title: Conductive polymeric ionic liquids for electroanalysis and solid-phase microextraction.
abstract: Three novel electropolymerizable thiophene-based ionic liquids (ILs) were synthesized and characterized as potential candidates for developing selective extraction media for chemical analysis. Electropolymerization of the bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-)) analogs successfully produced uniform polymeric thin-films on macro- and microelectrode substrates from both vinyl and methylimidazolium IL monomer derivatives. The resultant conducting polymer IL (CPIL) films were characterized by electrochemical methods and found to exhibit attractive behavior towards anionic species while simultaneously providing an exclusion barrier toward cationic species. Thermogravimetric analysis of the thiophene-based IL monomers established a high thermal stability, particularly for the methylimidazolium IL, which was stable until temperatures above 350 °C. Subsequently, the methylimidazolium IL was polymerized on 125 μm platinum wires and utilized for the first time as a sorbent coating for headspace solid-phase microextraction (HS-SPME). The sorbent coating was easily prepared in a reproducible manner, provided high thermal stability, and allowed for the gas chromatographic analysis of polar analytes. The normalized response of the poly[thioph-C6MIm][NTf2]-based sorbent coating exhibited higher extraction efficiency compared to an 85 μm polyacrylate fiber and excellent fiber-to-fiber reproducibility. Therefore, the electropolymerizable thiophene-based ILs were found to be viable new materials for the preparation of sorbent coatings for HS-SPME.
authors.affiliation: Department of Chemistry and Biochemistry, College of Natural Sciences and Mathematics, and School of Green Chemistry and Engineering, University of Toledo, 2801 West Bancroft Street, Toledo, OH 43606, USA.
authors.forename: Joshua A
authors.initials: JA
authors.lastname: Young
authors.affiliation: Department of Chemistry and Biochemistry, College of Natural Sciences and Mathematics, and School of Green Chemistry and Engineering, University of Toledo, 2801 West Bancroft Street, Toledo, OH 43606, USA.
authors.forename: Cheng
authors.initials: C
authors.lastname: Zhang
authors.affiliation: Department of Chemistry and Biochemistry, College of Natural Sciences and Mathematics, and School of Green Chemistry and Engineering, University of Toledo, 2801 West Bancroft Street, Toledo, OH 43606, USA.
authors.forename: Amila M
authors.initials: AM
authors.lastname: Devasurendra
authors.affiliation: Department of Medicinal and Biological Chemistry, College of Pharmacy and Pharmaceutical Sciences, and School of Green Chemistry and Engineering, University of Toledo, 2801 West Bancroft Street, Toledo, OH 43606, USA.
authors.forename: L M Viranga
authors.initials: LM
authors.lastname: Tillekeratne
authors.affiliation: Department of Chemistry and Biochemistry, College of Natural Sciences and Mathematics, and School of Green Chemistry and Engineering, University of Toledo, 2801 West Bancroft Street, Toledo, OH 43606, USA.
authors.forename: Jared L
authors.initials: JL
authors.lastname: Anderson
authors.affiliation: Department of Chemistry and Biochemistry, College of Natural Sciences and Mathematics, and School of Green Chemistry and Engineering, University of Toledo, 2801 West Bancroft Street, Toledo, OH 43606, USA. Electronic address: jon.kirchhoff@utoledo.edu.
authors.forename: Jon R
authors.initials: JR
authors.lastname: Kirchhoff
keywords: Electroanalysis; Electropolymerization; Ionic liquids; Modified electrodes; Solid-phase microextraction; Sorbent coatings