Solid-phase microextraction direct

Jurado C, Gimenez MP, Soriano T, Menendez M, and Repetto M (2000) Rapid analysis of amphetamine, methamphetamine, MDA, and MDMA in urine using solid-phase microextraction, direct on-fiber derivatization, and analysis by GC-MS. Journal of Analytical Toxicology 24(1) 11-16. 

Applications The potential of a variety of direct solid sampling methods for in-polymer additive analysis by GC has been reviewed and critically evaluated, in particular, static and dynamic headspace, solid-phase microextraction and thermal desorption [33]. It has been reported that many more products were identified after SPME-GC-MS than after DHS-GC-MS [35], Off-line use of an amino SPE cartridge for sample cleanup and enrichment, followed by TLC, has allowed detection of 11 synthetic colours in beverage products at sub-ppm level [36], SFE-TLC was also used for the analysis of a vitamin oil mixture [16]. 

Principles and Characteristics As mentioned already (Section 3.5.2) solid-phase microextraction involves the use of a micro-fibre which is exposed to the analyte(s) for a prespecified time. GC-MS is an ideal detector after SPME extraction/injection for both qualitative and quantitative analysis. For SPME-GC analysis, the fibre is forced into the chromatography capillary injector, where the entire extraction is desorbed. A high linear flow-rate of the carrier gas along the fibre is essential to ensure complete desorption of the analytes. Because no solvent is injected, and the analytes are rapidly desorbed on to the column, minimum detection limits are improved and resolution is maintained. Online coupling of conventional fibre-based SPME coupled with GC is now becoming routine. Automated SPME takes the sample directly from bottle to gas chromatograph. Split/splitless, on-column and PTV injection are compatible with SPME. SPME can also be used very effectively for sample introduction to fast GC systems, provided that a dedicated injector is used for this purpose [69,70],... 

Solid-phase microextraction has also been used for to determine volatile organic compounds in soil [26]. Target compounds were adsorbed directly from a head-space sample above a soil layer onto a fused-silica fibre. Vacuum distillation coupled with gas chromatography-mass spectrometry [27], head-... 

Nitrobenzene, 2,4-dinitrotoluene and 2,6-dinitrotoluene were determined in water by GC-EC or GC-CLD thermal energy analyzer (TEA) and by EI-MS, CI-MS and NICI-MS455, after solid-phase microextraction (SPME) with polydimethylsiloxane coated fiber. SPME is a technique to concentrate organic compounds dissolved in an aqueous matrix by adsorption on a solid stationary phase immobilized on a fused silica fiber. The analytes were thermally desorbed directly into the GC injector LOD was 9 pg/L for nitrobenzene and 15 pg/L for the dinitrotoluenes456. 

More recently, solid phase microextraction (SPME) [22] has been applied to the analysis of bug pheromones, using two techniques. In the first, headspace volatiles are trapped on the SPME fiber, analogous to trapping on SuperQ [e.g., 23]. Alternatively, if the source of the pheromone is known, the SPME fiber can be wiped on the cuticle to directly adsorb the compounds [24]. In either case, the fiber is then thermally desorbed directly into a GC or GC-MS. Whereas this method is excellent for analysis, with good recoveries, it does not provide a sample that can be used for bioassays or for isolation of an active compound. 

Solid-phase microextraction (SPME) is effectively a miniamrised version of SPE. Instead of using a packed cartridge, a rod is typically used, which is coated with the stationary phase. This is dipped into a solution of the analyte and allowed to extract for a pre-determined period of time. After this incubation period, the rod is removed from the solution and may be inserted directly into the injection system of the GC or HPLC. All of these operations can be automated on an autosampler. Clearly, the success of this technique depends intimately on the affinity of the analyte for the stationary phase. Frost, Hussain and Raghani [34] used SPME with GC-FID to measure benzyl chloride and chloroethylmethyl ether (amongst other process impurities) in pharmaceutical preparations. 

HSSPIVIE Headspace solid-phase microextraction a preconcentration technique that concentrates volatile analytes on a fiber than can be inserted directly into a GC... 

Arthur and Pawliszyn introduced solid-phase microextraction (SPME) in 1990 as a solvent-free sampling technique that reduces the steps of extraction, cleanup, and concentration to a unique step. SPME utilizes a small segment of fused-silica fiber coated with a polymeric phase to extract the analytes from the sample and to introduce them into a chromatographic system. Initially, SPME was used to analyze pollutants in water - via direct extraction. Subsequently, SPME was applied to more complex matrixes, such as solid samples or biological fluids. With these types of samples, direct SPME is not recommended nevertheless, the headspace mode (HSSPME) is an effective alternative to extracting volatile and semivolatile compounds from complex matrixes. (Adapted from Llompart et ah, 2001)... 

The extent of oxidative deterioration will determine the acceptability of a food product. Because of this, methods for determining the degree of oxidation are very useful to the food industry. There are many possible methods that can be utilized (see Commentary) however, due to the stability of some of the end products, and their direct relationship with rancidity, headspace GC provides a fast and reliable method for oxidation measurement. Headspace techniques include static, dynamic, and solid-phase microextraction (SPME) methods. 

Arthur, C.L., Potter, D., Bucholz, K., and Pawliszyn, J.B. 1992. Solid phase microextraction for the direct analysis of water Theory and practice. LC-GC 10 656-661. 

Figure 11.19 SPME-CE analysis of urine samples (a) blank urine (a) directly injected and extracted for (b) 5 (c) 10 and (d) 30 min (b) Urine spiked with barbiturates, extracted for (e) 30 and (f, g) 5 min. Peak identification is as follows 1, pentobartibal 2, butabarbital 3, secobarbital 4, amobarbital 5, aprobarbital 6, mephobarbital 7, butalbital 8, thiopental. Concentrations used are 0.15-1.0 ppm (e, f) and 0.05-0.3 ppm (g). Reprinted from Analytical Chemistry, 69, S. Li and S. G. Weber, Determination of barbiturates by solid-phase microextraction and capillary electrophoresis, pp. 1217-1222, copyright 1997, with permission from the American Chemical Society.

E. H. M. Koster, C. Wemes, J. B. Morsink and G. J. de Jong, Determination of lidocaine in plasma by direct solid-phase microextraction combined with gas chromatography , J. Chromatogr. B 739 175-182 (2000). 

The following table provides data on the common salts used for salting out in chromatographic headspace analysis, as applied to direct injection methods and to solid phase microextraction.1 2 Data are provided for the most commonly available salts, although others are possible. Sodium citrate, for example, occurs as the dihydrate and the pentahydrate. The pentahydrate is not as stable as the dihydrate, however, and dries out on exposure to air, forming cakes. Potassium carbonate occurs as the dihydrate, trihydrate, and sesquihydrate however, data are provided only for the anhydrous material. The solubility is provided as the number of grams that can dissolve in 100 ml of water at the indicated temperature. The vapor enhancement cited is the degree of increase of the concentration of vapor over the solution of a 2% (mass/mass) ethanol solution in water at 60°C.3... 

The most sensitive method for CVAA has recently been reported by Wooten et al. (39) using solid-phase microextraction to concentrate the derivatized analyte. Urine, with added ammonium acetate buffer and PhAsO as an internal standard, was derivatized directly with 1,3-propanedithiol and the derivative concentrated on a poly(dimethylsiloxane) (PDMS) solid-phase microextraction (SPME) fiber. Analysis was by automated GC/MS using SIM of the isotopic MH+ ions. An impressive detection limit of 7.4pg/ml was reported, using a benchtop GC/MS system. The method was validated using spiked human urine. 

Aroma compounds from vanilla beans have been extracted using several extraction procedures, using alcohols and organic solvents (Galletto and Hoffman, 1978 Dignum et al., 2002), direct thermal desorption (Hartman et al., 1992 Adedeji et al., 1993) and solid-phase microextraction (SPME) (Sostaric etal., 2000), followed by identification of the compounds by gas chromatography-mass spectrometry (GC-MS). 

These semi-preparative methods are useful where identification is required but for quantitative and comparative analytical purposes much more rapid sampling techniques, such as automated headspace and solid phase microextraction (SPME), may be preferred. Both of these techniques give similar results for most volatiles. In the former, the vapour above a heated sample is removed by a syringe or gas flushing and injected onto a GC column, either directly or after trapping on a suitable absorbent and thermal desorption. In SPME, the vapour is absorbed on to a suitable bonded medium on a special needle and then injected into the gas chromatogram. 

S. Fragueiro, I. Lavilla, C. Bendicho, Direct coupling of solid phase microextraction and quartz tube-atomic absorption spectrometry for selective and sensitive determination of methylmercury in seafood an assessment of chloride and hydride generation, J. Anal. Atom. Spectrom., 19 (2004), 250-254. 

Maurer has reviewed the application of LC-MS and LC-MS/MS to the detection of alkaloids in human biofluids [14]. Extraction techniques include liquid-liquid extraction relying upon the ionization of alkaloids in aqueous acid, solid phase extraction (SPE) in which alkaloids are cleaned up and concentrated from the biomatrix by adsorption and subsequent elution from a small cartridge of solid phase adsorbent, and solid-phase microextraction (SPME), in which analytes are adsorbed directly from the matrix or the headspace above the heated matrix onto a fine fiber of adsorbent on fused silica. The latter process is more commonly used with GC-M S but is finding increasing use with LC-MS. 

A recently developed technique, i.e. solid-phase microextraction (SPME), which collects vapors on a micro-liber coated with a gas chromatographic polymer phase (Chai and Pawliszyn, 1995 Grote and Pawliszyn, 1997), may be more promising than typical PSDs for long-term sampling as it permits the entire collected sample to be analyzed. The SPME liber can be exposed directly for rapid assessment of air quality or withdrawn into a tube that controls diffusion to the fiber for longterm sampling. 

Solid-phase microextraction (SPME) is a fast and solventless modification of SPE techniques [20]. SPME involves the use of fiber (fused silica fiber or polymer-coated fused fiber) coated by an adsorbent. The method is applied for extraction of different kinds of both volatile and nonvolatile analytes from different kinds of media, which can be in liquid or gas phase. In the direct extraction mode, coated fiber is immersed in the sample for a defined time, until equilibrium between the sample matrix and the solid phase is reached. The analyte is transported by diffusion directly to the extracting phase. In the next stage, the compound of interest... 

Headspace solid-phase microextraction (HS-SPME) is a rapid and solvent-free modification of the SPME technique in which a fine fused silica fiber with a polymeric coating is inserted into a headspace gas to extract organic compounds and directly transfer them into the injector of a gas chromatograph for thermal desorption and analysis. In this technique, the quantity of compounds extracted onto the fiber depends on the polarity and thickness of the stationary phase as well as on extraction time and concentration of volatiles in the sample. 

The most useful method for solvent residue analysis is GC. It can be performed by direct injection technique, or by headspace, solid phase microextraction (SPME), or single-drop microextraction (SOME) techniques [96]. GC has high selectivity, good specificity, is easy to perform, and involves simple sample preparation. Modem capillary GC allows separation of many compounds, together with their identification and quantification [96]. GC uses different detector systems, which are presented in Table 8.7. 

Extraction is the process of transferring a substance from a solid to a liquid phase or from a liquid to another liquid phase (immiscible with the former). From a practical viewpoint, the process can be achieved by leaching, which is transfer of compoimds from a solid phase to a solution (solid-liquid extraction, SEE) or by extraction via direct (liquid-liquid extraction, LEE) or indirect (SPE or solid phase microextraction, SPME) transfer of a substance from one liquid phase to another [75]. The efficiency of the extraction process is expressed as the percentage of extraction, which takes into accoimt the affinity of the investigated compoimds for both phases. In practice, a commonly used concept is that of recovery, understood as the degree of transition of a substance from one phase to another, expressed as a percentage. There are multiple methods for determining recovery. They can be divided into two classes ... 

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