Sample preparation matrices

Attempts to adapt MALDI-TOF to allow high-throughput analysis [48] have been made, but drawbacks still exist regarding pending sample preparation, matrix effects and the intrinsic inhomogeneity of the sample/matrix crystals combined with the positional resolution of the laser beam. Nevertheless, e.g. for oligonucleotides, it has been shown that autosampler arrays can provide rapid and reproducible results [49]. 

Sample preparation Matrix Analytes Analytical technique Detection Internal standard Ref. 

Standardization—External standards, standard additions, and internal standards are a common feature of many quantitative analyses. Suggested experiments using these standardization methods are found in later chapters. A good project experiment for introducing external standardization, standard additions, and the importance of the sample s matrix is to explore the effect of pH on the quantitative analysis of an acid-base indicator. Using bromothymol blue as an example, external standards can be prepared in a pH 9 buffer and used to analyze samples buffered to different pHs in the range of 6-10. Results can be compared with those obtained using a standard addition. 

The following experiments introduce students to the importance of sample preparation and methods for extracting analytes from their matrix. Each experiment includes a brief description of the sample and analyte, as well as the method of analysis used to measure the analyte s concentration. 

Before sample preparation, surrogate compounds must be added to the matrix. These are used to evaluate the efficiency of recovery of sample for any analytical method. Surrogate standards are often brominated, fluorinated, or isotopically labeled compounds that are not expected to be present in environmental media. If the surrogates are detected by GC/MS within the specified range, it is... 

Continuing calibration for a Series Method is performed using calibration check compounds. Surrogate compounds are added to the matrix before sample preparation to evaluate recovery levels. To check GC retention times, internal standards are added to a sample after its preparation for analysis. 

Standards used to constmct a cahbration curve must be prepared such that the matrix of the standard is identical to the sample s matrix because the values of the parameters k and b associated with a linear cahbration curve are matrix dependent. Many areas of chemical analysis are plagued by matrix effects, and it is often difficult to duphcate the sample matrix when preparing external standards. Because it is desirable to eliminate matrix effects, cahbration in the sample matrix itself can be performed. This approach is called the standard addition method (SAM) (14). In this method, the standards are added to the sample matrix and the response of the analyte plus the standard is monitored as a function of the added amount of the standard. The initial response is assumed to be Rq, and the relationship between the response and the concentration of the analyte is... 

Theoretical and applied aspects of microwave heating, as well as the advantages of its application are discussed for the individual analytical processes and also for the sample preparation procedures. Special attention is paid to the various preconcentration techniques, in part, sorption and extraction. Improvement of microwave-assisted solution preconcentration is shown on the example of separation of noble metals from matrix components by complexing sorbents. Advantages of microwave-assisted extraction and principles of choice of appropriate solvent are considered for the extraction of organic contaminants from solutions and solid samples by alcohols and room-temperature ionic liquids (RTILs). 

DEVELOPING SAMPLE PREPARATION AND DETERMINATION OF TOTAL IODINE IN COMPLEX ORGANIC MATRIX... 

The methods I- 4 of sample preparation are classics. As a mle they give a high value of blank and some of them take a lot of time. Microwave sample preparation is perspective, more convenient and much more faster procedure than classical mineralization. There are some problems with the combination Cendall-Kolthoff s kinetic method and microwave sample preparation which discussed. The experimental data of different complex organic matrix are demonstrated (food products on fat, peptides, hydrocarbone matrix, urine etc). 

Analyte(s) Sample matrix Sample preparation" Eirst EC mode Subsequent EC mode(s) Detection" Reference... 

LC is not only a powerful analytical method as such, but it also allows effective sample preparation for GC. The fractions of interest (heart-cuts) are collected and introduced into the GC. The GC column can then be used to separate the fractions of different polarity on the basis of volatility differences. The separation efficiency and selectivity of LC is needed to isolate the compounds of interest from a complex matrix. 

The coupling of supercritical fluid extraction (SEE) with gas chromatography (SEE-GC) provides an excellent example of the application of multidimensional chromatography principles to a sample preparation method. In SEE, the analytical matrix is packed into an extraction vessel and a supercritical fluid, usually carbon dioxide, is passed through it. The analyte matrix may be viewed as the stationary phase, while the supercritical fluid can be viewed as the mobile phase. In order to obtain an effective extraction, the solubility of the analyte in the supercritical fluid mobile phase must be considered, along with its affinity to the matrix stationary phase. The effluent from the extraction is then collected and transferred to a gas chromatograph. In his comprehensive text, Taylor provides an excellent description of the principles and applications of SEE (44), while Pawliszyn presents a description of the supercritical fluid as the mobile phase in his development of a kinetic model for the extraction process (45). 

Minerals generally present difficult problems in chemical analysis, and these problems grow more serious when the elements being determined are as difficult to separate as are those named above. The time and effort that x-ray emission spectrography can save are therefore great, but there are obstacles to be surmounted. Among these are (1) Absorption and enhancement effects are often serious. (2) The element of interest may be present at low concentration in a matrix that is unknown and variable. (3) Satisfactory standards are not always easy to obtain. (4) Simple equipment sometimes does not resolve important analytical lines- completely. (5) Sample preparation and particle size often influence the intensities of analytical lines Class II deviations (7.8) can be particularly serious with minerals. 

Margarine is an example of a solid sample where the materials of interest are soluble in one solvent (in this case methanol) whereas the matrix materials, largely triglycerides, are not. As a consequence, the sample preparation procedure is relatively simple. The chromatographic separation is achieved by using the dispersive interactions between the hydrocarbon chains of the fatty acids and the hydrocarbon chains of a reversed phase. 

This sample preparation involved, firstly, an extraction and the elimination of the solid matrix by filtration and, secondly, a concentration procedure employing a solid phase extraction cartridge. The compounds of interest were separated solely by dispersive interactions with the reversed phase. In the example given, the corn meal was spiked with the aflatoxins. 

The two examples of sample preparation for the analysis of trace material in liquid matrixes are typical of those met in the analytical laboratory. They are dealt with in two quite different ways one uses the now well established cartridge extraction technique which is the most common the other uses a unique type of stationary phase which separates simultaneously on two different principles. Firstly, due to its design it can exclude large molecules from the interacting surface secondly, small molecules that can penetrate to the retentive surface can be separated by dispersive interactions. The two examples given will be the determination of trimethoprim in blood serum and the determination of herbicides in pond water. 

Analysis of methyl parathion in sediments, soils, foods, and plant and animal tissues poses problems with extraction from the sample matrix, cleanup of samples, and selective detection. Sediments and soils have been analyzed primarily by GC/ECD or GC/FPD. Food, plant, and animal tissues have been analyzed primarily by GC/thermionic detector or GC/FPD, the recommended methods of the Association of Official Analytical Chemists (AOAC). Various extraction and cleanup methods (AOAC 1984 Belisle and Swineford 1988 Capriel et al. 1986 Kadoum 1968) and separation and detection techniques (Alak and Vo-Dinh 1987 Betowski and Jones 1988 Clark et al. 1985 Gillespie and Walters 1986 Koen and Huber 1970 Stan 1989 Stan and Mrowetz 1983 Udaya and Nanda 1981) have been used in an attempt to simplify sample preparation and improve sensitivity, reliability, and selectivity. A detection limit in the low-ppb range and recoveries of 100% were achieved in soil and plant and animal tissue by Kadoum (1968). GC/ECD analysis following extraction, cleanup, and partitioning with a hexane-acetonitrile system was used. 

Stable under the electron beam. These results assume that in the case of sample preparation according to the procedure (b) or (c) the removal of the fatty acid matrix was not complete. The residual fatty acid molecules resulted in the decrease in sample stability. 

Several methods are available for the analysis of trichloroethylene in biological media. The method of choice depends on the nature of the sample matrix cost of analysis required precision, accuracy, and detection limit and turnaround time of the method. The main analytical method used to analyze for the presence of trichloroethylene and its metabolites, trichloroethanol and TCA, in biological samples is separation by gas chromatography (GC) combined with detection by mass spectrometry (MS) or electron capture detection (ECD). Trichloroethylene and/or its metabolites have been detected in exhaled air, blood, urine, breast milk, and tissues. Details on sample preparation, analytical method, and sensitivity and accuracy of selected methods are provided in Table 6-1. 

In a study of dental silicate cements, Kent, Fletcher Wilson (1970) used electron probe analysis to study the fully set material. Their method of sample preparation varied slightly from the general one described above, in that they embedded their set cement in epoxy resin, polished the surface to flatness, and then coated it with a 2-nm carbon layer to provide electrical conductivity. They analysed the various areas of the cement for calcium, silicon, aluminium and phosphorus, and found that the cement comprised a matrix containing phosphorus, aluminium and calcium, but not silicon. The aluminosilicate glass was assumed to develop into a gel which was relatively depleted in calcium. 

Biological matrices are very complex apart from the analytes, they usually contain proteins, salts, aeids, bases, and various organie eompounds. Therefore, effeetive sample preparation must inelude partieulate eleanup to provide the component of interest in a solution, free from interfering matrix elements, and in an appropriate concentration. 

Definition of the reference material, i.e. the matrix, the properties to be certified, and their desired levels Design of a sampling procedure Design of a sample preparation procedure... 

---