Solid phase extraction analyte retention

Figure 2.12 Schematic representation of an on-line SPE-GC system consisting of three switching valves (VI-V3), two pumps (a solvent-delivery unit (SDU) pump and a syringe pump) and a GC system equipped with a solvent-vapour exit (SVE), an MS instrument detector, a retention gap, a retaining precolumn and an analytical column. Reprinted from Journal of Chromatography, AIIS, A. J. H. Eouter et al, Analysis of microcontaminants in aqueous samples hy fully automated on-line solid-phase extraction-gas chromatography-mass selective detection , pp. 67-83, copyright 1996, with permission from Elsevier Science.

A method which uses supercritical fluid/solid phase extraction/supercritical fluid chromatography (SE/SPE/SEC) has been developed for the analysis of trace constituents in complex matrices (67). By using this technique, extraction and clean-up are accomplished in one step using unmodified SC CO2. This step is monitored by a photodiode-array detector which allows fractionation. Eigure 10.14 shows a schematic representation of the SE/SPE/SEC set-up. This system allowed selective retention of the sample matrices while eluting and depositing the analytes of interest in the cryogenic trap. Application to the analysis of pesticides from lipid sample matrices have been reported. In this case, the lipids were completely separated from the pesticides. 

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). 

Agonists are particularly suited to reversed-phase solid-phase extraction due, in part, to their relatively nonpolar aliphatic moiety, which can interact with the hydrophobic octadecyl- and octyl-based sorbents of the cartridge (472, 473, 475, 480,486, 487). By adjusting the pH of the sample extracts at values greater than 10, optimum retention of the analytes can be achieved. Adsorption solid-phase extraction using a neutral alumina sorbent has also been described for improved cleanup of liver homogenates (482). 

Retention of the analyte on a solid-phase extractant, followed by dissolution in a clean matrix (such as dilute nitric acid) to remove interferences and preconcentrate the analyte. 

Chapuis F et al (2004) Retention mechanism of analytes in the solid-phase extraction process using molecularly imprinted polymers - application to the extraction of triazines from complex matrices. J Chromatogr B Anal Technol Biomed Life Sci 804(1) 93-101... 

The term solid-phase extraction was introduced by personnel of the J. T. Baker Company in 1982. The method consists of retention of the analytes from a liquid or gaseous sample to a solid stationary phase and subsequent removal of analytes using an appropriate eluent. The main purpose of SPE is isolation and preconcentration of compounds of interest or sample clean-up and simplification of the matrix. Application of this sample preparation technique also allows extract fractionation. As a result of significant reduction in the volume of organic solvents used, high recovery, and the possibility of process automation, SPE is a good alternative for conventional liquid-liquid extraction. According to their affinity for the compound of interest, stationary phases are classified as follows ... 

An alternative to liquid-liquid extraction is solid-phase extraction (SPE). With SPE a liquid sample is introduced into the top of a plastic syringe shape column containing a small amount (often 100- 500 mg) of a selective adsorbent (Figure 8.1). The adsorbents are of the same types as used for HPLC, typically silica, or bonded silica such as Cl 8, C8, C5, C2, cyano, phenyl, diol and ion-exchange materials. The properties of the adsorbents are similar to HPLC columns and so the same principles apply for retention and desorption of analytes. 

Sample injection in gas chromatography often seems deceptively simple a microlitre aliquot is rapidly injected into an inlet system, and elution and detection follow. Samples containing substantial amounts of non-volatile material, however, require one or more preparation steps in order to isolate volatile analytes from non-volatiles that would otherwise contaminate the inlet system and column, eventually leading to impaired chromatographic performance. Examples of such procedures include liquid-liquid extraction, solid-phase extraction and filtration. The use of a pre-column (viz. a retention gap or a guard column) is often required, even if prepared samples are used. 

FIGURE 17.3 The general scheme for performing solid-phase extraction consists of several sequential steps. S ample pretreatment is important to ensure analyte retention. (Reprinted from Wells [54], Copyright 2003, with permission from Elsevier Science.)... 

Solid-phase extraction (SPE) is a method of sample preparation that concen-Irates and purifies analytes from solution by sorption onto a disposable solid-phase cartridge, followed by elution of the analyte with a solvent appropriate for instrumental analysis. The mechanisms of retention include reversed phase, normal phase, and ion exchange. Traditionally, sample preparation consisted of sample dissolution, purification, and extraction that was carried out with liquid-liquid extraction. The disadvantages with liquid-liquid extraction include the use of large volumes of organic solvent, cumbersome glassware, and cost. Furthermore, liquid-liquid extraction often creates emulsions with aqueous samples that are difficult to extract, and liquid-liquid extraction is not easily automated. These difficulties are overcome with solid-phase extraction. Thus, solid-phase extraction was invented in the mid-1970s as an alternative approach to liquid-liquid extraction. 

Parameters of interest to determine for MIPs used as stationary phases in liquid chromatography are the retention factors [k = (t - t0)/to, where t is the retention of the analyte and t0 is the void], the separation factors (a = k1/k2, where k, and k2 are the retention factors of compound 1 and 2) and the resolution (R) [175, 176], For MIPs used as stationary phases in solid-phase extraction, the recovery is also of interest. 

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