Nano-structured self-doped polythiophene (SPT) electrodeposited in the presence of fluorinated organic acid was applied as a thermally stable conductive polymer-based solid-phase microextraction (SPME) fiber candidate. Quantitative determination of trace levels of phthalate esters including dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), and diethylhexyl phthalate (DEHP) was carried out using this novel fiber, coupling with gas chromatography-flame ionization detector (GC-FID). The SPT coating was proved to be stable at high temperatures (∼350°C) with a high extraction capacity and long lifetime (more than 60 times). Improved temperature resistance was obtained by the presence of sulfonated groups in the backbone of polymer. Thermal stability of novel SPT was superior to common polythiophene (synthesized in LiClO(4) ). The extraction procedure was optimized by means of the Taguchi orthogonal array experimental design with an OA(16) (4(5) ) matrix including extraction temperature, extraction time, salt concentration, stirring rate, and headspace volume. The good linearity was obtained for most compounds with correlation coefficients (R(2) ) of between 0.993 and 0.995. The detection limits were lower than 0.12 ng/mL for dimethyl phthalate, DEP, dibutyl phthalate, and diethylhexyl phthalate. The method was successfully applied to the analysis of water samples with the recoveries from 90±1 to 107±1%.
We report on a nanostructured self-doped polypyrrole (SPPy) film that was prepared by an electrochemical technique in an electrolyte containing fluorosulfonic acid as the sulfonation reagent. The film was applied as a new fiber material for solid-phase microextraction (SPME) of the pesticides lindane, heptachlor, aldrin, endosulfans I and II prior to their quantitation by GC with electron capture detection. The SPPy nanoparticles have a diameter of <100 nm. The introduction of covalently bound sulfo groups into the backbone of the polymer resulted in improved temperature resistance (~350°C) and satisfactory extraction efficiency. The thermal stability of the SPPy fiber is superior to common polypyrrole fibers. Extraction was optimized by means of the Taguchi orthogonal array experimental design with an OA 16 (4 5 ) matrix including extraction temperature, extraction time, salt concentration, stirring rate, and headspace volume. The method displays good repeatability (RSD<6%) and linearity (in the range from 0.78 to 100 ng mL −1 ; with an R 2 of >0.998. The detection limits are <0.23 ng mL −1 . The method was successfully applied to the analysis of the pesticides in skimmed milk and fruit juice samples, and recoveries are from 84±1 to 105±1%.
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