Halide-selective, proton-coupled anion transport by phenylthiosemicarbazones

Phenylthiosemicarbazones (PTSCs) are proton-coupled anion transporters with pH-switchable behaviour known to be regulated by an imine protonation equilibrium. Previously, chloride/nitrate exchange by PTSCs was found to be inactive at pH 7.2 due to locking of the thiourea anion binding site by an intramolecular hydrogen bond, and switched ON upon imine protonation at pH 4.5. The rate-determining process of the pH switch, however, was not examined. We here develop a new series of PTSCs and demonstrate their conformational behaviour by X-ray crystallographic analysis and pH-switchable anion transport properties by liposomal assays. We report the surprising finding that the protonated PTSCs are extremely selective for halides over oxyanions in membrane transport. Owing to the high chloride over nitrate selectivity, the pH-dependent chloride/nitrate exchange of PTSCs originates from the rate-limiting nitrate transport process being inhibited at neutral pH.

Halide-selective, proton-coupled anion transport by phenylthiosemicarbazones

Phenylthiosemicarbazones (PTSCs) are proton-coupled anion transporters with pH-switchable behaviour known to be regulated by an imine protonation equilibrium. Previously, chloride/nitrate exchange by PTSCs was found to be inactive at pH 7.2 due to locking of the thiourea anion binding site by an intramolecular hydrogen bond, and switched ON upon imine protonation at pH 4.5. The rate-determining process of the pH switch, however, was not examined. We here develop a new series of PTSCs and demonstrate their conformational behaviour by X-ray crystallographic analysis and pH-switchable anion transport properties by liposomal assays. We report the surprising finding that the protonated PTSCs are extremely selective for halides over oxyanions in membrane transport. Owing to the high chloride over nitrate selectivity, the pH-dependent chloride/nitrate exchange of PTSCs originates from the rate-limiting nitrate transport process being inhibited at neutral pH.

A headgroup linker perturbs pKavia acyl chain migration: designing base-labile supramolecular assemblies

Acyl chain transfer, which perturbs the protonation equilibrium of amine and reduces the apparent pKa by 2.0–2.5 units, is used to develop a liposome-based drug delivery system.

Synthesis, protonation equilibrium and peculiar thermal decomposition behavior of cyclo-tri-μ-imidotetraphosphate

The synthesis and isolation of the sodium salt ofcyclo-tri-μ-imidotetraphosphate,i.e.Na4cP4O9(NH)3·H2O, were achieved by the hydrolysis of Na4cP4O8(NH)4·2H2O under very weak acidic conditions,i.e.using 0.2 mol L−1propionic acid and the pH-controlled recrystallization procedure.

Binding of Coumarin 334 withβ-Cyclodextrin and with C-Hexylpyrogallol[4]arene: Opposite Fluorescence Behavior

We report here the structure of the host-guest complexes of Coumarin 334 (C334) withβ-cyclodextrin (β-CD) and with C-hexylpyrogallol[4]arene (C-HPA) and the effect of acidity on the neutral-cation equilibrium of C334 in water and in the presence of the host molecules. The structures of the host-guest complexes are proposed on the basis of the change of fluorescence on the addition ofβ-CD or C-HPA to C334 and by 2D ROESY spectroscopy. Opposite fluorescence behaviors, that is, quenching of fluorescence inβ-CD and enhancement of fluorescence in C-HPA are observed. Time-resolved fluorescence analysis is done for the complexation, and biexponential decay pattern is observed. The possible strong inclusion complexation with C-HPA is explained. The ground and the excited statepKavalues for the protonation equilibrium of C334 in water and the difficulty of protonation in the presence of the host molecules are discussed.