Vortex-assisted Matrix Solid-phase Research Articles

Isolation of DNA from plant tissues using a miniaturized matrix solid-phase dispersion approach featuring ionic liquid and magnetic ionic liquid solvents

The isolation of high-quality plant genomic DNA is a major prerequisite in many plant biomolecular analyses involving nucleic acid amplification. Conventional plant cell lysis and DNA extraction methods involve lengthy sample preparation procedures that often require large amounts of sample and chemicals, high temperatures and multiple liquid transfer steps which can introduce challenges for high throughput applications. In this study, a simple, rapid, miniaturized ionic liquid (IL)-based extraction method was developed for the isolation of genomic DNA from milligram fragments of Arabidopsis thaliana plant tissue. This method is based on a modification of vortex-assisted matrix solid-phase dispersion (VA-MSPD) in which the trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide ([P6,6,6,14+][NTf2-]) IL or trihexyl(tetradecyl)phosphonium tris(hexafluoroacetylaceto)nickelate(II) ([P6,6,6,14+][Ni(hfacac)3-]) magnetic IL (MIL) was directly applied to treated plant tissue (∼1.5 mg) and dispersed in an agate mortar to facilitate plant cell lysis and DNA extraction, followed by recovery of the mixture with a qPCR compatible co-solvent. This study represents the first approach to use ILs and MILs in a MSPD procedure to facilitate plant cell lysis and DNA extraction. The DNA-enriched IL- and MIL-cosolvent mixtures were directly integrated into the qPCR buffer without inhibiting the reaction while also circumventing the need for additional purification steps prior to DNA amplification. Under optimum conditions, the IL and MIL yielded 2.87 ± 0.28 and 1.97 ± 0.59 ng of DNA/mg of plant tissue, respectively. Furthermore, the mild extraction conditions used in the method enabled plant DNA in IL- and MIL-cosolvent mixtures to be preserved from degradation at room temperature.

Distribution in marine fish and EDI estimation of contaminants of emerging concern by vortex-assisted matrix solid-phase dispersion and HPLC-MS/MS

Due to their persistence or continuous discharge, toxic substances are present in the aquatic environment, and can bioaccumulate and biomagnify in the food web, generating a significant ecological risk and a threat to human health. The present study assess the occurrence and tissue (muscle, liver, stomach and gills) distribution of 59 anthropogenic contaminants of emerging concern (CECs) in marine fish from Brazil. A simpler and faster analytical methodology based on vortex-assisted matrix solid-phase dispersion (VA-MSPD) and liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed and validated. Limits of quantification ranged from 3.31 to 114 ng g−1 dw with recovery rates between 60 and 140 % and relative standard deviation below 20 %. The ultraviolet filters 4-hydroxybenzophenone (4HB) (benzophenone-3 metabolite) and benzocaine (Et-PABA), and the antibacterial salicylic acid were frequently accumulated in muscle and liver at concentrations between 39.5 and 21.0 ngg−1 dw. The determined concentrations resulted to be lower than the tolerable daily intake recommended by the European Food Safety Authority (EFSA).

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.

Vortex-assisted matrix solid-phase dispersion: An eco-friendly alternative for the determination of halogens in edible seaweed

Edible seaweed has been widely consumed around the world through oriental cuisine and it is important to monitor the levels of some elements, especially halogens. This study proposes, for the first time, the development of an analytical method using the vortex-assisted matrix solid-phase dispersion (VA-MSPD) combined with alkaline extraction of halogens (F, Cl, Br, and I) in edible seaweed for further determination by ion chromatography. The proposed method was evaluated using edible seaweed of the Nori (Porphyra spp.) type and applied to samples of the Wakame (Undaria pinnatifida), Kombu (Laminaria ochroleuca), and Hijiki (Hizikia fusiformis) types. Important VA-MSPD parameters were investigated and using 0.1 g sample, 1 g sea sand as solid support, 50 mmol L−1 (NH4)2CO3 as extraction solution, and 5 min of maceration, higher extraction efficiencies were obtained. The method was linear within the evaluated range (R2 > 0.99) for all elements and no matrix effect was observed. The detection limits of the method were 27, 26, 19, and 28 μg g−1 for F, Cl, Br, and I, respectively. The accuracy was evaluated by a recovery test (ranging from 92 to 108%) and analysis of certified reference materials for apple leaves (NIST 1515) and peach leaves (NIST 1547), which had a good agreement (ranging from 97 to 101%) with the certified values. Comparing the results with those obtained by inductively coupled plasma-mass spectrometry after microwave-induced combustion, no significant difference was found between the results, and the relative standard deviations were lower than 12%. The proposed method proved to be efficient for the determination of halogens in different algae species, showing advantages such as simplicity and low cost, combined to the use of a material from renewable sources (sea sand) as a solid support, contributing to the principles of Green Analytical Chemistry.

Binary Eluent Based Vortex-Assisted Matrix Solid-Phase Dispersion for the Extraction and Determination of Multicomponent from Musk by Gas Chromatography-Mass Spectrometry.

A green, flexible, and effective strategy was proposed to quantify four target compounds (muscone, ethyl palmitate, ethyl oleate, and ethylparaben) from musk by binary eluent based vortex-assisted matrix solid-phase dispersion (MSPD) extraction coupled with GC/MS. Single-factor tests and orthogonal design were employed to optimize the MSPD parameters. In addition, the binary eluent system, methanol, and ethyl acetate 3 : 7 (v/v) were used to extract the target analytes. Finally, C18 was applied as the easily available dispersant and the sample powder was ground for 2 min. Thereafter, the mixture was rapidly extracted with the binary eluents under whirling for 3 min. Eventually, the analysis of the samples was completed within 12 min by GC/MS. All correlation coefficients (r) of four targets were more than 0.9991. The recoveries of all target compounds ranged from 92.8% to 101% while their RSDs were less than 6.94%. There was no significant matrix interference for the analysis. Thus, the combination of vortex-assisted MSPD with GC/MS was considered as a novel, rapid, and environmentally friendly quantitative approach for musk samples.

Rapid and cost-effective multiresidue analysis of pharmaceuticals, personal care products, and antifouling booster biocides in marine sediments using matrix solid phase dispersion

Currently, there are many contaminants of concern that need to be accurately determined to help assess their potential environmental hazard. Despite their increasing interest, yet few environmental occurrence data exist, likely because they are present at low levels and in very complex matrices. Therefore, multiresidue analytical methods for their determination need to be highly sensitive, selective, and robust. Particularly, due to the trace levels of these chemicals in the environment, an extensive extraction procedure is required before determination. This work details the development of a fast and cheap vortex-assisted matrix solid-phase dispersion-high performance liquid chromatography tandem-mass spectrometry (VA-MSPD-HPLC-MS/MS) method for multiresidue determination of 59 contaminants of emerging concern (CECs) including pharmaceuticals, personal care products, and booster biocides, in sediment. The validated method provided high sensitivity (0.42–36.8 ngg−1 dw quantification limits), wide and good linearity (r2 > 0.999), satisfactory accuracy (60–140%), and precision below 20% for most target analytes. In comparison with previous methods, relying on traditional techniques, the proposed method demonstrated to be more environmentally friendly, cheaper, simpler, and faster.The method was applied to monitor the occurrence of these compounds in sediments collected in Brazil, using only 2 g dw sediment samples, free-solid support, and 5 mL methanol as extraction solvent. The UV filter avobenzone, the UV stabilizer and antifreeze methylbenzotriazole, the preservative methylparaben, the fluoroquinolone antibiotic ciprofloxacin, and the biocides irgarol and 4,5-dichloro-2-octyl-4-isothiazolin-3-one were determined at concentrations in the range 1.44–69.7 ngg−1 dw.

A Rapid High Throughput Vibration and Vortex-Assisted Matrix Solid Phase Dispersion for Simultaneous Extraction of Four Isoflavones for Quality Evaluation of Semen Sojae Praeparatum.

Isoflavones (daidzein, daidzin, genistein and genistin) were main chemical components and usually selected as markers for quality control of Traditional Chinese Medicine semen sojae praeparatum (SSP). High throughput vibration and vortex-assisted matrix solid phase dispersion and high performance liquid chromatography with diode array detection were developed to simultaneously extract and quantify four isoflavones in SSP. Some parameters influencing extraction efficiency of isoflavones by vortex-assisted matrix solid phase dispersion such as sorbent type, ratio of sample to sorbent, crushing time, vibration frequency, methanol concentration, eluting solvent volume and vortex time were optimized. It was found that the best extraction yields of four isoflavones were obtained when the sample (20 mg) and SBA-3 (40 mg) was crushed by ball mill machine for 2 min at vibration frequency of 800 times per minute. Methanol/water (1.5 ml, 8:2, v/v) solution was dropped into the treated sample and vortexed for 3 min. The recoveries of the four isoflavones ranged from 86.1 to 94.8% and all relative standard deviations were less than 5%. A good linearity (r > 0.9994) was achieved within the range 0.5–125 μg/ml. It was concluded that the high throughput vibration and vortex-assisted matrix solid-phase dispersion coupled with high performance liquid chromatography was user-friendly extraction and quantification method of multiple isoflavones for quality evaluation of SSP.

Determination of phenolic acids and flavonoids from Myrciaria cauliflora edible part employing vortex-assisted matrix solid-phase dispersion (VA-MSPD) and UHPLC-MS/MS

In the present study, for the first time, vortex-assisted matrix solid-phase dispersion (VA-MSPD) is used to determine phenolic compounds in the edible part of Myrciaria cauliflora combined with ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) analysis. Under the optimized extraction conditions, the VA-MSPD method used a small amount of sample (25 mg), C18 (100 mg) as a solid support, a small volume of methanol (6 mL) as elution solvent and reduced time of grinding and vortex agitation (90 s). The proposed method showed good linearity (r ≥ 0.99) for all compounds, with detection limits in the range of 0.9˗99 μg kg−1. The matrix effect was between ˗0.8 and +52 %. This method allowed the quantification of four phenolic acids (4-hydroxybenzoic acid, gallic acid, p-coumaric acid and ellagic acid) and four flavonoids (myricetin, (+)-catechin, naringenin and quercetin) in M. cauliflora edible part harvested in different years. Ellagic acid was found with the highest abundance ranging from 470 to 709 mg kg−1. These results support the high potential of VA-MSPD to be applied in the determination of the phenolic compounds of fruit matrices, as well as, requiring a low solvent volume, a small amount of sample and solid support and features easy handling and short analysis time.

Extraction of chlorothalonil, dichlofluanid, DCOIT, and TCMTB from fish tissues employing the vortex assisted matrix solid-phase dispersion

This paper reports the development and optimization of a method based on vortex assisted matrix solid-phase extraction (VA-MSPD) and gas chromatography with electron capture detection for the evaluation of booster biocides in fish tissues. Some parameters that affect the method performance were evaluated and suitable recoveries were obtained with 0.2 g sample, 2.0 g reused end capped C18, 0.2 g sodium sulfate and 5 mL ethyl acetate (35 mmol L−1 acetic acid). After validation, the method was applied to both species Mugil liza and Cynoscion guatucupa and to different tissues of Micropogonias furnieri. Analytical recoveries ranged from 60 to 126% whereas relative standard deviation was below 18%. The limit of quantification value of chlorothalonil was 125 ng g−1 while the one of dichlofluanid, DCOIT and TCMTB was 625 ng g−1. The use of VA-MSPD for this proposal has shown to be a promising alternative since it is fast, simple and low cost. Besides, this is the first study that aims at extracting DCOIT and TCMTB from fish samples.

Optimization of Matrix Solid-Phase Dispersion Method for Extraction of Aflatoxins from Cornmeal

An extraction method for simultaneous determination of aflatoxins (AFLAs) G2, G1, B2, and B1 in cornmeal, based on vortex-assisted matrix solid-phase dispersion (MSPD) and high-performance liquid chromatography (HPLC) with fluorescence detection was optimized by a central composite design, validated and applied. Multivariate analysis was performed to evaluate the effect of cornmeal composition on AFLA extraction. The amount and proportion of solid support (celite and C18) and volume of elution solvent (methanol and acetonitrile) were the variables tested. The mobile phase of methanol/acetonitrile/water (24:14:62, v/v/v) in isocratic elution mode provided satisfactory AFLA separation. The best recoveries (85.7 to 114.8%) were obtained when the sample preparation contained 25 mg C18 as solid support and 10 mL of elution solvent. The limits of detection ranged from 0.01 to 0.04 ng g−1, and the limits of quantification varied from 0.02 to 0.1 ng g−1. The optimized method was suitable for coarse and medium grind cornmeal. Multivariate correlation analysis showed that the main interferers for AFLA recovery were proteins and sugars.

Antifouling booster biocide extraction from marine sediments: a fast and simple method based on vortex-assisted matrix solid-phase extraction.

This paper reports the development of an analytical method employing vortex-assisted matrix solid-phase dispersion (MSPD) for the extraction of diuron, Irgarol 1051, TCMTB (2-thiocyanomethylthiobenzothiazole), DCOIT (4,5-dichloro-2-n-octyl-3-(2H)-isothiazolin-3-one), and dichlofluanid from sediment samples. Separation and determination were performed by liquid chromatography tandem-mass spectrometry. Important MSPD parameters, such as sample mass, mass of C18, and type and volume of extraction solvent, were investigated by response surface methodology. Quantitative recoveries were obtained with 2.0g of sediment sample, 0.25g of C18 as the solid support, and 10mL of methanol as the extraction solvent. The MSPD method was suitable for the extraction and determination of antifouling biocides in sediment samples, with recoveries between 61 and 103% and a relative standard deviation lower than 19%. Limits of quantification between 0.5 and 5ngg-1 were obtained. Vortex-assisted MPSD was shown to be fast and easy to use, with the advantages of low cost and reduced solvent consumption compared to the commonly employed techniques for the extraction of booster biocides from sediment samples. Finally, the developed method was applied to real samples. Results revealed that the developed extraction method is effective and simple, thus allowing the determination of biocides in sediment samples.

Determination of ibuprofen enantiomers in breast milk using vortex-assisted matrix solid-phase dispersion and direct chiral liquid chromatography

A mixture of β-cyclodextrin (β-CD) and primary and secondary amine (PSA) sorbents was employed for the extraction and quantification of ibuprofen enantiomers from human breast milk, combining a vortex-assisted matrix solid-phase dispersion method (MSPD) and direct chiral liquid chromatography (CLC) with ultraviolet detection (UV). The MSPD sample preparation procedure was optimized focusing on both the type and amount of dispersion/sorption sorbents and the nature of the elution solvent, in order to obtain acceptable recoveries and avoiding enantiomer conversion. These MSPD parameters were optimized with the aid of an experimental design approach. Hence, a factorial design was used for identification of the main variables affecting the extraction process of ibuprofen enantiomers. Under optimum selected conditions, MSPD combined with direct CLC-UV was successfully applied for ibuprofen enantiomeric determination in breast milk at enantiomer levels between 0.15 and 6.0μgg−1. The proposed analytical method also provided good repeatability, with relative standard deviations of 6.4% and 8.3% for the intra-day and inter-day precision, respectively.

New environmentally friendly MSPD solid support based on golden mussel shell: characterization and application for extraction of organic contaminants from mussel tissue.

The use of golden mussel shells as a solid support in vortex-assisted matrix solid-phase dispersion (MSPD) was evaluated for the first time for extraction of residues of 11 pesticides and nine pharmaceutical and personal care products from mussel tissue samples. After they had been washed, dried, and milled, the mussel shells were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, infrared spectroscopy, and Brunauer-Emmett-Teller analysis. The MSPD procedure with analysis by liquid chromatography-tandem mass spectrometry allowed the determination of target analytes at trace concentrations (nanograms per gram), with mean recoveries ranging from 61 to 107 % and relative standard deviations lower than 18 %. The optimized method consisted of dispersion of 0.5 g of mussel tissue, 0.5 g of NaSO4, and 0.5 g of golden mussel shell for 5 min, and subsequent extraction with 5 mL of ethyl acetate. The matrix effect was evaluated, and a low effect was found for all compounds. The results showed that mussel shell is an effective material and a less expensive material than materials that have traditionally been used, i.e., it may be used in the MSPD dispersion step during the extraction of pesticides and pharmaceutical and personal care products from golden mussel tissues. Graphical Abstract Vortex-assited matrix solid-phase dispersion for extraction of 11 pesticides and 9 PPCPs care products from mussel tissue samples.

Study of vortex-assisted MSPD and LC-MS/MS using alternative solid supports for pharmaceutical extraction from marketed fish

A procedure based on vortex-assisted matrix solid-phase dispersion (MSPD) for the extraction of 15 pharmaceuticals from fish samples with determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was validated. Florisil, C18, diatomaceous earth, chitin, and chitosan were evaluated as solid supports. Best results were obtained with 0.5 g of diatomaceous earth, 0.5 g of sodium sulfate, and 5 mL of methanol. Analytical recoveries ranged from 58 to 128 % with relative standard deviation (RSD) lower than 15 %. Limit of quantification (LOQ) values for the 15 compounds ranged from 5 to 1000 ng g(-1). The method under investigation has shown to be a simple and fast extraction tool with minimum instrumentation and low amount of reagent, resulting in method low cost. Besides, alternative materials, such as chitin and chitosan, which were applied to the dispersion step for the first time, were found to be interesting alternatives.