Matrix Solid-phase Dispersion Microextraction Research Articles

Polyamide and deep eutectic solvent assisted matrix solid-phase dispersion microextraction for strong hydrophobic compounds

This paper proposes a simple, efficient, and green matrix solid-phase dispersion microextraction (MSPDM) method that uses polyamide as a dispersant and deep eutectic solvent (DES) as an eluant to extract terpenoids and alkaloid compounds from linderae radix. The main extraction parameters, including the amount of dispersant, grinding time, molar ratio of the DES components, type of dispersant, and type of DES, were optimized using single-factor experiments. The response surface methodology and the Box–Behnken design were used for further optimization. Satisfactory linearity (R2 > 0.999), precision (0.018%–2.215%), and accuracy (recovery >80%) were acquired for all target analytes. The results indicate that the developed method is promising and sustainable for extracting active ingredients from natural products.

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.

Nanographite-assisted matrix solid phase dispersion microextraction of active and toxic compounds from complex food matrices using cyclodextrin aqueous solution as elution solvent.

In this study, a cyclodextrin aqueous solution was used as an environmentally friendly eluent to simultaneously extract active and toxic compounds from food matrices with the aid of nanographite-assisted matrix solid phase dispersion microextraction (NG-MSPDM). The NG-MSPDM procedure was optimized by single-factor experiments and response surface methodology to obtain optimum conditions. The proposed method achieved excellent linearity at 0.10-20μg/mL for all target analytes with a coefficient of correction (R2)≥0.9909, limits of detection < 52.01ng/mL, satisfactory reproducibility below 3.21%, and acceptable recoveries of 82.0-112%. To accurately determine the target components in the complex matrix, collision cross-section values of the analytes were obtained using ion mobility quadrupole time-of-flight mass spectrometry (IM-Q-TOF/MS). Results indicated that the NG-MSPDM method successfully achieved the simultaneous extraction of flavonoids and phenoxyacetic herbicides from Alpinia officinarum.

Nano-ZnO-assisted matrix solid phase dispersion microextraction combined with an in situ DES-based aqueous two-phase system for the enrichment of multiple active compounds in honeysuckles

In this work, a novel method of matrix solid phase dispersion-assisted aqueous two-phase system microextraction as sample pretreatment was developed, and ultra-high performance liquid chromatography was used to separate multiple active compounds in honeysuckles. Nano-ZnO was used as the adsorbent for matrix solid phase dispersion microextraction, and green deep eutectic solvents were used as the extraction solvent for enrichment of target analytes in an aqueous two-phase system. In this work, single-factor experiments and Box-Behnken experimental design combined with response surface methodology were used to study and optimize the parameters of matrix solid phase dispersion-assisted aqueous two-phase system microextraction. The fitted models extracted from chlorogenic acid, loganin, sweroside, rutin, luteoloside, isochlorogenic acid A, and isochlorogenic acid C were successfully established and validated. Based on the optimal conditions, the correlation coefficient ranges from 0.9983 to 0.9998, and the detection limits of each analyte are in the range of 1.360–13.531 ng/mL, indicating that the method has a good linear calibration curve and good sensitivity. The recoveries of the seven target analytes in honeysuckles at two levels of intensification are between 71.35% and 104.77%, and the relative standard deviations are lower than 4.28%, showing that the mentioned method has satisfactory recovery efficiency and high reproducibility. In conclusion, this study demonstrates that matrix solid phase dispersion-assisted aqueous two-phase system microextraction is a novel method that is efficient, environmentally friendly and economical and has the potential to extract multiple active components from honeysuckles.

Carbonized biosorbent assisted matrix solid-phase dispersion microextraction for active compounds from functional food

In this study, mangosteen peel based activated carbon was prepared and first applied as adsorbent in matrix solid-phase dispersion (MSPD) for simultaneously extraction of flavonoids from Dendrobium huoshanense prior to their separation and determination by ultra-high performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UHPLC-Q-TOF/MS). The MSPD-UHPLC-Q-TOF/MS method was validated exhaustively. Good linearities (r2 ≥ 0.9929) were obtained for all target analytes. The limits of detection was in the range of 0.00387–0.159 μg/g. Satisfactory recoveries of six target compounds were between 80.02 and 99.49% and 85.32–99.86% for the low and high spiked level, respectively. Furthermore, relative to other common sorbent, the prepared mangosteen peel based activated carbon was less expensive and more environmentally-friendly. Consequently, the proposed method was a simple, efficient, low-cost, eco-friendly, time-saving and sensitive approach that could be successfully applied to the extraction and determination of flavonoids compounds in complex matrix.

Boron Nitride Nanoplates-Assisted Matrix Solid-Phase Dispersion Microextraction of Alkaloids from Plant Tea by Ultrahigh-Performance Liquid Chromatography Coupled with Ion Mobility Quadrupole Time-of-Flight Mass Spectrometry

Boron nitride nanoplates-assisted matrix solid-phase dispersion method was established to microextract the alkaloids from medical plant. The target compounds were identified by ultrahigh-performance liquid chromatography coupled with ion mobility quadrupole time-of-flight mass. During experiment process, several important parameters including the type of dispersant, the amount of dispersant, the grinding time and the type of elution solvent were optimized. At last, the boron nitride nanoplatelets was chosen as best dispersant and the microcosmic morphologies of it were identified by scanning electron microscope (SEM) and transmission electron microscope (TEM). Due to the special property of boron nitride nanoplatelets the cost of this experiment was saved greatly especially in elution volume (200 μL), sample amount (50 mg) and extraction time (2 min). With the best condition, good linearity (r2>0.9993) and satisfactory recoveries (80%-100%) were obtained. The inter-day and intra-day precision were acceptable with the RSDs lower than 1.9% and 4.84% respectively. The limits of detection were ranged from 2.54 to 15 ng mL-1 and the limits of quantitation were 8.47 to 50 ng mL-1. At present, the proposed method has been successfully applied for the determination of liensinine, isoliensinine and neferine in lotus plumule.

Establishment of Deep-Eutectic-Solvent-Assisted Matrix Solid-Phase Dispersion Extraction for the Determination of Four Flavonoids in Scutellariae Radix Based on the Concept of Quality by Design.

Sample preparation is the most crucial step in analytical schemes. Micro-matrix solid-phase dispersion, as a method for microextraction of analytes, has prevailed recently for its low sample and extraction solvent consumption. However, small amounts of adsorbent or sample, or a short extraction time, always bring uncertainty to the result when using this method. The aim was to develop a simple and reliable method of deep-eutectic-solvent-assisted ultrasonic-synchronized matrix solid-phase dispersion microextraction for the analysis of four flavonoids in Scutellariae Radix based on the concept of quality by design. The ZSM-5 molecular sieve was used as a new adsorbent in the micro-matrix solid-phase dispersion process. Single-factor and Box-Behnken designs were used to construct the design space. Verification of the experiment demonstrated that the design space is robust. Under optimal conditions, all analytes showed good linearity (R2 > 0.999), high reproducibility (RSD < 2.24%) and stability (RSD < 2.87%), and satisfactory recoveries (95.90-102.31%), which indicated that the established method is reliable and reproducible. Moreover, it has been successfully applied to determine the flavonoids in nine batches of Scutellariae Radix. The results indicate a great potential for analyzing complicated samples especially with small amount and helping to promote the quality control of the sample preparation process for traditional Chinese medicines. A systematic approach using a facile deep-eutectic-solvent-assisted ultrasonic-synchronized matrix solid-phase dispersion extraction coupled with HPLC for the analysis of flavonoids in Scutellariae Radix has been developed based on the concept of quality by design.

A simple and environmentally-friendly method by pipette-tip matrix solid-phase dispersion microextraction coupled with high-performance liquid chromatography for the simultaneous determination of lignans and terpenes

A simple and efficient ultra-miniaturized pipette-tip matrix solid-phase dispersion microextraction using molecular sieve as adsorbent has been developed to simultaneously determine honokiol, magnolol, costunlide and dehydrocostus lactone in a complex Chinese medicine. The types of adsorbent and elution solventswere optimized by single factor experiment. Adsorbent/sample ratio, grinding time and elution volume were optimized by Box-Behnken design (BBD). The optimum extraction is: using SBA-3 as an adsorbent, 200 μL of methanol as elution solvent, 2:1 of sample/adsorbent ratio and 130 s of grinding time. The proposed method applied in real samples provides good linearity (R2 > 0.9999), sufficient accuracy, high reproducibility (RSD<4.93%) and satisfactory recoveries (91.4%–101.4%). Compared with the conventional methods, it is featured with a tiny amount of sample and adsorbent consumption (3 mg of sample and 6 mg of SBA-3) which accompanied with the advantage of rapid, simple, cheap and environment-friendly. Moreover, it shows great potential on analyzing precious or rare amounts of complicated samples.

Cucurbituril and zwitterionic surfactant-based matrix solid-phase dispersion microextraction to simultaneously determine terpenoids from Radix Curcumae.

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 70mg of cucurbituril as adsorbent, 149 s as the optimum grinding time, and 228mM of 3-(N,N-dimethylpalmitylammonio)propanesulfonate aqueous solution (pH6.5) 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.

In situ antioxidation-assisted matrix solid-phase dispersion microextraction and discrimination of chiral flavonoids from citrus fruit via ion mobility quadrupole time-of-flight high-resolution mass spectrometry

A simple and sensitive in situ antioxidation process assisted with a matrix solid-phase dispersion method for extracting chiral flavonoids in citrus fruit was established, and samples were further analyzed using ion mobility quadrupole time-of-flight high-resolution mass spectrometry. The collision cross-sections of the target compounds were studied using single-field and stepped-field methods. The optimal conditions were obtained using 30 mg of C18 as a dispersant, methanol as an elution solvent and 0.6 mM 1,1-diphenyl-2-picrylhydrazyl (DPPH) as a radical solution. Additionally, the method showed satisfactory limits of detection (3.70–6.52 ng/mL) and good recoveries (96.78–104.67%) for four flavonoids in citrus fruit. The IC50 values of DPPH radical-scavenging activities ranged from 817.8 to 981.55 μg/mL for tested samples. The method was a good alternative for the microextraction and determination of antioxidant capacity and chiral differentiation of narirutin, naringin, hesperidin and neohesperidin in citrus fruit.

Metal-organic framework assisted matrix solid-phase dispersion microextraction of saponins using response surface methodology.

An efficient and simple metal-organic framework (MOF) assisted matrix solid-phase dispersion (MSPD) microextraction was developed for the extraction of the five saponins in P. ginseng leaves. The target analyses were detected by ultra high performance chromatography coupled with time-of-flight MS. Experimental conditions for MSPD microextraction were optimized by the Box-Behnken design of the response surface methodology. The optimal conditions were as follows: 20 mg adsorbent, 80% methanol-water solution for elution, 60 s grinding time, and the MOF-808 as the adsorbent. With the final optimized method, the calibration curves for five saponins showed good linearity (R2 > 0.998) within range of 0.01-100 μg/mL. In addition, analytical recoveries ranged from 87.04 to 103.78%, with the RSD below 5%. The limit of detection and LOQ range from 0.087 to 0.114 μg/mL and 0.292 to 0.379 μg/mL, respectively. Compared with the traditional extraction method and published methods, the newly MOF-assisted MSPD extract exhibited higher extraction efficiency, simpler operation, and provided a cleaner extract with low consumption of organic reagents that was applied for rapid evaluation and quality control of active compounds from plants.

Ultrasound-enhanced matrix solid-phase dispersion micro-extraction applying Mesoporous Molecular Sieve SBA-15 for the determination of multiple compounds in Fructus Psoraleae

An efficient ultrasound enhanced matrix solid-phase dispersion micro-extraction method was established for the extraction and determination of multiple ingredients (psoralenoside, isopsoralenoside, psoralen, isopsoralen, bavachin, psoralidin, isobavachalcone and bakuchiol) from Fructus Psoraleae applying ultra-high-performance liquid chromatography. The experimental factors affecting the extraction efficiency, including extraction solvent concentration, extraction solvent volume and ultrasound time, were optimized by the design of experiments methodology. Central composite design was applied in this optimization approach as a quadratic model. Under optimum conditions, good linear regression (r2 > 0.9999) and recovery (96.8%–104%, RSD<3.73%) for targets were attained. In addition, the intra-day of analytes was below 4.42% and inter-day precision of analytes was below 2.08%. This proposed method only required small amounts of reagent (0.5 mL) and materials usage (20 mg). Thus, the present study applied the efficient method to exhibit fast preparation and determination of eight ingredients of continents in Fructus Psoraleae.

Calixarene and ionic liquid assisted matrix solid-phase dispersion microextraction of organic acids from fruit

A rapid and effective method was successfully established for the extraction and determination of chlorogenic acid, protocatechuic acid, malic acid, caffeic acid and gallic acid in fruit (chaenomeles speciosa) via matrix solid-phase dispersion (MSPD) microextraction combined with ultra-high performance liquid chromatography with quadrupole time-of-flight tandem mass spectrometry (UHPLC-Q-TOF/MS). Several major extraction parameters were investigated and optimized, such as the type of sorbent, the amount of sorbent, the grinding time, the type and concentration of the eluting solvent. The optimal extraction conditions were obtained by using 20 mg of calix[8]arene as dispersing adsorbent, selecting 60 s as the appropriate grinding time and applying 250 mM of 1-dodecyl-3-methylimidazolium bromide as eluent solvent. Moreover, the calibration curves of the analytes were in the range of 0.01–500 μg/mL with the determination coefficients (r2) higher than 0.9995. The limits of detection and limits of quantification were in the range of 0.202–1.056 ng/mL and 0.674–3.521 ng/mL, respectively. The recoveries of the target compounds at two spiked levels were between 82.19 and 113.36%. Furthermore, this method had acceptable reproducibility (RSD ≤ 3.84%). The proposed approach combined the advantages of MSPD microextraction with UHPLC-Q-TOF/MS, and could be applicable for the analysis organic acids in fruit.

Quantification of eight active ingredients in crude and processed radix polygoni multiflori applying miniaturized matrix solid-phase dispersion microextraction followed by UHPLC.

A rapid, efficient, and green sample preparation method has been developed to extract eight active ingredients (gallic acid, catechins, epicatechin, polydatin, 2,3,5,4'-tetrahydroxystilbene-2-O-β-d-glucoside, resveratrol, emodin, and physcion) in radix polygoni multiflori by miniaturized matrix solid-phase dispersion microextraction. Simple and sensitive ultra high performance liquid chromatography combined with ultraviolet detection has been applied to analyze the multiple compounds. The best results were obtained by adding 25mg sample into 25mg adsorbent and grinding for 2min with disorganized silica as adsorbent and 1mL 150mM 1-dodecyl-3-methylimidazolium bromide as a green eluting solvent. Good linearity (r2 >0.998) for each analyte was obtained by this method. The intra-day and inter-day precision (RSD) were both below 5.31%, and the recoveries of the analytes ranged from 93.3 to 100.0%. This simple miniaturized matrix solid-phase dispersion microextraction method for analyzing the compounds in radix polygoni multiflori needs a short time and requires little sample and reagent. Thus, this method is far more eco-friendly and efficient than traditional extraction methods (reflux and ultrasound-assisted extraction). The present investigation provided a promising method for the fast preparation and discrimination of chemical differences in crude and processed radix polygoni multiflori.

Graphene nanoplatelets based matrix solid-phase dispersion microextraction for phenolic acids by ultrahigh performance liquid chromatography with electrochemical detection

A simple, rapid and eco-friendly approach based on matrix solid-phase dispersion microextraction (MSPDM) followed by ultrahigh performance liquid chromatography coupled with electrochemical detection (UHPLC-ECD) was presented for the microextraction and determination of six phenolic acids in a plant preparation (Danshen tablets). The parameters that influenced the extraction performance of phenolic acids were investigated and optimized. The optimal MSPDM conditions were determined as follows: sorbent, using graphene nanoplatelets with sample/sorbent ratio of 1:1, grinding time set at 60 s, and 0.2 mL of water as elution solvent. Under the optimum conditions, the validation experiments indicated that the proposed method exhibited good linearity (r2 ≥ 0.9991), excellent precision (RSD ≤ 4.57%), and satisfactory recoveries (82.34–98.34%). The limits of detection were from 1.19 to 4.62 ng/mL for six phenolic acids. Compared with other reported methods, this proposal required less sample, solvent and extraction time. Consequently, the proposed method was successfully used to the extraction and determination of phenolic acids in Danshen tablets.

Determination of natural phenols in olive fruits by chitosan assisted matrix solid-phase dispersion microextraction and ultrahigh performance liquid chromatography with quadrupole time-of-flight tandem mass spectrometry

A simple, efficient and low-cost method based on matrix solid-phase dispersion (MSPD) microextraction and ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight tandem mass spectrometry (UHPLC-Q-TOF/MS) was developed for the determination of seven main natural phenols (gallic acid, hydroxytyrosol, methyl gallate, luteolin 7-O-β-d-glucoside, rutin, ellagic acid and oleuropein) and other eleven compounds in olive fruits. The experimental conditions for the MSPD extraction, including the type of adsorbent, the amount of dispersing sorbent, the grinding time, and the type of elution solvent were investigated and optimized. The optimized parameters were determined to be that middle-molecular-weight chitosan was used as adsorbent, the amount of middle-molecular-weight chitosan was selected to be 25mg, the grinding time was chosen to be 60s, and methanol: water (6:4, v:v) was used as elution solvent. Compared with reported methods, the proposed method was more simple, rapid, and efficient. Moreover, this method required less extraction time and less amount of sample and solvent. The method showed good linearity (r2≥0.9909) for the seven analytes, with the limits of detection in the range of 69.6–358.4ng/g. And recoveries were above 80.06%. The methodology was successfully applied to the extraction and determination of seven phenolic compounds in olive fruits（Canarii fructus）.

ChemInform Abstract: Carbon Nanotubes: Solid‐phase Extraction

AbstractReview: 181 refs.

Matrix Solid-Phase DispersionMicroextraction and Determination of Pesticide Residues in Medicinal Herbs by Gas Chromatography with a Nitrogen-Phosphorus Detector

A gas chromatography method for the determination of residues of 6 pesticides in Isatis indigotica Fort and Paeonia lactiflora Pall is described. Optimizations of different parameters were performed. The method used 0.5 g herb sample, silica gel as the matrix solid-phase dispersion sorbent, and acetone as the eluting solvent. Recoveries at spiked concentrations between 0.1 and 5 mg/kg were between 80.63 and 110.12%, with relative standard deviations ranging from 0.43 to 17.67%. The limits of quantitation were 0.01 mg/kg for metalaxyl, triadimefon, and paclobutrazol and 0.05 mg/kg for vinclozolin, tebuconazole, and fenarimol. The method may be useful as a screening protocol for the determination of these pesticides in medicinal herb samples.

Matrix Solid-Phase Dispersion Micro-Extraction of Pesticides from Single Insects with Subsequent GC–MS Analysis

A simple multiresidue method based on matrix solid-phase dispersion (MSPD) micro-extraction was studied to determine various organophosphorus (OPPs) and pyrethroid pesticides in single insects. Optimisation of the relevant parameters showed that, in the case of OPPs and permethrin, extraction from 40 mg of isopod (Porcellio scaber) and the use of C8-bonded silica and 100 μL of ethyl acetate were the best conditions, while silica and 3.5 mL of n-hexane were optimal for the less polar pyrethroids. Subsequently, 1 μL (ethyl acetate) or 20 μL (n-hexane) of the extracts were analysed by GC–MS without any further clean-up. The limits of detection (LODs), in the SIM mode, were 5–80 ng g−1 for most OPPs and trans-permethrin (cis-permethrin 0.3 ng g−1) when using the C8-bonded silica/ethyl acetate procedure, and 5–35 ng g−1 for the pyrethroids when using the silica/n-hexane procedure. The recoveries of the OPPs and pyrethroids from the isopods were 52–94%. The practicality of the proposed method was studied for pesticides in isopods which had been fed polluted leaves.

Matrix solid-phase dispersion microextraction and determination by high-performance liquid chromatography with UV detection of pesticide residues in citrus fruit

A multiresidue method based on matrix solid-phase dispersion (MSPD) microextraction was studied to determine the carbamate, benfuracarb, and urea insecticides, diflubenzuron, flufenoxuron hexaflumuron and hexythiazox, used in control of citrus pests. Optimisation of different parameters, such as the type of solid support for matrix dispersion, elution solvents and the clean-up step were carried out. The method used 0.5 g of orange sample, C 8 bonded silica as MSPD sorbent and dichloromethane as eluting solvent. Recoveries, at spiked concentrations below the maximum residue levels established by Spanish Government, were between 74 and 84% with relative standard deviations ranging from 2 to 4%. The limits of quantification were from 0.15 to 0.25 μg/g using high-performance liquid chromatography with UV detection at 200 nm. The method may be useful as a screening protocol for the determination of these newly developed pesticides in citrus samples.