• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2466-2470
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• 2007

A new highly salicylate-selective PVC membrane electrode based on tripodal tris-thiourea derivatives, L1 and L2, as neutral carriers is described. The electrodes display an excellent potentiometric response to salicylate ions and an anti-Hofmeister selectivity sequence in the following order: Salicylate? > ClO4 ? > Benzoate? > I? >NO3? > NO2? > Maleate? > Acetate? > Lactate? > Fumarate?. It also exhibited a near-Nernstian potential in a linear range of 5.0 × 10?5 - 1.0 × 10?1 M with a detection limit of 9.0 × 10?5 mol/L and a slope of ?59.9 mV/decade at a pH of 7.0 in a saline buffer solution at 25 oC. The stability constant (log KS) of the anionsionophore complex was also determined at 25 oC by a conductometric titration in DMSO solution.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2303-2308
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• 2009

A thiocyanate poly(vinyl chloride) (PVC) membrane electrode based on [1,2-bis(diphenylphosphino)ethane]dihalopalladium( II), [(dppe)$PdX_2$, X = Cl ($L^1$), X = I ($L^2$)] as active sensor has been developed. The diiodopalladium complex, [(dppe)$PdI_2](L^2$) displays an anti-Hofmeister selectivity sequence: $SCN^-\;>\;I^-\;>\;{ClO_4}^-\;>\;Sal^-\;>\;Br^-\;>\;{NO_2}^-\;>\;{HPO_4}^-\;>\;AcO^-\;>\;{NO_3}^-\;>\;{H_2PO_4}^-\;>\;{CO_3}^{2-}$. The electrode exhibits a Nernstian response (-59.8 mV/decade) over a wide linear concentration range of thiocyanate ($(1.0\;{\times}\;10^{-1}\;to\;5.0\;{\times}\;10^{-6}$ M), low detection limit ($(1.1\;{\times}\;10^{-6}$ M), fast response $(t_{90%}$ = 24 s), and applicability over a wide pH range (3.5∼11). Addition of anionic sites, potassium tetrakis[p-chlorophenyl] borate (KTpClPB) is shown to improve potentiometric anion selectivity, suggesting that the palladium complex may operate as a partially charged carrier-type ionophore within the polymer membrane phase. The reaction mechanism is discussed with respect to UV-Vis and IR spectroscopy. Application of the electrode to the potentiometric titration of thiocyanate ion with silver nitrate is reported.