This critical review presents information on known and innovative approaches to the manufacture of fibre coatings used in solid-phase microextraction (SPME). The properties, advantages and drawbacks of the different types of commercially available SPME fibre coatings are discussed in detail, as are those of novel types of coatings and the methodologies of their preparation. The applications of fibre coatings in the solid-phase microextraction of a broad spectrum of analytes are analysed, with particular emphasis on the sampling of polar analytes from polar matrices (174 references).

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A new sorption system for isolation/enrichment of polar organic analytes from aqueous samples was obtained by substantial modification of the solid-phase microextraction (SPME) probe. In this system, polar sorbents are separated from the sample by a hydrophobic membrane. The new membrane SPME (M-SPME) probe was made utilizing polyethylene glycol (PEG) (molecular weight = 20 kDa) and polydimethylsiloxane (PDMS) as the membrane material. In this probe, PEG behaves as a pseudo-liquid at the extraction stage, whereas, up to now, it has mainly been used as a cross-linked solid adsorbent. It has been found that such M-SPME fiber may be successfully used at the sample pretreatment stage. It is sufficiently robust and thermally stable; the latter feature permits the usage of thermal desorption for the liberation of analytes. Comparison of our probe with the commercially available polyacrylic (PA) SPME fiber, using a mixture of phenols and gas chromatography as the final determination technique, demonstrated the highly effective nature of the new sorptive system; ca. 10 times higher than in the case of the PA fiber.

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