Transfer of actinide ion at the interface between aqueous and nitrobenzene solutions studied by controlled-potential electrolysis at the interface

A novel electrochemical method based on controlled-potential electrolysis has been developed for the elucidation of the ion transfer at the interface between two immiscible electrolyte solutions (ITIES). A relationship between the applied interfacial potential (E_app) and the amount of the ion transferred (A_tr) was investigated after an electrolytic equilibrium was attained by controlled-potential electrolysis. The A_tr was determined chemically or radiometrically instead of by current measurement. It was found that (i) controlled-potential electrolysis was applicable to the study of the transfer of such hydrophilic ions as transition metal ions which gave no appreciable current within the potential window in voltammetry or polarography at ITIES, (ii) controlled-potential electrolysis in combination with a sensitive analytical method enabled a study of the transfer reaction of an ion of very dilute concentration, and (iii) even when the transfer reaction of an ion was irreversible or quasi-reversible, a standard ion transfer potential could be determined by controlled-potential electrolysis without using a kinetic parameter. The controlled-potential electrolysis method developed was applied to the transfer reactions of actinide ions such as UO₂ ²⁺ and Am³⁺ from aqueous solution to nitrobenzene solution in the absence or presence of an ionophore facilitating the transfer. The Gibbs energy for the transfer of actinide ion and a stability constant of the complex between an actinide ion and the ionophore in nitrobenzene solution were determined from log D versus E_app plots (D the ratio of the concentration of the ion in nitrobenzene solution to that in aqueous solution). The feasibility of controlled-potential electrolysis as a method for electrolytic separation of actinide ions is discussed.     

Correlation of the gibbs free energy of transfer of fluoride ion from water to other solvents with solvent actidity and polarity parameters

Linear free energy relationships between the free energy of transfer of fluoride ion from water to other solvents or solvent mixtures and each of several parameters describing the acidity of the solvent were found. The correlation is about of the same quality for the A parameter of Swain or the acceptor number, AN, and almost as good for the parameter of Taft. The correlation was somewhat poorer with the E _T (30) parameter.     

Fluorescence energy transfer probes based on the guanine quadruplex formation for the fluorometric detection of potassium ion

Dual-labeled oligonucleotide derivative, FAT-0, carrying 6-carboxyfluorescein (FAM) and 6-carboxy-tetramethylrhodamine (TAMRA) labels at 5′- and 3′-termini of thrombin-binding aptamer (TBA) sequence 5′-GGTTGGTGTGGTTGG-3′ and its derivatives, FAT-n (n = 3, 5, and 7) were designed and synthesized. FAT-n derivatives contained a T_mA spacer (m = 2, 4, and 6, respectively) at 5′-end of TBA sequence. The probes were developed to estimate the spacer effect on FRET efficiency and to identify the best probe for sensing of K⁺. Circular dichroism (CD), UV-vis absorption, and fluorescence studies revealed that all FAT-n probes could form the intramolecular tetraplex structures after binding K⁺. Association constants of particular K⁺/FAT-n complexes were determined using different experimental approaches. Suitability of particular probes for sensitive monitoring of K⁺ in intra- and extracellular conditions was examined and discussed. Calibration graphs of fluorescence ratio were linear in the K⁺ concentration range of 2-10 mM for extracellular conditions showing sensitivity of 1.2% mM⁻¹ K⁺ and for intracellular conditions in the range of 100-200 mM with sensitivity of 0.49% mM⁻¹ K⁺.     

Effect of the aqueous–organic solvent structure on the cobalticenium–cobaltocene redox potential: The redox couple as a basis for determination of the single ion transfer energies

The redox potentials of the cobalticenium–cobaltocene couple have been determined voltammetrically in several aqueous–organic mixed solvents. The cosolvents studied were dimethylformamide, acetone, 1,4-dioxane (all three disrupting the 3D network of the water’s hydrogen bonds), propylenecarbonate (at low content structure-making, at higher – structure-breaking), and glycerol that incorporates into the 3D network. Cobalticenium spectra demonstrate the absence of ion pairs and solute–cosolvent complexes. The liquid junction potentials water-mixed solvent in the range of the cosolvent concentrations studied are small. At equal volume fractions of structure-breaking cosolvents the shifts of redox potential relative to water are similar. The potential shifts are more than by order of magnitude higher than those corresponding to the change of the mixed solvent’s dielectric constant. This is explained as due to disruption of the water hydrogen bonded structure, and disappearance therefore of the water anomalous dielectric response. The cobalticenium redox potential in the hypothetic “structureless” water was estimated as being ∼70 mV more positive than in real water. This is the potential that should be compared directly with the data for practically unstructured aprotic solvents.