Matrix Solid-phase Extraction Research Articles

Ultrasound-assisted matrix solid-phase extraction based on deep eutectic solvents and zinc oxide: Extraction and determination of six active ingredients in Ligustri Lucidi Fructus.

In this study, we propose a novel strategy utilizing deep eutectic solvents (DESs) as both the extraction solvent and dispersing liquid, with nanometer zinc oxide (ZnO) serving as the adsorbent. This method incorporates ultrasound-assisted matrix solid phase dispersion (UA-MSPD) for the extraction of six active components (salidroside, echinacoside, acteoside, specnuezhenide, nuezhenoside G13, and oleanolic acid) from Ligustri Lucidi Fructus samples. The extracts were then analyzed using high-performance liquid chromatography equipped with a diode array detector. The effects of various parameters such as dispersant dosage, DESs volume, grinding time, ultrasonication duration, and eluent volume on extraction recovery were investigated and optimized using a central composite design under response surface methodology. The optimized conditions yielded detection limits ranging from 0.003 to 0.01mg/g and relative standard deviations of 8.7% or lower. Extraction recoveries varied between 93% and 98%. The method demonstrated excellent linearity for the analytes (R2 ≥ 0.9997). The simple, green, and efficient DESs/ZnO-UA-MSPD technique proved to be rapid, accurate, and reliable for extracting and analyzing the six active ingredients in Ligustri Lucidi Fructus samples.

Recent Advances in Sample Preparation for Cosmetics and Personal Care Products Analysis.

The use of cosmetics and personal care products is increasing worldwide. Their high matrix complexity, together with the wide range of products currently marketed under different forms imply a challenge for their analysis, most of them requiring a sample pre-treatment step before analysis. Classical sample preparation methodologies involve large amounts of organic solvents as well as multiple steps resulting in large time consumption. Therefore, in recent years, the trends have been moved towards the development of simple, sustainable, and environmentally friendly methodologies in two ways: (i) the miniaturization of conventional procedures allowing a reduction in the consumption of solvents and reagents; and (ii) the development and application of sorbent- and liquid-based microextraction technologies to obtain a high analyte enrichment, avoiding or significantly reducing the use of organic solvents. This review provides an overview of analytical methodology during the last ten years, placing special emphasis on sample preparation to analyse cosmetics and personal care products. The use of liquid–liquid and solid–liquid extraction (LLE, SLE), ultrasound-assisted extraction (UAE), solid-phase extraction (SPE), pressurized liquid extraction (PLE), matrix solid-phase extraction (MSPD), and liquid- and sorbent-based microextraction techniques will be reviewed. The most recent advances and future trends including the development of new materials and green solvents will be also addressed.

A study of the spatial distribution patterns of airborne polycyclic aromatic hydrocarbons in crowberry (Empetrum nigrum) in Ilulissat, Greenland

Polycyclic aromatic hydrocarbons (PAHs) are produced by anthropogenic activities, such as traffic and domestic heating. Due to their adverse effects to humans and natural habitats, the presence of PAHs in the environment needs to be monitored. Plants are known as natural accumulators of persistent organic pollutants (POPs) and can therefore be used for the monitoring of PAHs emitted into the environment. Contamination by PAHs also occurs in the Arctic such as Greenland due to long-range transport through air. However, as anthropogenic activities in the Arctic are increasing, there is a need to investigate the distribution of PAHs due to local emission sources. In this study, we present a systematic sampling approach to identify the influence of PAH sources in an area next to the town of Ilulissat in Greenland. Composite crowberry samples have been collected north of Ilulissat, where the town itself, an incineration site and Ilulissat airport are possible emission sources for PAHs. Matrix solid-phase extraction was used for the extraction of PAHs and the chemical analysis was performed by gas chromatography with mass spectrometry detection (GC-MS). In total, 18 out of 19 investigated PAHs could be detected in Empetrum nigrum in a concentration range of 0.69 to 93.01μg/kgdry weight. Higher concentrations for most of the targeted PAHs were found close to the suspected emission sources and also along the road connecting them. For pyrene, the correlation between the concentration and the distance from the emission sources could be modelled and visualized using a two-dimensional exponential variogram and ordinary kriging. The range in which the samples were spatially correlated was approximately 500m. Our results show that local emission sources contribute to the spatial distribution patterns of PAHs. Monitoring of pollution by airborne PAHs is therefore needed even in areas far from major pollution sources such as Ilulissat, Greenland. E. nigrum showed to be a feasible species for biomonitoring of PAHs due to its large abundance in the sampling area and its widespread availability in the Artic region.

Surface-enhanced Raman Spectroscopy Coupled with Dispersive Solid-phase Extraction for the Rapid Detection of Tricyclazole Residues in Rice and Brassica campestris L. ssp. chinensis var. utilis Tsen.

An efficient methodology has been developed to determine the tricyclazole residue in matrix based on surface-enhanced Raman scattering (SERS) coupled with dispersible matrix solid-phase extraction. After pretreatment and test conditions optimization, peaks at 1373 and 1317 cm-1 in the SERS spectrum were respectively selected as quantitative peaks for rice and Brassica campestris L. ssp. chinensis var. utilis Tsen, respectively. The matrix standard curve-external standard method was used to quantitatively conduct a statistical analysis. The correlation between the quantitative peak response and tricyclazole concentration showed a significant linear relationship with a correlation coefficient of R2 > 0.99. The lowest spiked concentration was determined to be the quantitative limit that was below the maximum residue limits of tricyclazole. This study provides a sensitive, stable and rapid approach for the analysis of tricyclazole in above matrix via SERS, and it will be a useful complement to the quantitative analysis of tricyclazole in a complex matrix.

Preparation and application of simetryn-imprinted nanoparticles in triazine herbicide residue analysis.

This work provides a simple and rapid method for synthesis uniform simetryn imprinted nanoparticles, which can be used to pretreat the tested samples before detecting. A series of computational approach were employed for design simetryn-imprinted polymer. Based on the conclusion of theoretical calculation, the simetryn imprinted nanoparticles were synthesized using simetryn as template, methacrylic acid as monomer with different solvent volume and synthesis conditions. The obtained nanoparticles have small size, uniform distribution and high imprinted factor. Scatchard analysis and quantum chemical calculations were applied for evaluating the interaction of simetryn with methacrylic acid in the imprinting process. The selectivity and recognition ability of the simetryn imprinted nanoparticles for six triazine herbicides and two other type herbicides were investigated. The results show that the simetryn imprinted nanoparticles had high selectivity and binding capacity and could be used for the separation and enrichment of four triazine pesticide residues from actual samples. A method of molecularly imprinted matrix solid phase extraction ultra-performance liquid chromatography tandem mass spectrometry was established for detecting four kinds of triazine herbicide residues in tobacco. The recovery rate of terbuthylazine, simetryn, atrazine, and prometryn in tobacco was 84.03-119.05%, and the relative standard deviation was 0.35-10.12%.

A composite consisting of sulfo-functionalized magnetic graphene and mesoporous silica for extraction of metformin and glimepiride prior to their determination by liquid chromatography tandem mass spectrometry.

A new sorbent was synthesized for restricted-access matrix solid phase extraction (RAM-SPE) of the diabetes drugs metformin (MET) and glimepiride (Glim). Mesoporous silica layers were placed on Fe3O4-magnetized graphene modified with sulfo-functionalized pore walls (denoted as magG@mSiO2-SO3H composites). The composites have a large specific surface (173m2·g-1), appropriate pore sizes (typically 3.7nm), and sulfo-functionalized pore walls. Magnetic separation can be accomplished within 10s. The unique properties of the composites allow both MET and Glim to be selectively and quickly extracted from plasma sample. Following magnetic separation and elution by 50% aqueous acetonitrile with 4% ammonium solution, the two drugs were quantified by LC-MS/MS analysis. The assay has high selectivity, good linearity (2.5-4000ng•mL-1 for MET and 0.02-1600ng•mL-1 for Glim), a low detection limit (as low as 60pg•mL-1 for MET and 1pg•mL-1 for Glim), excellent recovery (above 92.2%), and good precision (RSDs <12%). The method was successfully applied in a pharmacokinetic study in beagle dogs. Graphical abstract Schematic representation of the synthesis of sulfo-functionalized magnetic graphene/mesoporous silica composites, giving a material of type magG@mSiO2-SO3H. Results showed its great potential as a feasible and alternative adsorbent for the selective extraction of MET and Glim from complicated biological samples.

Matrix solid-phase dispersion based on magnetic ionic liquids: An alternative sample preparation approach for the extraction of pesticides from vegetables

In this study, we propose, for the first time, the direct use of a magnetic ionic liquid (MIL) in a matrix solid-phase extraction procedure. Because of the magnetic properties, the MIL can be harvested directly after the extraction step, using a magnet, while its hydrophobic nature makes feasible the extraction of analytes. Raw vegetables of high water content can be analyzed without any pretreatment. The viscous nature of the selected MIL assists in blending with the matrix, while its hydrophobicity facilitates easier separation and retrieval. Additionally, no solid dispersing materials or co-sorbents are needed. A simple, low-cost analytical method for the determination of multi-class pesticides residues in raw vegetables was developed, with satisfactory recoveries.

Concentrations, source identification and eco-toxicological risk of polycyclic aromatic hydrocarbons in agricultural soils of Kenya, Eastern Africa

This study evaluated the concentrations, distribution, source and potential toxicological risk of 16 polycyclic aromatic hydrocarbons (PAHs) in agricultural soils in Kenya, East Africa. A total of 69 soil samples were analysed from five agricultural sites. Matrix solid-phase extraction was used for sample extraction before analysis using high-performance liquid chromatography. A total organic carbon analyser was used to assess the organic carbon content of all of the soil samples. The overall concentrations of PAHs varied from 2593.05 ng/g (Maai Mahiu) to 4356.15 ng/g (Mount Suswa) with a mean value of 3353.04 ± 2179.81 ng/g. Lower-molecular-weight (2-, 3- and 4-ring) PAHs were dominant in the soils. Anthracene had the highest mean concentration with a value of 1048.92 ng/g and ranged from 614.37 ng/g in Narok to 2416.95 ng/g in Mount Suswa. Identification of potential sources of PAHs revealed that pollution from PAHs in Kenyan soil samples was primarily derived from pyrogenic sources linked to biomass combustion and from vehicle and coal combustion. The risk assessment indicated a high eco-toxicological risk associated with the majority of the 16 PAHs in Kenyan agricultural soils. All of the RQ∑16PAHs (NCs) in all of the study sites showed values higher than 800. Similarly, all of the RQ∑16PAHs (MPCs) were also found to be greater than 1.00 in all study sites, which indicated potential risk. Therefore, certain measures need to be established to control and mitigate pollution.

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.

Silica Modified with Polyaniline as a Potential Sorbent for Matrix Solid Phase Dispersion (MSPD) and Dispersive Solid Phase Extraction (d-SPE) of Plant Samples.

Polyaniline (PANI) is one of the best known conductive polymers with multiple applications. Recently, it was also used in separation techniques, mostly as a component of composites for solid-phase microextraction (SPME). In the present paper, sorbent obtained by in situ polymerization of aniline directly on silica gel particles (Si-PANI) was used for dispersive solid phase extraction (d-SPE) and matrix solid–phase extraction (MSPD). The efficiency of both techniques was evaluated with the use of high performance liquid chromatography with diode array detection (HPLC-DAD) quantitative analysis. The quality of the sorbent was verified by Raman spectroscopy and microscopy combined with automated procedure using computer image analysis. For extraction experiments, triterpenes were chosen as model compounds. The optimal conditions were as follows: protonated Si-PANI impregnated with water, 160/1 sorbent/analyte ratio, 3 min of extraction time, 4 min of desorption time and methanolic solution of ammonia for elution of analytes. The proposed procedure was successfully used for pretreatment of plant samples.

Preparation of carbon-functionalized magnetic graphene/mesoporous silica composites for selective extraction of miglitol and voglibose in rat plasma

In this work, magnetic graphene/mesoporous silica composites with carbon-functionalized pore-walls (denoted as MG@mSiO2-C composites) were synthesized and applied as restricted access matrix solid phase extraction (RAM-SPE) adsorbents for the determination of miglitol and voglibose in rat plasma by LC-MS/MS. The MG@mSiO2-C composites were synthesized by using the template (Cetyltrimethyl Ammonium Bromide, CTAB) as carbon source with sulfuric acid pretreated. The obtained nano-composites were proven to have many unique properties such as large specific surface area of 277.1 cm2 g−1, uniform mesopores with average pore size of 3.35 nm, and carbon-functionalized pore-walls. Taking advantage of the hydrophilic interaction between carbon and glycans, α-glucosidase inhibitors (miglitol and voglibose) could be directly extracted from rat plasma with no need of other pre-treatment procedures. The SPE conditions such as the adsorbent amount, elution solvent type, adsorption time and elution time were optimized. For both miglitol and voglibose, good linearities of 10–2000 ng mL−1 were obtained with determination coefficients (R2) > 0.99. The intra-day and inter-day RSDs were 3.3–6.9% (n = 6) and 6.0–8.0% (n = 6), respectively. The recoveries were in the range of 99.9–100.4% and the sensitivities were as low as 2–2.5 ng mL−1 (LOD). This MG@mSiO2-C composites-based RAM-SPE method offers high extraction efficiency for the determination of α-glucosidase inhibitor in plasma.

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.

Preparation of magnetic graphene/mesoporous silica composites with phenyl-functionalized pore-walls as the restricted access matrix solid phase extraction adsorbent for the rapid extraction of parabens from water-based skin toners

In this work, phenyl-functionalized magnetic graphene/mesoporous silica composites (MG-mSiO2-Ph) were prepared and applied as restricted access matrix solid phase extraction (RAM-SPE) adsorbents to determine the parabens in commercially available retail cosmetics. MG-mSiO2-Ph composites were synthesized by a surfactant-mediated co-condensation reaction in which mesoporous silica with phenyl-functionalized pore-walls was coated on a magnetic graphene sheet. The obtained nano-composites were proven to be of sufficient quality for an ideal RAM-SPE adsorbent with a large specific surface area of 369m2g−1, uniform mesopores of 2.8nm, and special phenyl-functionalized pore-walls. Parabens, such as methyl paraben, ethyl paraben and propyl paraben, were extracted from water-based skin toners using one step of the RAM-SPE and were then analysed by a HPLC-DAD system. The SPE conditions were optimized by studying the parameters, such as the adsorbent amount, elution solvent type, adsorption time and desorption time, that influence the extraction efficiency. For each analyte, there were good linearities of approximately 0.10–120μgmL−1 with determination coefficients (R2)>0.995. The sensitivity was as low as 0.01–0.025μgmL−1 for the LOD, and the percent recoveries were 98.37–105.84%. The intra-day and inter-day RSDs were 1.44–6.11% (n=6) and 3.12–11.70% (n=6), respectively. The results indicated that this method with novel RAM-SPE adsorbents is sensitive and convenient. The results also offered an attractive alternative for the extraction and determination of paraben preservatives in a complex matrix, such as cosmetics.

Advances on the development of detection methods for the phthalate esters in food

Phthalate esters are most widely used as plasticizers which have toxicity and carcinogenicity. Phthalate esters are found as contaminants in many food products and they are a branch of compounds, homologues and isomers, which present similar structures and properties. And the residue contents vary a lot in different matrices. Efficient sample pretreatment, highly selective separation mode, sensitive detection methods as well as reducing background interference are challenges for their determination in complex samples. In this paper, some sample pretreatment methods such as liquid-liquid extraction, liquid-liquid micro-extraction, solid phase extraction, solid phase micro-extraction, matrix solid-phase extraction and other traditional and new types of extraction and purification technology applied in the food samples are reviewed. The characteristics of analytical methods including gas chromatography, liquid chromatography, tandem mass spectrometry, high resolution mass spectrometry, enzyme-linked immunoassay, and ion mobility spectrometry are also discussed.

A combined technique for the pretreatment of ultra trace bisphenol A in environmental water based on magnetic matrix solid phase extraction assisted dispersive liquid–liquid microextraction

Magnetic matrix solid phase dispersion (MMSPD) assisted dispersive liquid–liquid microextraction (DLLME) for the ultrasensitive determination of bisphenol A (BPA) in environmental water was developed with HPLC-FLU detection.

Quantification of penoxsulam in soil and rice samples by matrix solid phase extraction and liquid-liquid extraction followed by HPLC-UV method.

The paper exploits the development of novel, simple and sensitive methodology involving matrix solid phase dispersion (MSPD) and the comparison of MSPD with liquid-liquid extraction (LLE) for the evaluation of residual penoxsulam in soil and rice samples. Extracted samples were analyzed by high-performance liquid chromatography (HPLC) with ultraviolet detector at 230nm. Both methods were optimized, considering different parameters, and under optimum conditions, the mean recoveries obtained were in the range of 85-104% for MSPD and 78.8-90.7% for LLE. Precision values expressed as relative standard deviation (RSD) were ≤10 for MSPD and ≤15 for LLE. Linearity for penoxsulam was in the range of 0.01-20μgmL(-1) with limits of detection and limits of quantification of 0.01 and 0.03mgkg(-1), respectively.

Estimating uncertainty in matrix solid phase extraction methodology for the determination of chlorinated compounds in fish

In this study, a detailed process of uncertainty estimation associated with matrix solid phase dispersion method (MSPD) for the extraction of organochlorinated compounds from fish coupled with gas chromatography is given. The evaluation of uncertainty arising from trueness using fully nested experimental designs is presented by estimating proportional bias, in terms of recovery. The uncertainty of measurements associated with the actual chromatographic process was also estimated. The methodology was applied for the determination of selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in real fish samples, from selected study locations in Western Greece (Mesologgi lagoon and Trichonida lake), based on chromatographic techniques. The sources of uncertainty are presented along with the calculated combined uncertainty terms derived from the analytical procedure and chromatographic process. The estimation of uncertainty was included in the presentation of final determinations.

Analysis of cypermethrin residues and its main degradation products in soil and formulation samples by gas chromatography-electron impact-mass spectrometry in the selective ion monitoring mode

A fast, simple and inexpensive sample preparation method based on the matrix solid-phase extraction (SPE) technique is proposed for the isolation of cypermethrin and its metabolite residues from soils. Both the extraction and clean-up procedures were carried out in two steps and target compounds were determined by gas chromatography coupled with electron-impact mass spectrometry (GC-EI/MS). The characteristic ions and fragmentation mechanism of cypermethrin were evaluated by electron impact ionization mass spectrometry (EI/MS). After the optimization of different parameters, such as the extraction solvent, the pesticide was extracted from the matrix with methanol/acetone in a Soxhlet extractor, cleaned up on a Florisil column by elution with a mixture of 30% ethyl acetate in n-hexane and analyzed by gas chromatography-electron impact ionization mass spectrometry (GC-EI/MS) in the selected ion-monitoring mode (SIM) with permethrin as internal standard. Recovery was in the range 77–118% with relative standard deviations (RSD) between 2.5% and 10.2%. The limit of detection (LOD) was 6.5 µg/kg for cypermethrin. The developed method was linear in the injection range 6–30 ng, with correlation coefficients greater than 0.9957.

Analysis of multi-class preservatives in leave-on and rinse-off cosmetics by matrix solid-phase dispersion

Matrix solid-phase extraction has been successfully applied for the determination of multi-class preservatives in a wide variety of cosmetic samples including rinse-off and leave-on products. After extraction, derivatization with acetic anhydride, and gas chromatography-mass spectrometry analysis were performed. Optimization studies were done on real non-spiked and spiked leave-on and rinse-off cosmetic samples. The selection of the most suitable extraction conditions was made using statistical tools such as ANOVA, as well as factorial experimental designs. The final optimized conditions were common for both groups of cosmetics and included the dispersion of the sample with Florisil (1:4), and the elution of the MSPD column with 5 mL of hexane/acetone (1:1). After derivatization, the extract was analyzed without any further clean-up or concentration step. Accuracy, precision, linearity and detection limits were evaluated to assess the performance of the proposed method. The recovery studies on leave-on and rinse-off cosmetics gave satisfactory values (>78% for all analytes in all the samples) with an average relative standard deviation value of 4.2%. The quantification limits were well below those set by the international cosmetic regulations, making this multi-component analytical method suitable for routine control. The analysis of a broad range of cosmetics including body milk, moisturizing creams, anti-stretch marks creams, hand creams, deodorant, shampoos, liquid soaps, makeup, sun milk, hand soaps, among others, demonstrated the high use of most of the target preservatives, especially butylated hydroxytoluene, methylparaben, propylparaben, and butylparaben.

Matrix solid-phase dispersion extraction and gas chromatographic screening of polychlorinated biphenyls in fish

A matrix solid-phase extraction (MSPD) and gas chromatographic-electron-capture detection method for determining polychlorinated biphenyls (PCBs) in fish (grass carp) is described. The method uses an octadecylsilyl-derivatized silica and acidic silica gel-based MSPD co-column for direct in-line clean-up. The performance of the method compares favourably with that of the traditional approach but the sample size, analysis time and overall cost are lower. The method may serve as a screening protocol for the isolation and determination of PCBs in fish.