Extraction techniques matrix solid phase dispersion

When liquid samples such as serum, plasma, milk, or honey are not to be extracted using direct liquid-liquid partitions with organic solvents but through use of solid-phase extraction or matrix solid-phase dispersion techniques, dilution with water (323, 324), phosphate buffer saline (325), or phosphoric acid (326, 327) is often the only sample preparation procedure applied. Milk analysis sometimes requires further pretreatment for fat removal (328). Centrifugation at about 7000g at 4-10 C for 20 min is the usually applied procedure for making the fat floating on top of milk readily eliminated. 

In our laboratory, an on-flow LC-NMR-MS screening (Figure 5.1.1) was applied to both saponin fractions which were not separated into pure compounds by classical column chromatography and further to total asterosaponin fractions obtained by the micropreparative technique, matrix solid-phase dispersion (MSPD) extraction [45] (see Figure 5.1.2). The LC-NMR-MS hyphenation is set up in the widely used parallel configuration of NMR and mass spectrometer (Figure 5.1.3). Typically, absolute amounts of asterosaponin mixtures of about 500 xg - 1 mg are injected onto the column. 

A technique that attempts to combine the extraction and SPE into a single step is matrix solid-phase dispersion (MSPD). In this technique, a nonpolar (such as Cig) SPE sorbent is blended directly into tissue matrix, the mixture is packaged into an SPE cartridge, and the cartridge is eluted like a typical SPE cartridge. The advantage of MSPD is reduced sample size and increased efficiency due to a reduced number of steps. 

Solid-phase sorbents are also used in a technique known as matrix solid-phase dispersion (MSPD). MSPD is a patented process first reported in 1989 for conducting the simultaneous disruption and extraction of solid and semi-solid samples. The technique is rapid and requires low volumes (ca. 10 mL) of solvents. One problem that has hindered further progress in pesticide residues analysis is the high ratio of sorbent to sample, typically 0.5-2 g of sorbent per 0.5 g of sample. This limits the sample size and creates problems with representative sub-sampling. It permits complete fractionation of the sample matrix components and also the ability to elute selectively a single compound or class of compounds from the same sample. Excellent reviews of the practical and theoretical aspects of MSPD " and applications in food analysis were presented by Barker.Torres et reported the use of MSPD for the... 

In the past two decades quite a few new techniques have emerged for the treatment of aqueous samples prior to organic analysis. Perhaps the most important development is that of solid-phase extraction (SPE), which has successfully replaced many off-line steps. This technique can be considered to have introduced a genuine new era in sample handling [1]. The many varieties in which the technique is available and can be applied have made it the key step in handling of aqueous samples. Among the successful varieties are solid-phase microextraction (SPME), matrix solid-phase dispersion, disk extraction and immunosorbent extraction. Several reviews covering these topics have appeared in the literature in the past decade (see e.g. Refs. [2,3] for nonylphenol... 

In matrix solid-phase dispersion (MSPD) the sample is mixed with a suitable powdered solid-phase until a homogeneous dry, free flowing powder is obtained with the sample dispersed over the entire material. A wide variety of solid-phase materials can be used, but for the non-ionic surfactants usually a reversed-phase C18 type of sorbent is applied. The mixture is subsequently (usually dry) packed into a glass column. Next, the analytes of interest are eluted with a suitable solvent or solvent mixture. The competition between reversed-phase hydrophobic chains in the dispersed solid-phase and the solvents results in separation of lipids from analytes. Separation of analytes and interfering substances can also be achieved if polarity differences are present. The MSPD technique has been proven to be successful for a variety of matrices and a wide range of compounds [43], thanks to its sequential extraction matrices analysed include fish tissues [44,45] as well as other diverse materials [46,47]. 

In contrast to the solid-phase extraction approach, only nonpolar Cis-deriva-tized silica has been used as the sorbent in matrix solid-phase dispersion technique. This technique has been successfully applied in the determination of furazolidone in meat (66), milk (181), and swine tissues (180). 

A matrix solid-phase dispersion technique has been further applied for the determination of oxytetracycline, tetracycline, and chlortetracycline in milk (290, 311), using octadecylsilyl- (Cjg) derivatized silica as the solid phase. To facilitate extraction of the tetracycline antibiotics from milk, addition of an equal ratio of EDTA to oxalic acid has been found advantageous. 

Starting with a description of the analytical challenge in Chapter 19, the third part, which is devoted to analytical attitudes, proceeds with a detailed description in Chapter 20 of modern sample preparation procedures including solid-phase extraction, matrix solid-phase dispersion, use of restricted-access media, supercritical fluid extraction, and immunoaffinity cleanup. Flexible derivatization techniques including fluorescence, ultraviolet-visible, enzymatic, and photochemical derivatization procedures are presented in Chapter 21. 

Figure 5.1.2 Matrix solid-phase dispersion (MSPD) extraction as a micro-preparative extraction technique for an on-flow LC-NMR-MS screening. Since the latter requires only sample amounts in the 0.5-2 mg range, the sample preparation can be achieved by fast small-scale extraction procedures, such as MSPD. This is a sample preparation technique that combines both sample homogenisation and extraction of compounds of interest in one single step starting from the intact sample material. Thus, it simplifies the extraction and clean-up steps, reduces the sample manipulation and is much faster than conventional techniques. It is therefore very well suited for a rough separation of extracts into classes of compounds of similar polarities, which can then be submitted to LC-NMR-MS analysis...

Matrix solid-phase dispersion (MSPD) is the extraction method of choice for the analysis of solid samples, such as plant material, foodstuffs or tissue samples [26]. This method has been developed especially for solid or viscous matrices. MSPD is preferable to other extraction techniques, because the solid or viscous sample can be directly mixed with the sorbent material of the stationary phase [27]. As the carotenoid stereoisomers stay bound in their biological matrix until the elution step, they are protected against isomerisation and oxidation [28]. The extraction scheme of MSPD is shown in Figure 5.2.1. 

A variety of solvent extraction techniques have been used to extract antioxidants from food matrices. The most commonly used is maceration or homogenization of the sample with an extraction solvent however, alternative procedures have been developed including pressurized fluid extraction (PFE), ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE), and matrix solid-phase dispersion (MSPD), among others. The principles of each extraction technique will be briefly discussed. 

An evaluation of the scientific literature reveals that over 500 papers on veterinary drug residue analysis were published in the 5-year period of 2005-2009. Liquid extraction (LE) and liquid-solid extraction (LSE) were found to be very popular sample treatment techniques that were used in 30% and 60% of the reported studies, respectively. Here, LE includes all liquid-based approaches such as liquid-liquid extraction (LLE), extrelut liquid-liquid extraction, liquid-liquid micro-extraction, and pressurized liquid extraction (PLE). LSE includes solid phase extraction (SPE) and all other sorbent-based extraction procedures, such as solid phase micro-extraction (SPME), stir bar sorptive extraction (SBSE), restricted-access materials (RAM), turbulent-flow chromatography (TEC), dispersive SPE (dSPE), and matrix solid phase dispersion... 

Matrix solid phase dispersion (MSPD) is an effective sample preparation technique that combines extraction and purification in one step. Barker et al. defined MSPD procedures as those that use dispersing sorbents with chemical modification of the silica surface (e.g.. Cl8, C8). Samples are blended and dispersed on particles (diameters of 40-100 p.m) using a glass or agate mortar and pestle (Pig. 4.3). The use of ceramic or clay mortars and pestles can result in loss of analytes. A disadvantage of the method is the traditionally high sorbent sample ratios... 

Several extraction techniques have been reported in the literature for the analysis of sulfonamides. Because of their polar nature, sulfonamides are readily extracted by organic solvents ° ° the most commonly used are acetonitrile.Other organic solvents used for analyte extraction and protein precipitation include dichloromethane, " acetone, ethanol, chloroform, and ethyl acetate, " which are often used either alone or in conjunction with one another. Other techniques used for protein precipitation include the use of acids such as perchloric or formic and the use of basic buffers such as potassium hydrogen phosphate and ammonium sulfate. In the case of honey, the use of acids such as trichloroacetic, " " hydrochloric, and phosphoric is necessary for hydrolysis, releasing carbohydrate-bound sulfonamide residues. Other extraction techniques reported in the literature include the use of pressurized liquid extractions, " matrix solid-phase dispersion, and magnetic molec-ularly imprinted polymers. Of additional note, several authors have observed that analyte recoveries were largely... 

Some techniques that combine the properties of extraction and cleanup are supercritical fluid extraction (SEE) and matrix solid-phase dispersion (MSPD). Supercritical fluids, i.e., at a temperature and pressure in excess of their critical point, have unique properties for selective extraction of analytes from a sample. Solid samples are mixed with an inert dispersant, such as hydromatrix, and the mixture packed into the cell of the SEE apparatus. The sample is extracted with supercritical CO2, with or without addition of organic modifier, and the extracted analytes may be collected inline or offline on suitable adsorbents (Figure 3). Further cleanup of the sample extract may be performed using SPE. MSPD is based on intimate mixing of animal tissue sample with a bonded silica, such as Cig, and packing of the blended material into a column from which interferences can be eluted by washing with solvents and the analytes eluted using a selective solvent. 

Extraction of pesticide residues from liquid samples can be performed using a solid sorbent material. Currently available sorbent extraction techniques include (1) solid-phase extraction (SPE), (2) solid-phase microextraction (SPME), and (3) stir-bar sorptive extraction (SBSE). In the case of solid samples, a liquid extraction of pesticide residues (transfer into a solution) usually precedes the sorption step thus, it should be considered rather as a clean-up than an extraction. Matrix solid-phase dispersion (MSPD) represents a unique SPE approach that combines extraction and clean-up of solid or semisolid food samples in one step. In MSPD, the sample is mixed with a sorbent (Florisil, Cig, Cg) that serves as a solid support in sample disruption and dispersion. The resulting mix is packed into a column from which the analytes are eluted while separated matrix components are retained by the sorbent. The main drawbacks of this approach comprise rather small sample sizes ( 0.5g) and a relatively high consumption of expensive sorbents. 

Matrix solid-phase dispersion (MSPD) is an SPE variant where samples are ground and mixed with a support. In the initial application, samples were placed in a disposable column previously packed with Florisil, which trapped the fat from the sample and allowed the compounds of interest to be eluted. This has successfully been applied to the determination of lipophilic pesticides from both fatty and non-fatty matrixes. Recently, an orthogonal technique, dispersive solid-phase extraction, for the isolation and analysis of a variety of pesticides on numerous food matrixes has been introduced. The technique is called QuEChERS, which stands for quick, easy, cheap, effective, rugged, and safe. The technique offers advantages in time and solvent usage since it uses approximately 10 ml of solvent per sample when compared to the potentially hundreds of milliliters of solvent used for more standard extraction and isolation protocols. It uses a combination of MgS04 and primary secondary amine (PSA) sorbent not only to remove water and non-target compounds, but also isolate the compounds of interest. 

Whichever technique is used for extraction, an additional clean-up procedure is usually included prior to chromatographic analysis in order to minimize matrix effects caused by the presence of coextracted compounds. Sorbent-based (extraction and clean-up) techniques such as SPE [42,43], solid-phase microextraction (SPME) [44-46], matrix solid-phase dispersion (MSPD) [47,48], and MIPs [49,50] are among the most conunonly used. SPE can be used as a direct extraction technique for liquid... 

Today, sample preparation is maybe the step that most influences the accuracy of the whole analytic method, with the extraction of pesticide residues from environmental matrices the key factor for achieving it. There is no question that in the first decade of the century, SPE technique [72] is the most employed alternative to the classical solid-liquid [13] and liquid-liquid [14] extractions. These classical techniques present multiple disadvantages such as the low recovery of polar pesticides and transformation products (in the case of liquid-liquid extractions) and use of large volumes of solvents. Furthermore, several variants emerged based on the SPE technique solid-phase microextraction (SPME) [72-74], in-tube solid-phase microextraction [72,75,76], matrix solid-phase dispersion [72,77,78], and stir-bar sorptive extraction [72,79]. 

The extraction of EDCs from biological samples is often more complex than from aqueous and solid samples because of matrix interferences. Various techniques like acidic digestion, saponification, liquid-liquid partition, matrix sohd-phase dispersion (MSPD), as well as Soxhlet... 

Solid-phase microextraction (SPME) was developed to address the need to facilitate rapid sample preparation both in the laboratory and onsite where the investigated system is located. In this technique, a small amount of extracting phase dispersed on a solid support is exposed to the sample for a well-defined period of time. In one approach, a partitioning equilibrium between the sample matrix and extraction phase is reached. In this case, convection conditions do not affect the amount extracted. In the second approach utilizing short time pre-equilibrium extraction, if convection/agitation is constant, the amount of analyte extracted is related to extraction time. Quantification can then be performed based on timed... 

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