Solid-phase microextraction (SPME) fiber coatings based on conductive polypyrrole films were prepared for the electrochemical extraction and desorption of ionic analytes. Simple preparation of each of the PPY extraction coatings on a platinum wire was possible with a constant potential method, but more importantly, cycling of the film between oxidation and reduction potentials facilitated the extraction and desorption of ionic analytes. The analytes were desorbed into a sample aliquot of water and were determined by flow injection analysis using a mass spectrometer. The fiber coatings and the developed electrochemical SPME method were found to be stable and reproducible (RSD < 5%; N = 5) and could be extended to several cations and anions, confirming the versatility of the approach. Preconcentration of the analyte on the fiber was also possible by repeating the processes to increase the amount of analyte extracted.
In-tube solid-phase microextraction (SPME) based on a polypyrrole (PPY)-coated capillary was investigated for the extraction of aromatic compounds from aqueous solutions. The PPY-coated capillary was coupled on-line to HPLC that was programmed with an autosampler to achieve automated in-tube SPME and HPLC analysis. Three groups of aromatics, including both polar and nonpolar compounds, were examined. The results demonstrated that the PPY coating had a higher extraction efficiency than the currently used commercial capillary coatings, especially for polycyclic aromatic compounds and polar aromatics due to the increasing pi-pi interactions, interactions by polar functional groups, and hydrophobic interactions between the polymer and the analytes. In addition to the functional groups in the PPY coating, which contributed to the higher extraction efficiency and selectivity toward analytes, the coating's porous surface structure,which was revealed by electron microscopy experiments, provided a high surface area that allowed for high extraction efficiency. It was found that the extraction efficiency and selectivity could be tuned by changing the coating thickness. The preliminary study of the extraction mechanism indicated that analytes were extracted onto the PPY coating mainly by an adsorption mechanism. The method was used for the extraction and analysis of both polar and nonpolar aromatics in aqueous samples.
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