Matrix Solid-phase Dispersion Process Research Articles

A dual preconcentration method by combining micro matrix solid-phase dispersion extraction with field-enhanced sample injection and micelle to cyclodextrin stacking for sensitive analysis of neutral coumarins.

A rapid, sensitive, environmental friendly dual preconcentration method by combining micro matrix solid-phase dispersion extraction with field-enhanced sample injection and micelle to cyclodextrin stacking has been developed for the determination of furocoumarins. Molecular sieve, KIT-6, was used as an adsorbent in micro matrix solid-phase dispersion process. The important parameters affecting off-line and online CE preconcentration efficiency were optimized. Under the optimal experimental conditions, all analytes showed good linearity (R2 >0.999). The LODs of notopterol, isoimperatorin, and imperatorin were 0.1μg/mL, 1.2mg/kg, and 1.0mg/kg, respectively. Compared with the normal CE method, the enrichment times were up to 300. Moreover, Angelicae Dahuricae Radix was used as the mode of complex solid sample matrix to demonstrate the prospect of application of this methodology. The results showed the proposed strategy is promising for determining trace furocoumarins in complex matrix samples, which might be applied as a powerful and economic tool in monitoring illegal cosmetic adding.

Analysis of Melamine in Milk Powder by CNT-MIP with Matrix Solid Phase Dispersion and LC-MS/MS

In this work, a simple and selective method based on matrix solid phase dispersion (MSPD) using molecularly imprinted polymers (MIPs) as sorbents was successfully developed for the determination of melamine (MEL) in milk powder. The MIPs have been prepared by surface imprinted polymerization method using carbon nanotube (CNT) as support, MEL as template molecule, γ-aminopropyltriethoxysilane as functional monomer, and tetraethyl orthosilicate as cross-linking agent. The MIPs were characterized by Fourier transform infrared spectrometer and scanning electron microscopy. At the same time, the adsorption isotherm, dynamic adsorption, and selective adsorption of MIPs to MEL were also studied. The prepared MIPs were used as dispersant of MSPD to extraction and separate MEL in milk powder. We optimized the extraction conditions as follows: the ratio of MIPs to sample was 2:3; the dispersion time was 10 min; washing solvent was 2.0 mL acetonitrile; and elution solvent was 4.0 mL ammonium methanol (5:95, v/v). Once the MSPD process was completed, the MEL extracted from milk powder was determined by LC-MS/MS. Under the optimal conditions, the limit of detection of MEL was 0.2 ng g−1. The relative standard deviations of intra-day and inter-day were obtained in the range of 0.4∼5.1 %. The satisfied recoveries of MEL were 92.5∼97.2 %. The MIP-MSPD method has some advantages, such as higher selectivity, lower cost of preparation, less time consuming and organic solvent consumption, simpler sample pretreatment procedure, and higher extraction recovery compared with those existing methods which were used for determination of MEL.

Analysis of malachite green in aquatic products by carbon nanotube-based molecularly imprinted - matrix solid phase dispersion.

A simple method based on matrix solid phase dispersion (MSPD) using molecularly imprinted polymers (MIPs) as sorbents for selective extraction of malachite green (MG) from aquatic products was developed. The MIPs were prepared by using carbon nanotube as support, MG as template, methacrylic acid as functional monomer, ethyleneglycol dimethacrylate as crosslinker and methylene chloride as solvent. The MIPs were characterized by Fourier transform infrared spectrometry and transmission electron microscopy. The isothermal adsorption, kinetics absorption and selective adsorption experiments were carried out. We optimized the extraction conditions as follows: the ratio of MIPs to sample was 2:3, the dispersion time was 15min, washing solvent was 4mL 50% aqueous methanol and elution solvent was 3mL methanol-acetic acid (98: 2, v/v). Once the MSPD process was completed, the MG extracted from aquatic products was determined by high performance liquid chromatography. The detection limit of MG was 0.7μgkg(-1). The relative standard deviations of intra-day and inter-day were obtained in the range of 0.9%-4.7% and 3.4%-9.8%, respectively. In order to evaluate the applicability and reliability of the proposed method, it was applied to determine MG in different aquatic products samples including fish, shrimp, squid and crabs. The satisfied recoveries were in the range of 89.2%-104.6%. The results showed that this method is faster, simpler and makes extraction and purification in the same system.

Determination of aflatoxins in rice samples by ultrasound-assisted matrix solid-phase dispersion.

This work describes the application of ultrasound-assisted matrix solid-phase dispersion as an extraction and sample preparation approach for aflatoxins (B1, B2, G1 and G2) and subsequent determination of them by high-performance liquid chromatography-fluorescence detection. A Box-Behnken design in combination with response surface methodology was used to determine the affecting parameters on the extraction procedure. The influence of different variables including type of dispersing phase, sample-to-dispersing phase ratio, type and quantity of clean-up phase, ultrasonication time, ultrasonication temperature, nature and volume of the elution solvent was investigated in the optimization study. C18, primary-secondary amine (PSA) and acetonitrile were selected as dispersing phase, clean-up phase and elution solvent, respectively. The obtained optimized values were sample-to-dispersing phase ratio of 1 : 1, 60 mg of PSA, 11 min ultrasonication time, 30°C ultrasonication temperature and 4 mL acetonitrile. Under the optimal conditions, the limits of detection were ranged from 0.09 to 0.14 ng g(-1) and the precisions [relative standard deviation (RSD%)] were <8.6%. The recoveries of the matrix solid-phase dispersion process ranged from 78 to 83% with RSD <10% in all cases. Finally, this method was successfully applied to the extraction of trace amounts of aflatoxins in rice samples.

Multivariate optimisation of an ultrasound assisted-matrix solid-phase dispersion method combined with LC-fluorescence detection for simultaneous extraction and determination of aflatoxins in pistachio nut samples

This paper describes the application of ultrasound-assisted matrix solid-phase dispersion as an extraction and clean-up procedure for aflatoxins (B1, B2, G1 and G2) and subsequent determination by LC-fluorescence detection. A Box–Behnken design was used to determine the parameters influencing the extraction procedure through response surface methodology and experimental design. The influence of different variables including type of dispersing phase, sample-to-dispersing phase ratio, type and quantity of clean-up phase, ultrasonication time, ultrasonication temperature, nature and volume of the elution solvent were investigated in the optimisation study. C18, graphitic carbon black and acetonitrile were selected as dispersing phase, clean-up phase and elution solvent, respectively. The optimised values were sample-to-dispersing phase ratio of 1:1, 50 mg of graphitic carbon black, 11 min ultrasonication time, 30°C ultrasonication temperature and 3 ml acetonitrile. Under the optimal conditions the limits of detection (LODs) were ranged from 0.04–0.11 µg kg−1 and the relative standard deviations (RSDs) of the extraction method were less than 8.6%. The recoveries of the matrix solid-phase dispersion process ranged from 74% to 78% with relative standard deviation lower than 9% in all cases. Finally, the matrix solid-phase dispersion was successfully applied to extraction of trace amounts of aflatoxins in pistachio samples.

Extraction of Anthraquinones from Rhubarb by a Molecularly Imprinted–Matrix Solid-Phase Dispersion Method with HPLC Detection

A simple method based on matrix solid-phase dispersion for selective extraction of anthraquinones from rhubarb samples was developed using a molecularly imprinted polymer as sorbent. The molecularly imprinted polymer was prepared using emodin as the template molecule, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linking agent. The polymer was characterized by scanning electron microscopy and Fourier-transform infrared spectrometry. Isothermal adsorption and dynamic adsorption experiments were performed. The best extraction conditions for anthraquinones were obtained at a ratio of molecularly imprinted polymer to sample of 1:1, a dispersion time of 5 minutes, with 5% aqueous methanol as the washing solvent, and an elution solvent of methanol-acetic acid (99:1, v/v). Once the matrix solid-phase dispersion process was optimized, the extract was reacted with 8% hydrochloric acid for hydrolysis. The anthraquinones extracted from rhubarb were determined by liquid chromatography. The detection limits of chrysophanol, emodin, physcion, and aloe-emodin were 0.23, 0.24, 0.28, and 0.27 µg mL−1, respectively. The proposed method was compared with the method in Chinese pharmacopoeia, and the results show that the extraction yield of anthraquinones obtained by molecularly imprinted polymer–matrix solid-phase dispersion method was higher. Moreover, the proposed method is faster and simpler and can achieve extraction and purification in the same system.

Matrix solid‐phase dispersion with sand in chromatographic analysis of essential oils in herbs

Matrix solid-phase dispersion (MSPD) is a very simple, cheap and relatively quick sample preparation procedure which involves simultaneous disruption and extraction of various solid and semi-solid samples due to the direct mechanical blending of the sample with a SPE sorbent, mainly C(18). Little is known about MSPD application as a sample preparation method for the analysis of essential oil components in herbs. To evaluate if C(18) sorbent, commonly used in MSPD process, can be substituted with sand in the procedure of essential oil analysis. Essential oil extracts were obtained from mint, sage, chamomile, marjoram, savory and oregano using MSPD with C(18) sorbent or sand, pressurised liquid extraction and steam distillation. Their qualitative and quantitative compositions ware established by GC-MS and GC-FID. The results prove that C(18) sorbent can be substituted with sand in the procedure of essential oil analysis in herbs. The recoveries of essential oil components estimated using MSPD/sand are almost equal to those using pressurised liquid extraction. The results presented in the paper reveal that MSPD with sand is suitable for the isolation of essential oil components from herbs. Its extraction efficiency is equivalent to pressurised liquid extraction, recognised as one of the most efficient extraction methods. The cost of MSPD procedure for essential oil analysis can be significantly diminished by substituting C(18) with sand.

Application of the MSPD Technique for the HPLC Analysis of Rutin in Sambucus nigra L.: The Linear Correlation of the Matrix Solid-Phase Dispersion Process

This paper presents possibilities of estimating the true value of an analyte concentration in a plant material by means of the matrix solid-phase dispersion (MSPD) based on the law of the partition process and on the properly adapted equations associated with this process. This idea has been developed for analysis of rutin amount in Sambucus nigra L. (elderberry). The effects of experimental variables, such as the mass ratio of sorbent to plant matrix and buffer pH, have been studied. Rutin amounts estimated using MSPD were verified with the amounts obtained by employing pressurized liquid extraction (PLE). The extracts were analyzed by high-performance liquid chromatography (HPLC). To obtain the true value of rutin concentration in elderberry, the MSPD process should be carried out in the conditions for which the dependence between the reciprocal of the analyte yield and sorbent mass/plant mass ratio is linear. Rutin yield estimated by MSPD in such conditions equal 2.90% w/w and is almost the same as the amount obtained by PLE (2.88% w/w). The results show that PLE, which recently has been more and more frequently used in the analysis of herb material and which requires the application of expensive PLE equipment, can be replaced by the relatively cheap and effective MSPD process.

Molecularly imprinted matrix solid-phase dispersion for extraction of chloramphenicol in fish tissues coupled with high-performance liquid chromatography determination

The synthesis and evaluation of a molecularly imprinted polymer (MIP) as a selective matrix solid-phase dispersion (MSPD) sorbent, coupled with high-performance liquid chromatography for the efficient determination of chloramphenicol (CAP) in fish tissues are studied. The polymer was prepared using CAP as the template molecule, vinylpyridine as the functional monomer and ethylene glycol dimethacrylate as the cross-linking monomer, and sodium dodecyl sulfate as the surfactant in the presence of water as a solvent by miniemulsion polymerization. The CAP-imprinted polymers and nonimprinted polymers (NIPs) were characterized by Fourier transform IR spectroscopy, scanning electron microscopy, and static adsorption experiments. The CAP-imprinted material prepared showed high adsorption capacity, significant selectivity, and good site accessibility. The maximum static adsorption capacity of the CAP-imprinted and the NIP material for CAP was 78.4 and 59.9 mg g(-1), respectively. The relative selectivity factors of this CAP-imprinted material were larger than 1.9. Several parameters influencing the MSPD process were optimized. Finally, the CAP-imprinted polymers were used as the sorbent in MSPD to determine CAP in three kinds of fishes and resulted in satisfactory recovery in the range 89.8-101.43%. CAP-imprinted polymer as a sorbent in MSPD is better than C18 and attapulgite in terms of both recovery and percent relative standard deviation. The baseline noise was measured from a chromatogram of a blank fish sample which was treated after the MSPD procedure using CAP-imprinted polymer as a sorbent. Signal values of 3 times the noise (signal-to-noise ratio of 3) and 10 times the noise (signal-to-noise ratio of 10) were used to calculate the limit of detection and the limit of quantitation of the calibration curve. The limit of detection for CAP was 1.2 ng g(-1) and the limit of quantitation was 3.9 ng g(-1).

Development of a matrix solid-phase dispersion method for the determination of polycyclic aromatic hydrocarbons in sewage sludge samples

A new, single-step extraction and purification method based on matrix solid-phase dispersion (MSPD) was developed to determine 17 polycyclic aromatic hydrocarbons (PAHs) in sewage sludge samples. The MSPD method consists of sample homogenisation, exhaustive extraction and clean-up by a single process. The different operational parameters of the method, such as the type of dispersant, type and amount of additives, clean-up co-sorbent and extractive solvent were evaluated. Reversed-phase (C18) and polymeric (Oasis HLB and Oasis MAX) materials, as well as normal phase sorbents (Florisil, silica, neutral alumina) and an inert support (sand) were tested to assess the sorbents effect on the yield and selectivity of the MSPD process. Analysis of extracts was performed by high performance liquid chromatography (HPLC) coupled with fluorescence detection. Quantification limits obtained for all of these considered compounds (between 0.0001 and 0.005 μg g −1 dry mass) were well below of the limits recommended in the EU. The extraction yields for the different compounds obtained by MSPD ranged from 76.3% to 103.6%. On the other hand, the extraction efficiency of the optimised method is compared with that achieved by microwave-assisted extraction and the method was applied to the analysis of real sewage sludge samples. A certified reference material (sewage sludge (BCR 088)) and a reference material (sewage sludge (RTC-CNS312-04)) were used to validate the proposed method.

Application of matrix solid-phase dispersion to the propham and maleic hydrazide determination in potatoes by differential pulse voltammetry and HPLC

The application of the matrix solid-phase dispersion (MSPD) process as sample treatment in connection with the electrochemical detection is studied for the first time. For this purpose, a novel methodology is introduced for the extraction of propham and maleic hydrazide herbicides from potatoes samples based in the MSPD process prior to their electrochemical detection. Potato samples disruption was done by blending them with C 8 bonded-phase and selective herbicide extraction was achieved by successive treatment of the blended with 50 mM phosphate buffer pH 7.4 (for maleic hydrazide) and methanol (for propham). The extraction procedure efficiency was estimated using differential pulse voltammetry in potato samples spiked with the herbicides yielding recovery values of 98% and 68% for propham and maleic hydrazide, respectively. No significant adverse effect of the MSPD process was observed on the herbicides electrochemical signals. For comparison, recovery studies using HPLC with UV detection were carried out and a good correlation in the results obtained by using both techniques was observed.

Multi-residue screening of chlorinated and brominated compounds from aquaculture samples using matrix solid-phase dispersion—gas chromatography–mass spectrometry

An effective multiresidual method for the trace analysis of fifteen compounds from a diverse group of pesticides, polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyl (PCBs) and polybrominated biphenyl (PBBs) in aquaculture feed is described. The analytical procedure is based on the matrix solid-phase dispersion (MSPD) of feed sample and subsequent elution with hexane. The MSPD process was evaluated using an asymmetrical experimental design 2 33 2//9. Factors such as C 18 sorbent amount, kind of adsorbents, solvent volume and elution mode were considered. The results suggest that the operational MSPD conditions are elution with pressure, 1 g of C 18, basic alumina as adsorbent and 30 mL of hexane. The overall method including MSPD procedure and GC coupled to mass spectrometry (MS/MS) has been applied to several samples of aquaculture feed and marine species. Precision and accuracy of the analytical method were determined using the reference material from the International Atomic Energy Agency (IAEA-406), showing a good agreement to the referenced values.

Extracción de polifenoles bioactivos del bagazo de uva mediante un método de dispersión de matriz en fase sólida

A matrix solid-phase dispersion process to extract polyphenols from grape marc, a winemaking byproduct, has been optimized by Response Surface Methodology. The dependent variables evaluated were the total polyphenols content, flavanols, hydrocynnamates, and flavonoids. The performance of the extraction method in terms of linearity and precision has also been assessed. The optimized MSPD method provides good results to extract polyphenols from white winemaking byproducts, much less studied than those from red wines, requiring low solvent consumption and being low cost and fast (15 min). The analytical instrumentation is available almost everywhere, thus becoming a ready-to-use methodology for virtually any control or winery laboratory. The optimized method has been applied to a set of bagasse samples from Albariño grapes (Vitis vinifera sp) cultivated in Galicia (NW Spain) and coming from five different types of grapevine training techniques. The vine training factor was significant on the basis of the content of the different groups of polyphenols determined in the MSPD extracts.