title: Fluorophilic ionophores for potentiometric pH determinations with fluorous membranes of exceptional selectivity.
abstract: Ionophore-doped sensor membranes exhibit greater selectivities and wider measuring ranges when they are prepared with noncoordinating matrixes. Since fluorous phases are the least polar and least polarizable liquid phases known, a fluorous phase was used for this work as the membrane matrix for a series of ionophore-based sensors to explore the ultimate limit of selectivity. Fluorous pH electrode membranes, each comprised of perfluoroperhydrophenanthrene, sodium tetrakis[3,5-bis(perfluorohexyl)phenyl]borate, and one of four fluorophilic H(+)-selective ionophores were prepared. All the ionophores are highly fluorinated trialkylamines containing three electron withdrawing perfluoroalkyl groups shielded from the central nitrogen by alkyl spacers of varying lengths: [CF(3)(CF(2))(7)(CH(2))(3)](2)[CF(3)(CF(2))(6)CH(2)]N, [CF(3)(CF(2))(7)(CH(2))(3)](2)(CF(3)CH(2))N, [CF(3)(CF(2))(7)(CH(2))(3)](3)N, and [CF(3)(CF(2))(7)(CH(2))(5)](3)N. Their pKa values in the fluorous matrix are as high as 15.4 +/- 0.3, and the corresponding electrodes exhibit logarithmic selectivity coefficients for H(+) over K(+) as low as <-12.8. The pKa and selectivity follow the trends expected from the degree of shielding and the length of the perfluoroalkyl chains of the ionophores. These electrodes are the first fluorous ionophore-based sensors described in the literature. The selectivities of the sensor containing [CF(3)(CF(2))(7)(CH(2))(5)](3)N are not only greater than those of analogous sensors with nonfluorous membranes but were of the same magnitude as the best ionophore-based pH sensors ever reported.
authors.affiliation: Department of Chemistry, University of Minnesota, 207 Pleasant Street South East, Minneapolis, Minnesota 55455, USA.
authors.forename: Paul G
authors.initials: PG
authors.lastname: Boswell
authors.forename: Csongor
authors.initials: C
authors.lastname: Szíjjartó
authors.forename: Markus
authors.initials: M
authors.lastname: Jurisch
authors.forename: John A
authors.initials: JA
authors.lastname: Gladysz
authors.forename: József
authors.initials: J
authors.lastname: Rabai
authors.forename: Philippe
authors.initials: P
authors.lastname: Bühlmann
mesh_terms: D004563:Electrochemistry / Q000379:methods*; D005461:Fluorine / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D008567:Membranes, Artificial; D012680:Sensitivity and Specificity
chemical_list: D008567:Membranes, Artificial; D005461:Fluorine