoresis (CZE). The fused silica capillaries were coated with 1% hexadimethrine bromide solution to satisfy the condition of the same EOF direction between the test anions and capillary. The background solution was 100 mM borax buffer (pH 9.2). The proposed method was performed by a CZE system equipped with a diode array detector, and the detection wavelength was monitored at 192 nm. The separation voltage was −20 kV. The group of micelles and target analytes was stacked by field-enhanced sample injection at −10 kV for 180 s. The second stacking step used 60% MeOH to serve as an organic solvent where the analytes were brought by the micelles to the MSS boundary. The enrichment factors of As(Ⅴ), As(Ⅲ), disodium methyl arsonate hexahydrate (MMA), and dimethylarsinic acid (DMA) were 1230, 840, 3820, and 1450, respectively, compared to typical injections in CZE. The limits of detection (S/N = 3) ranged from 0.382 to 0.911 ng mL−1. The intracapillary repeatabilities (%RSD, n = 3) were 0.5–1.0% for migration time and 0.3–0.7% for peak areas. The technology of two-step stacking by MSS in co-EOF CZE together with a simple extraction procedure for As(Ⅴ), As(Ⅲ), MMA and DMA were demonstrated in kelp and rice samples. [ABSTRACT FROM AUTHOR]

• A CE–ESI-Q-TOF-MS method was developed for analysis of natural flavonoids. • HCA and PLS-DA were applied for citrus fruits differentiation. • The proposed method is rapid, efficient, economical. A rapid, efficient and simple method using capillary electrophoresis-electrospray ionization-quadrupole time-of-flight mass spectrometry (CE-ESI-Q-TOF-MS) was developed for the determination of the eight flavonoids (schaftoside, rutin, hesperidin, naringenin, naringin, violanthin, hesperitin and kaempferol) in 23 citrus samples. CE and ESI-Q-TOF conditions (e.g. nebulizer gas pressure, drying gas flow rate and temperature, sheath liquid composition, BGE composition and pH) were studied to obtain an optimal analytical identification and separation. The linear calibration was investigated ranged from 10 to 300 μg/mL for the six analytes, and had a good linearity with correlation coefficient of determination ranged from 0.9901 to 0.9995. The repeatability was tested by intra (n = 3) and the RSDs for migration time and peak area were within 0.43–2.30 % and 13.02–24.60 %, respectively. In addition, 23 investigated citrus samples were classified into 3 clusters according to different recognition program modes hierarchical cluster analysis and partial least squares discriminant analysis based on the peak areas of 8 target components. [ABSTRACT FROM AUTHOR]

A rapid, efficient, and environmentally friendly matrix solid‐phase dispersion microextraction was established to determine and quantify terpenoids in Radix Curcumae using ultra‐high‐performance liquid chromatography with a diode array detector. Various parameters affecting the extraction were investigated in detail, such as the grinding time, amount of adsorbent, type and concentration of elution solvent, and pH. The optimization of single‐factor and response surface methodology was performed to confirm the best conditions in this procedure. The final optimized conditions were obtained by applying 70 mg of cucurbituril as adsorbent, 149 s as the optimum grinding time, and 228 mM of 3‐(N,N‐dimethylpalmitylammonio)propanesulfonate aqueous solution (pH 6.5) as the optimal elution solvent. The validated method showed a satisfactory linear range of 0.10–10 µg/mL for curdione and furanodiene, 0.01–10 µg/mL for isocurcumenol and germacrone, and 0.05–10 µg/mL for furanodienone, while the correlation coefficients ranged from 0.9945 to 0.9970. The recoveries of the investigated analytes at two spiked concentration levels (0.1 and 1.0 µg/mL) ranged from 96.53 to 104.60%. In addition, this method displayed acceptable reproducibility (relative standard deviation ≤ 3.66%). The results showed that the newly proposed matrix solid‐phase dispersion microextraction method was successfully applied to analyze curdione, isocurcumenol, furanodienone, germacrone and furanodiene in Radix Curcumae samples. [ABSTRACT FROM AUTHOR]

[Display omitted] • A plant sorbent assisted mini-SPE method is proposed. • Novel microwave-induced activated carbons was utilized as the plant sorbent in this work. • Activated carbon was prepared by microwave chemical reaction from hawthorn leaves. • The approach was successfully applied in the extraction of multiple pesticide residues in Dendrobium officinale. A simple and green plant sorbent-based miniaturized solid phase extraction (mini-SPE) method was presented for the detection of multi-pesticide residues in Dendrobium officinale by ultra-high performance liquid chromatography combined with quadrupole time-of-flight mass spectrometry. Activated carbons prepared from hawthorn leaves were used as a green sorbent in microwave (MW) assisted mini-SPE process. Various parameters such as the type and concentration of extraction solvent, MW time and MW temperature, were investigated in detail to obtain the optimum conditions in this procedure. Under the final optimized conditions, this method displayed a satisfactory linearity, with its correlation coefficients ranged from 0.9927 to 0.9991. The limits of detection ranged between 0.08 and 1.35 ng/mL for the seven pesticides. And the recoveries of the pesticides in Dendrobium officinale ranged from 81.17 to 106.12% at two spiked levels (0.05 and 5 ug/mL), indicating the accuracy of the proposed mini-SPE method was acceptable. Besides, the reproducibility of the method was satisfactory, with the RSDs lower than 0.37% for retention time, 3.72% for peak area, respectively. The proposed mini-SPE method was efficiently applied for the determination and extraction of the pesticides in Dendrobium officinale, thus demonstrating that this method was reliable. [ABSTRACT FROM AUTHOR]

• An in situ effervescence reaction-assisted MCAE method is proposed. • Ganoderma lucidum samples are mechanically ground with solid acid-base reagents. • Ganoderic acids are extracted by water instead of an organic solvent. • The approach has the advantages of simple operation and high efficiency. The aim of this work was to develop a simple, green and low-consumption method for the extraction of ganoderic acids. An in situ effervescence reaction-assisted mechanochemical extraction method was proposed, and the effects of independent variations in terms of sodium bicarbonate concentration, milling time, and liquid/solid ratio (mL/g) were investigated by means of a response surface methodology (RSM) Box-Behnken design (BBD). The highest yields of ganoderic acids were achieved by grinding a Ganoderma lucidum sample with sodium bicarbonate (372.60 mg/g) and citric acid for 0.87 min with a water to material ratio of 10.58 mL. The linear calibration ranges were from 0.01–5 μg/mL for the six analytes and had good linearity with a correlation coefficient of determination higher than 0.9991. In addition, the obtained LODs of the six target analytes were 1.46 − 2.97 ng/mL, and the LOQs calculated as ten times the signal-to-noise ratio were 4.88 − 9.90 ng/mL. The proposed method was successfully applied to the Ganoderma lucidum samples. [ABSTRACT FROM AUTHOR]

• LC × LC/Q-TOF MS method was applied to determine 19 active constituents in chrysanthemum species. • Principal component analysis was performed to study the clustering of different chrysanthemum species. • Partial least squares discriminant analysis (PLS-DA) was used to establish a classification model. • Hierarchical cluster analysis (HCA) was used to generate a dendrogram for similarity measurement. An effective comprehensive two-dimensional liquid chromatography (LC × LC) coupled with quadrupole time-of-flight mass spectrometry (Q-TOF/MS) method was developed for quantitative determination of 19 active constituents in chrysanthemum species. Separation was achieved on a LC × LC system, with Zorbax Eclipse Plus C18 column (2.1 × 100 mm, 3.5 μm) used in the first dimension (1D), Poroshell 120 Bonus-RP column (3.0 × 50 mm, 2.7 μm) in the second dimension (2D). An optimal flow rate of 0.1 mL/min in 1D combined with 2.0 mL/min in 2D was utilized to improve the resolution and peak shape of the analytes. A synchronized gradient elution program was optimized to make for the 2D chromatographic resolution and the final peak capacity. The established method was then applied for the contents determination of the 19 analytes in all the chrysanthemum samples collected. Based on the content data set of these components, principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA), and hierarchical cluster analysis (HCA) were performed to distinguish the chrysanthemum of different varieties. 29 selected chrysanthemum products were classified into five clusters, with Chuju, Jinzhanju, Taiju and Wanshouju distinguished from each other. However, Hangbaiju, Huangju, Gongju, and Xueju clustered into a group due to their similarities in the analytes content. This study shows that LC × LC/Q-TOF MS in combination with PCA, PLS-DA and HCA can be applied successfully as an effective method for the classification and quality control of chrysanthemum. [ABSTRACT FROM AUTHOR]