Fluorous polymeric membranes for Lonophore based Ion selective potentiometry: How inert is teflon AF?

Chun Ze Lai, Secil S. Koseoglu, Elizabeth C. Lugert, Paul G. Boswell, J. Rábai, Timothy P. Lodge, Philippe Bühlmann

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

Fluorous media are the least polar and polarizable condensed phases known. Their use as membrane materials considerably increases the selectivity and robustness of ion selective electrodes (ISEs). In this research, a fluorous amorphous perfluoropolymer was used for the first time as a matrix for an ISE membrane. Electrodes for pH measurements with membranes composed of poly[4,5 difluoro-2,2- bis(trifluoromethyl)-1,3-dioxole]-co-poly(tetrafluoroethylene) (87% dioxole monomer content; known as Teflon AF2400) as polymer matrix, a linear perfluorooligoether as plasticizer, sodium tetrakis[3,5-bis(perfluoro- hexyl)phenyl]borate providing for ionic sites, and bis[(perfluorooctyl)propyl]- 2,2,2-trifluoroethylamine as H + ionophore were investigated. All electrodes had excellent potentiometric selectivities, showed Nernstian responses to H + over a wide pH range, exhibited enhanced mechanical stability, and maintained their selectivity over at least 4 weeks. For membranes of low ionophore concentration, the polymer affected the sensor selectivity noticeably at polymer concentrations exceeding 15%. Also, the membrane resistance increased quite strongly at high polymer concentrations, which cannot be explained by the Mackie-Meares obstruction model. The selectivities and resistances depend on the polymer concentration because of a functional group associated with Teflon AF2400, with a concentration of one functional group per 854 monomer units of the polymer. In the fluorous environment of these membranes, this functional group binds to Na +, K +, Ca2 +, and the unprotonated ionophore with binding constants of 10 3.5, 10 18, 10 6.8, and 10 4.4M -1, respectively. Potentiometric and spectroscopic evidence indicates that these functional groups are COOH groups formed by the hydrolysis of carboxylic acid fluoride (COF) groups originally present in Teflon AF2400. The use of higher ionophore concentrations removes the undesirable effect of these COOH groups almost completely. Alternatively, the C(=0)F groups can be eliminated chemically, or they can be used to readily introduce new functionalities.

Original languageEnglish
Pages (from-to)1598-1606
Number of pages9
JournalJournal of the American Chemical Society
Volume131
Issue number4
DOIs
Publication statusPublished - Feb 4 2009

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Potentiometry
Polymeric membranes
Polytetrafluoroethylene
Polytetrafluoroethylenes
Ionophores
Polymers
Ions
Membranes
Functional groups
Ion-Selective Electrodes
Ion selective electrodes
Electrodes
Monomers
Plasticizers
Borates
Mechanical stability
Carboxylic Acids
Polymer matrix
Fluorides
Carboxylic acids

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Fluorous polymeric membranes for Lonophore based Ion selective potentiometry : How inert is teflon AF? / Lai, Chun Ze; Koseoglu, Secil S.; Lugert, Elizabeth C.; Boswell, Paul G.; Rábai, J.; Lodge, Timothy P.; Bühlmann, Philippe.

In: Journal of the American Chemical Society, Vol. 131, No. 4, 04.02.2009, p. 1598-1606.

Research output: Contribution to journalArticle

Lai, Chun Ze ; Koseoglu, Secil S. ; Lugert, Elizabeth C. ; Boswell, Paul G. ; Rábai, J. ; Lodge, Timothy P. ; Bühlmann, Philippe. / Fluorous polymeric membranes for Lonophore based Ion selective potentiometry : How inert is teflon AF?. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 4. pp. 1598-1606.
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