Food analysis extraction

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... 

Applications The majority of SFE applications involves the extraction of dry solid matrices. Supercritical fluid extraction has demonstrated great utility for the extraction of organic analytes from a wide variety of solid matrices. The combination of fast extractions and easy solvent evaporation has resulted in numerous applications for SFE. Important areas of analytical SFE are environmental analysis (41 %), food analysis (38 %) and polymer characterisation (11%) [292], Determination of additives in polymers is considered attractive by SFE because (i) the SCF can more quickly permeate throughout the polymer matrix compared to conventional solvents, resulting in a rapid extraction (ii) the polymer matrix is (generally) not soluble in SCFs, so that polymer dissolution and subsequent precipitation are not necessary and (iii) organic solvents are not required, or are used only in very small quantities, reducing preparation time and disposal costs [359]. 

So far, LSE is the most popular for extracting contaminants in food. However, over the last years LPME in its different application modes (single drop microextraction, dispersive liquid-liquid microextraction and hollow fiber-LPME) has been increasingly applied to food analysis because of its simplicity, effectiveness, rapidity, and low consumption of organic solvents. Different applications have been recently reviewed by Asensio-Ramos et al. [112]... 

Retinoids The challenge in fat-soluble vitamins analysis is to separate them from the lipid fraction that contains interferents. Alkaline hydrolysis, followed by LLE, is widely applied to remove triglycerides. This technique converts the vitamin A ester to all-trani-retinol. A milder process, which does not hydrolyze vitamin A ester, is alcoholysis carried out with metha-nolic KOH solution under specific conditions that favor alcoholysis rather than saponification. A more accurate explanation of this technique is reported in the book Food Analysis by FIPLC [409]. For some kind of matrices a simple liquid extraction can be sufficient with [421-423] or without [424,425] the purification... 

Extraction of fat by supercritical carbon dioxide was investigated as an important option for minimizing the expanded use of frequently flammable and carcinogenic solvents in food analysis. Unfortunately, the presence of moisture in foods has an adverse effect on the quantitative extraction of fat by supercritical fluid extraction (SEE). Hence, samples have to be lyophilized first. The total fat content of freeze-dried meat and oilseed samples was found to be comparable to values derived from Soxhlet-extracted samples (26). Besides, only small amounts of residual lipids could be recovered by an additional extraction of the SFE-extracted matrix by the Bligh and Dyer solvent extraction procedure. As far as the minor constituents are concerned, it was found that the extraction recovery ranged from 99% for PC to 88% for PA. Hence, Snyder et al. concluded that SFE can be used as a rapid, automated method to obtain total fat, including total phospholipids, from foods (26). 

In a method proposed by Booth et al. (141) for the determination of phylloquinone in various food types, extracted samples are subjected to silica solid-phase extraction followed, in the case of meat or milk samples, by further purification using reversed-phase solid-phase extraction or liquid-phase reduction extraction, respectively. The final test solution is analyzed by NARP-HPLC, and the fluorescent hydroquinone reduction products of phylloquinone and the internal standard are produced online using a postcolumn chemical reactor packed with zinc metal. 2, 3 -Dihydrophylloquinone, a synthetic analog of phylloquinone, is a suitable internal standard for the analysis of vegetable juice, whole milk, and spinach. Another synthetic analog, Ku23), is used for the analysis of bread and beef, because a contaminant in the test solution coelutes with dihydro-phylloquinone. 

For some foods, incomplete extraction of color is obtained, probably due to the high binding affinity of dyes to the bulk of the food matrix, especially to proteins, lipids, and carbohydrates (156,161,162). This problem can be overcome by the use of selected solvents or enzymes to digest the food prior to extraction. Petroleum ether can be used to extract lipids (163). Acetone can be used to remove lipids and coagulate protein (164). Enzymes, such as amyloglucosidase (165,166), papain (167), lipase, pectinase, cellulase, and phospholipase, added to the sample and incubated under optimum pH and temperature conditions release synthetic colors bound to or associated with the food matrix. Furthermore, enzyme digestion can solubilize some foods, enabling analysis to be continued (156). 

This paper shows a nice example for solving an important analytical problem using MISPE. Mycotoxins and particularly zearalenone (ZON) and /nmv-a-zearalenol (a-ZOL) present an everyday problem in food analysis. Existing sample clean-up techniques have different drawbacks. Liquid-liquid extraction is characterized by... 

Considering the importance to characterise food products, the analytical quality control needs methods that are able to extract useful information from the food matrix. Infact, each food product on the market can be viewed as a typical piece that can be characterised by some precise analytical indices. It is not important to know all the quantitative aspects that characterise the products, but it is sufficient to create a map of analytical semi-quali-quantitative signals that constitutes the product fingerprint. Since the majority of the methods reported for food analysis... 

E. Anklam, H. Berg, L. Mathiasson, M. Sharman and F. Ulberth, Supercritical fluid extraction (SFE) in food analysis a review , Food Additive Contam. 15 729-750 (1998). 

As sample extraction and sample handling are of general consideration for the more exotic biological matrices often found in food analysis, the application of IPCR in the research project MYCOPLEX [89], founded by the European Union, promises interesting new developments. This project is dedicated to the detection by IPCR of ochra- and aflatoxins in milk and coffee, focusing on sensitivity and simplified antigen extraction by dilution of the samples. 

The representativeness of a spiking experiment to asses the method bias is an important issue in food analysis. It has been questioned whether one can evaluate the extraction of substances in a matrix by means of a spiking experiment. The extraction efficiency of incurred and spiked analytes is seldom the same. For some substances, it is hard to find real blank materials. Furthermore, several parameters have influence on the uncertainty of the experimentally determined method bias [32]. It should be stressed that, as it may be concentration-dependent, the method bias should be evaluated for the entire concentration range of the analytical method. 

Anklam, E., Berg, H., Mathiasson, L., Sharman, M., and Ulberth, F. 1998. Supercritical fluid extraction (SEE) in food analysis A review. Food Additives Contaminants Part A, 15 729-50. 

Chemat F. Tomao V. Virot M. 2009. Ultrasound-assisted extraction in food analysis. In Handbook of Food Analysis Instruments (Semih, O., Ed.). CRC Press, Boca Raton, FL, pp. 85-104. 

SBSE can be successfully used in the analysis of environmental samples [93-97] and for food analysis [98, 99]. PDMS is the most commonly used polymer, primarily because of its thermal stability and durability. SBSE has been modified by application of derivatization with different reagents (acetic anhydride, BSTFA, etc) [100-104]. This approach is suitable for the extraction of compounds requiring derivatization. The use of multistep derivatization with several extraction elements (each reaction is performed on a different stir bar) allows efficient extraction, desorption, and chromatographic analysis of compounds with different functional groups (e.g., phenols, steroids, amines, thiazoles, ketones). Acetic anhydride (ester formation), ethyl chloroformate (reaction of acids and amines), tetraethyloborane, and sodium bis-trimethylotrifluoroacetamide have been used for extraction and simultaneous derivatization [105]. 

There are many examples in the literature for applications of LC-NMR in the pharmaceutical industry. In the area of natural products, LC-NMR has been applied to screen plant constituents from crude extracts [54,57,67,68] and to analyze plant and marine alkaloids [69-72], flavonoids [73], sesquiterpene lactones [74,75], saponins [58,76], vitamin E homologues [77], and antifungal and bacterial constituents [56,78,79] as examples. In the field of drug metabolism, LC-NMR has been extensively applied for the identihcation of metabolites [42, 80-88] and even polar [89] or unstable metabolites [43]. And hnally, LC-NMR has been used for areas such degradation products [90-93], drug impurities [94-102], drug discovery [103,104], and food analysis [105-107]. 

Daft (1988) employed a photoionization detector and an electrolytic conductivity detector connected in series to a capillary GC to detect 1,1-dichloroethane at ng /g levels in fumigants and industrial chemical residues of various foods (e.g., diary products, meat, vegetables, and soda). Typically, foods were extracted with isooctane and injected in GC column for analysis. However, foods containing lipid and fat were subjected to further clean-up on micro-florisil column prior to GC analysis. 

Changes in the focus of SFE can be easily followed through its reported applications. Thus, in 1993 [3], environmental applications prevailed (45.9% versus 21.9% devoted to foods and 11.6% to industrial analyses). By 1996, however, SFE applications to food analysis had risen to 38%, environmental uses fallen to 41% and industrial analyses levelled off at 11% [48]. More recently [17], the extraction of food components (particularly fat) has become one of the major applications of SFE, so much so that the current boom in SF extractor sales has been ascribed to it. The book by Luque de Castro et al. [3] contains comprehensive tables of SFE applications in various fields. Also, one review of SFE in food analysis [148] includes four tables with applications involving the extraction of fat from various types of sample (viz. meat and animal products, fish, cereal, seed and animal feed, plants and vegetables). On a more specific level, Eller and King reviewed determinations of the fat content in foods [149]. Finally, the Analytical Chemistry issues devoted to reviewing techniques provide periodic updates on SFE and SFC [150]. 

Another extraction method that has been used in soil analysis (Fish and Revesz, 1996) and works for food analysis is microwave solvent extraction. It consists of placing a sample in an open or closed container capable of high pressure and heated by microwave energy, causing extraction of the analyte (Fish and Revesz, 1996). This method is yet another form of solvent extraction and differs in how the sample is heated. Its advantages lie in the fact that it can replace traditional solvent extraction and sonication with a fast and safe method of liquid-solid extraction. 

Supercritical fluid extraction (SFE) has been applied to a broader range of samples. Generally, the applications of SFE have been developed as a faster and less solvent-intensive alternative to traditional extraction schemes. Environmental and food analysis are the main field of applications of SFE (21) however, a wide range of applications have been focused on the extraction of drugs and active compounds from different types of matrices that are commented below. 

A number of very good reviews on food analysis can be found in the literature [7-12]. Table 3 presents a very limited representation of the kind of work involved in a food laboratory. All basic constituents of foodstuffs - proteins, lipids, carbohydrates and vitamins - are amenable to liquid chromatography. Various types of columns and detectors used for those analysis demonstrate the versatility of the technique. Almost any type of food matrix can be extracted in order to identify and quantitate trace amounts of analytes. 

Liquid membrane ISEs can be used, after the necessary calibration procedure, to measure the appropriate cation or anion in liquid foods, solid foods taken into solution or suspension properly, food extractions, etc., providing always that the sample solutions do not contain significant concentrations of interfering ions or contaminating substances. It shovdd be remembered that, in the majority of instances, apphcation of hquid membrane ISEs in food analysis will be carried out in under quahty control conditions, and will involve samples of generally well-known composition and analyte ranges. 

The validation of the microwave-assisted extraction technique was performed by comparing the values obtained to that of the standard samples and by performing conventional prescribed official methods associated with each products under study. Table 2 presents a summary of data presented in references [19] and [20]. The results demonstrate that, in all cases, the microwave-assisted extraction procedures yielded data that were, for all practical purposes, similar to the accreditation values of fat content obtained for the same samples using conventional official methods. These results support the current trend whereby several microwave-assisted extraction methods are being evaluated for accreditation purposes. This trend is not exclusive to food analysis [27]. 

In this introduction, we have presented an overview of the benefits of applying the technique of SFE to the area of food analysis. There are substantially reduced costs derived from use of SFE versus traditional extraction in the areas of solvent purchase costs, solvent disposal costs, reduced labour charges, and even less need to repeat experiments due to reduced human errors in the overall analytical scheme. Moreover, productivity can be improved and the use of environmentally-unfriendly solvents is greatly reduced. In the rest of this chapter we will explore the fundamental principles of SFE in more detail, discuss some of the aspects of current SFE instrumentation, present a number of examples of applying SFE to food samples, and briefly summarise some hints for methods development. 

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