Analytical Sciences

Abstract − Analytical Sciences, 20(11), 1559 (2004).

Facilitated Sulfate Transfer across the Nitrobenzene-Water Interface as Mediated by Hydrogen-Bonding Ionophores
Seiichi NISHIZAWA, Tomoyuki KAMAISHI, Tomoyuki YOKOBORI, Ryo KATO, Ying-Yu CUI, Takeshi SHIOYA, and Norio TERAMAE
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan
Facilitated SO42- transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, α,α′-bis(N′-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO42- whereas its counterpart, N-(p-nitrophenyl)-N′-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO42- in the bulk NB phase, the SO42- transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO42- and ionophore, even under the condition of [SO42-]aq » [1]org. Such an exclusive formation of the 1:2 (SO42- to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, α,α′-bis(N′-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO42- with bis-thiourea 1 is further compared to that of HPO42- and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors.