Extraction solvents, choice

Extraction and Extractive Distillation. The choice of an extraction or extractive distillation solvent depends upon its boiling point, polarity, thermal stabiUty, selectivity, aromatics capacity, and upon the feed aromatic content (see Extraction). Capacity, defined as the quantity of material that is extracted from the feed by a given quantity of solvent, must be balanced against selectivity, defined as the degree to which the solvent extracts the aromatics in the feed in preference to paraffins and other materials. Most high capacity solvents have low selectivity. The ultimate choice of solvent is deterrnined by economics. The most important extraction processes use either sulfolane or glycols as the polar extraction solvent. 

The data were collected using fluorescence measurements, which allow both identification and quantitation of the fluorophore in solvent extraction. Important experimental considerations such as solvent choice, temperature, and concentrations of the modifier and the analytes are discussed. The utility of this method as a means of simplifying complex PAH mixtures is also evaluated. In addition, the coupling of cyclodextrin-modified solvent extraction with luminescence measurements for qualitative evaluation of components in mixtures will be discussed briefly. 

Consequently, separate experiments for the determination of extraction efficiency are often not required. An expert statement based on the results of metabolism studies is sufficient in most cases. These statements should also refer to the extraction solvent used for the analysis of samples of supervised trials. Residue levels found in these trials are the criterion for GAP and the basis for the setting of MRLs. Even if a solvent with insufficient extraction efficiency is used for samples from supervised trials, the later choice of better solvents would not result in lower safety for the consumer. 

The most critical decision to be made is the choice of the best solvent to facilitate extraction of the drug residue while minimizing interference. A review of available solubility, logP, and pK /pKb data for the marker residue can become an important first step in the selection of the best extraction solvents to try. A selected list of solvents from the literature methods include individual solvents (n-hexane, " dichloromethane, ethyl acetate, acetone, acetonitrile, methanol, and water ) mixtures of solvents (dichloromethane-methanol-acetic acid, isooctane-ethyl acetate, methanol-water, and acetonitrile-water ), and aqueous buffer solutions (phosphate and sodium sulfate ). Hexane is a very nonpolar solvent and could be chosen as an extraction solvent if the analyte is also very nonpolar. For example, Serrano et al used n-hexane to extract the very nonpolar polychlorinated biphenyls (PCBs) from fat, liver, and kidney of whale. One advantage of using n-hexane as an extraction solvent for fat tissue is that the fat itself will be completely dissolved, but this will necessitate an additional cleanup step to remove the substantial fat matrix. The choice of chlorinated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride should be avoided owing to safety and environmental concerns with these solvents. Diethyl ether and ethyl acetate are other relatively nonpolar solvents that are appropriate for extraction of nonpolar analytes. Diethyl ether or ethyl acetate may also be combined with hexane (or other hydrocarbon solvent) to create an extraction solvent that has a polarity intermediate between the two solvents. For example, Gerhardt et a/. used a combination of isooctane and ethyl acetate for the extraction of several ionophores from various animal tissues. 

Supercritical fluid extraction (SFE) is a technique in which a supercritical fluid [formed when the critical temperature Tf) and critical pressure Pf) for the fluid are exceeded simultaneously] is used as an extraction solvent instead of an organic solvent. By far the most common choice of a supercritical fluid is carbon dioxide (CO2) because CO2 has a low critical temperature (re = 31.1 °C), is inexpensive, and is safe." SFE has the advantage of lower viscosity and improved diffusion coefficients relative to traditional organic solvents. Also, if supercritical CO2 is used as the extraction solvent, the solvent (CO2) can easily be removed by bringing the extract to atmospheric pressure. Supercritical CO2 itself is a very nonpolar solvent that may not have broad applicability as an extraction solvent. To overcome this problem, modifiers such as methanol can be used to increase the polarity of the SFE extraction solvent. Another problem associated with SFE using CO2 is the co-extraction of lipids and other nonpolar interferents. To overcome this problem, a combination of SFE with SPE can be used. Stolker et al." provided a review of several SFE/SPE methods described in the literature. 

Until this point, the sample preparation techniques under discussion have relied upon differences in polarity to separate the analyte and the sample matrix in contrast, ultraflltration and on-line dialysis rely upon differences in molecular size between the analyte and matrix components to effect a separation. In ultrafiltration, a centrifugal force is applied across a membrane filter which has a molecular weight cut-off intended to isolate the analyte from larger matrix components. Furusawa incorporated an ultrafiltration step into his separation of sulfadimethoxine from chicken tissue extracts. Some cleanup of the sample extract may be necessary prior to ultrafiltration, or the ultrafiltration membranes can become clogged and ineffective. Also, one must ensure that the choice of membrane filter for ultrafiltration is appropriate in terms of both the molecular weight cut-off and compatibility with the extraction solvent used. 

The polarity index is a measure of the polarity of the solvent, which is often the most important factor in the solvent choice for the particular application. In extraction processes, the tenet that like dissolves like (and conversely, opposites do not attract ) is the primary consideration in choosing the solvent for extraction, partitioning, and/or analytical conditions. For example, hexane often provides a selective extraction for nonpolar analytes, and toluene may provide more selectivity for aromatic analytes. 

Soil samples are generally extracted with one or more organic solvents mixed with up to 10% (v/v) water. A wide variety of solvents is used for extraction, the choice... 

Principles and Characteristics A first step in additive analysis is the identification of the matrix. In this respect the objective for most polymer analyses for R D purposes is merely the definition of the most appropriate extraction conditions (solvent choice), whereas in rubber or coatings analysis usually the simultaneous characterisation of the polymeric components and the additives is at stake. In fact, one of the most basic tests to carry out on a rubber sample is to determine the base polymer. Figure 2.1 shows the broad variety of additive containing polymeric matrices. 

For polymer/additive analysis complete dissolution is not a prerequisite. Rather, the solvent should at least swell the polymer by diffusion, which allows the physically blended additives to dissolve. True dissolution occurs predominantly when polymer chain lengths are small, on the order of 5000-10 000 Da. Solvent choice for dissolution or extraction should take into account restrictions imposed by further analysis steps (compatibility with chromatographic and/or spectroscopic requirements). When microwave extraction of additives from a polymer is followed by HPLC analysis, the solvent must be compatible with the HPLC mobile phase so that solvent exchange is not required before analysis. 

Successful extraction of additives from polymeric matrices requires a proper selection of organic solvents. Solvent choice was based on the following solvent properties ... 

The static ASE mode may lead to incomplete extraction because of the limited volume of solvent used. Dynamic ASE yields faster extractions by continuously providing fresh extraction solvent to the sample, but obviously requires a larger solvent volume than static ASE and is therefore less suited for trace analysis. In practice, a combination of static and dynamic extraction is often considered to be the best choice. 

For sample (a), a glass bottle with a screw top is the preferred choice. Assuming it is a clean bottle, the glass will add nothing to the sample which might cause interferences. If organic compounds in the water are likely to be lost to the inside of the bottle by adsorption, a suitable extracting solvent is added to the bottle... 

A pivotal step in the analytical process is sample preparation. Frequently liquid-liquid extractions (LLEs) are used. Solvents, pH, and multiple back extractions are all manipulated to increase selectivity and decrease unwanted contaminants before injection on the GC system. Solid phase extraction (SPE) is more convenient than it used to be because of an increase in commercially available SPE columns. SPE columns are packed with an inert material that binds the drug of interest, allowing impurities to pass through. As with LEE, solvent choices and pH affect retention and recovery. There are three commercially available types of SPE columns, diatomaceous earth (which uses the same principles as LLE), polystyrene-divinylbenzene copolymer, and mixed mode bonded silica (Franke and de Zeeuw, 1998). 

There is no universal solvent, and solvent selection must be made individually for each separation problem. The specific choice must be based on a general knowledge of the different interactions in both phases. Among the desirable features for the extracting solvent are the following ... 

Thus, to conduct successful analyses for many organic and inorganic compounds at trace concentrations, it is necessary to extract these compounds and use a concentration step prior to analysis. Many of the techniques developed for preconcentration are described in specialized books [10]. Proper choice of the extracting solvent can often be the critical step in the procedure. 

Thorium sulfate, being less soluble than rare earth metals sulfates, can be separated by fractional crystallization. Usually, solvent extraction methods are applied to obtain high purity thorium and for separation from rare earths. In many solvent extraction processes, an aqueous solution of tributyl phosphate is the extraction solvent of choice. 

SOLVENT Choice. Solvent extraction is limited to water immiscible solvents. Solid adsorbents do not have this limitation, so miscible solvents, desirable for subsequent analytical or bioassay purposes, can be used. For example, DMSO is preferred for mutagenicity screening and has been used to elute the adsorbed organic material (211-213, 216, 235, 328). For analytical purposes, acid, base, and neutral eluents can be employed for on-column fractionation of the adsorbed organic solutes (78, 80,196). 

In general liquid standards are prepared in a solvent matrix which should be the same as the matrix of the unknown. In many cases the liquid may be an extraction solvent or simply a dilution solvent, depending on the type of analysis and the form of the original sample. If the solvent choice is left to the analyst (as opposed to being prescribed by a procedure), the solvent has to be chosen such that it does not interfere with any of the potential sample components. For trace analysis it is important that the solvent be checked for impurities and that these impurities will not be confused with sample components. Chromatographing the solvent at the maximum sensitivity to be used in the analysis is referred to as "blanking the solvent." It is very important to blank the solvent each time it is used to be sure it has not been inadvertently contaminated. Also in trace analysis it is preferred to have a solvent elute from the column following the sample components of interest rather than ahead of the sample. 

The most common method for the separation and concentration of flavor chemicals before chromatography is solvent extraction. If the aroma active components in a sample are less than a microgram/liter then solvent extraction followed by fractional distillation can be used to concentrate the analytes above 1 4g/liter. This is done for two reasons (1) to remove the odorants from some of the interfering substances and nonvolatiles, and (2) to concentrate the sample for greater sensitivity. The choice of solvent(s) depends on a number of issues, but similar results can be obtained with many solvents. Table Gl.1.2 lists a number of solvents, their polarity, and physical properties. Pentane is the least polar and ethyl acetate the most. The sample must be an aqueous or dilute sample, dissolved or slurried into water to a final concentration of 80% to 90% water. Dilute aqueous samples will present the greatest polarity difference between the solvent and the sample, driving more volatiles into the extracting solvent. 

Polyphenolics constitute a wide range of chemical compounds composed of aromatic ring(s) with one or more hydroxyl substituents, including their functional derivatives. Methods for extraction and isolation of polyphenolics from plant material are described in this unit. Extraction and isolation are the first important steps for separation, characterization, and quantification of polyphenolics from plant material. Polyphenolics are often most soluble in organic solvents less polar than water. The solubility is dependent on the polar properties of the polyphenolics. The correct selection of the extracting solvent is not as simple as it may seem. Aqueous methanol is a popular choice of solvent (see Background Information). 

Extraction is an essential step when analyzing solid samples. In some cases homogenization with a solvent suffices, but in others the sample must first be coimninuted. Water, solutions of acetic acid or sodium chloride, or more complex saline solutions are used as solvents. Mixtures of water and methanol or water and ethanol are also employed. The choice of solvent depends on the degree of selectivity desired in the extraction and whether the extraction yield is intended for quantitative analysis. Optimization of the extraction procedure is required in all cases, to fit the nature of the sample to be analyzed and the range of molecular weights of the peptides to be separated. For example, water has been used as the extraction solvent for cheese (33) and legumes (34). Saline solutions have been utilized to extract peptides from meat (35-38) and flour (39,40). Benedito de Barber et al. (41) examined differences in the extractability of amino acids and short peptides in various solvents (1M acetic acid, 70% ethanol, and distilled water) they concluded that extraction with 1M acetic acid yielded the maximum amino acid and peptide contents. 

Some factors will condition the choice of the cleanup procedure, namely (a) the extraction solvent used in the previous stage, (b) the concentration of the carbohydrates present in relation to potential interfering compounds, and (c) the complexity of the analyzed food. Additionally, the nature of these interferents and the need to minimize the loss of analyte during the cleanup will become key aspects to be considered. In any case, and regardless of the final method chosen, it is essential that the percentage recovery of the cleanup procedure be determined. The most frequently utilized procedures will be commented next. 

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