Electrochemical behavior of [UO_2Cl_4]~(2-) in 1-ethyl-3-methylimidazolium based ionic liquids

In order to examine the chemical form of uranyl species in 1-ethyl-3-methylimidazolium(EMI) based ionic liquids,UV-visible absorption spectra of solutions prepared by dissolving [EMI] 2 [UO2Cl4] into a mixture of EMICl and EMIBF 4(50:50 mol%) were measured.As a result,it was confirmed that uranyl species in the mixture of EMICl and EMIBF 4 existed as [UO2Cl4]2-.Cyclic voltammograms(CVs) of [UO2Cl4]2-in the mixture were measured at 25 ℃ using a Pt working electrode,a Pt wire counter electrode,and an Ag/Ag + reference electrode(0.01 M AgNO 3,0.1 M tetrabutylammonium perchlorate in acetonitrile) in a glove box under an Ar atmosphere.Peaks corresponding to one redox couple were observed around-1.05 V(Epc) and-0.92 V(Epa) vs.ferrocene/ferrocenium ion(Fc/Fc +).The potential differences between two peaks(Ep) increased from 101 to 152 mV with an increase in the scan rate from 50 to 300 mV s-1,while the(Epc+Epa)/2 value was constant,-0.989 V vs.Fc/Fc + regardless of the scan rate.Furthermore,the diffusion coefficient of [UO2Cl4]2-and the standard rate constant were estimated to be 3.7 × 10-8 cm 2 s-1 and(2.7-2.8) × 10-4 cm s-1 at 25 oC.By using the diffusion coefficient and the standard rate constant,the simulation of CVs was performed based on the reaction,[UO2Cl4]2-+ e = [UO2Cl4]3-.The simulated CVs were found to be consistent with the experimental ones.From these results,it is concluded that [UO2Cl4]2-in the mixture of EMICl and EMIBF 4 is reduced to [UO2Cl4]3-quasi-reversibly at-0.989 V vs.Fc/Fc +.     

Stability of pyrrolidone derivatives against γ-ray irradiation

To evaluate the stability of N-alkylated pyrrolidone derivatives(NRPs),which are supposed to be used as precipitants for U(VI) and Pu(IV,VI) species in HNO 3 media,under irradiation environment,some candidate NRPs were irradiated by γ-ray.Irradiation to HNO 3 solutions up to 6 mol dm 3(= M) containing 2 M N-n-butyl-2-pyrrolidone(NBP),one of NRPs with lower hydrophobicity,has revealed that the residual ratios of NBP in the samples of HNO 3 up to 3 M decreased identically and linearly.Approximately 20% of NBP was found to be degraded after the irradiation at 1 MGy.It was also found that the decrease in the precipitation ratio of UO 2 2+(P.R.,%) was gentle and that the P.R.values were relatively in accordance with the residual ratios of NBP.On the other hand,the degradation of the samples irradiated in 6 M HNO 3 was found more distinguished.It was proposed from the analyses of degraded compounds that the degradation of NBP in HNO 3 by γ-ray irradiation started from the cleavage of the pyrrolidone ring by the addition of oxygen atom originating from HNO 3,followed by the formation of chain compounds by the successive addition of oxygen,leading to the generation of oxalic acid and acetic acid.The stability of other NRPs in 3 M HNO 3 was evaluated to be nearly identical with that of NBP except lower P.R.values of the samples containing NRPs with higher hydrophobicity irradiated at more than 0.5 MGy.     

A dendron of subphthalocyanine trefoil

The synthesis of a dendron composed of tetrameric subphthalocyanine (SubPc) is accomplished by substituting the chlorine groups with phenoxy groups at the axial positions of SubPc with SubPc-triol. The present molecular design of the SubPc-triol introduces three phenol groups at the peripheral positions of the SubPc macrocycle as a tritopic template to construct SubPc dendrons. The self-polycondensation of SubPc-triol as a ‘divergent’ synthesis only gave a trace amount of the hyperbranched arrays due to poor solubility of the SubPc-triol. In contrast, a ‘convergent’ synthesis with the terminal SubPc improved the solubility throughout the reaction and a tetrameric SubPc dendron was obtained in moderate isolated yield.     

Soluble-insoluble-soluble transitions of aqueous poly(N-vinylacetamide-co-acrylic acid) solutions

Several poly(N-vinylacetamide-co-acrylic acid)s with various copolymer compositions have been synthesized, and their unique phase-transition behavior in aqueous salt (Na2SO4 or NaCl) solutions was investigated. Copolymers containing more than 51 mol % N-vinylacetamide (NVA) show reentrant soluble-insoluble-soluble transitions with increasing temperature. The soluble-insoluble transition temperature (T(p1)) increased linearly with increasing NVA content, whereas the insoluble-soluble transition temperature (T(p2)) was almost constant irrespective of the NVA content. Potentiometric titration of the copolymer solutions suggested that the acrylic acid (AA) carboxyl groups form hydrogen bonds with the NVA amide groups even under soluble conditions. Dehydration of the NVA amides and their consequent hydrogen bonding with the AA carboxyl groups during the soluble-insoluble transition process was indicated by FTIR measurements. Addition of salt (Na2SO4 or NaCl) to the aqueous media reduces the solvent quality and enhances the intra- and interchain interactions of the copolymers. Thus, T(p1) was observed to decrease and T(p2) was observed to increase with increasing salt concentration. However, the addition of urea to the media reverses the concentration dependence of T(p1) and T(p2) by disturbing the intra- and interchain interactions of the copolymers.     

Recent analytical methodologies on equilibrium, kinetics, and dynamics at liquid/liquid interface

The form of liquid/liquid interface is flexible and it cannot be fixed at a spatial position. Also the interface is prevented from any physical contact by the organic phase and aqueous phase. In addition, analytical methods operated in vacuo cannot be applied. These restrictions depressed the development of liquid/liquid interfacial chemistry. However, the modification of liquid/liquid interfacial form and original analytical methods have been invented interdependently. The present review classifies the forms of liquid/liquid interface first, and it arrays the related analytical methods with brief explanations. It dominantly deals with recent reports of analytical methodologies, which were published in 2001-2004, on equilibrium, kinetics, and dynamics of substances at liquid/liquid interface, but it also includes historically important studies.     

Measurement of ordered associate of protonated tetraphenylporphine formed at toluene/aqueous H2SO4 interface by attenuated total internal reflection spectroscopy with polarized light

Attenuated total internal reflection (ATR) spectroscopy with an s- or p-polarized visible light was examined for some species of protonated 5,10,15,20-tetraphenylporphine (tpp) at toluene/aqueous H₂SO₄ (3-6 mol dm⁻³) interface. Tpp initially dissolved in the toluene phase was diprotonated at the interface to form monomeric H₂tpp²⁺, the absorption peak of which was 438 nm. At the same time, a long H₂tpp²⁺ oligomer was formed, the absorption peak of which was 448 nm. The two interfacial species were transient. Just after their disappearance, a rod-shaped H₂tpp²⁺ associate was formed at the interface, the absorption peak of which was 417 and 478 nm. The former and latter wavelengths corresponded to H- and J-bands of the associate, respectively. Theoretical calculation of the strength of electric field of light at the interface allowed one to estimate the interfacial concentration of the three species with measured reflection absorbance (A_R). The monomeric H₂tpp²⁺ and its oligomer were at sub-monolayer levels, whereas the associate was at a multilayer level. Reflection absorption anisotropy (K_R), which was calculated from A_R with the s- and p-polarized lights, was adopted for the evaluation of out-of-plane orientation of the interfacial species for the first time. The K_R value suggested that the rod-shaped associate lay at the interface.     

In situ measurements of emission transition dipole moment of individual ordered microdomain of diprotonated tetraphenylporphine aggregate formed at dodecane/aqueous H<Subscript>2</Subscript>SO<Subscript>4</Subscript> interface

Rhombic-ordered microdomains of diprotonated 5,10,15,20-tetraphenylporphine aggregate, whose sizes were 10–200 μm, were formed at dodecane/aqueous H₂SO₄ interfaces. The light excitation of their two absorption bands (410 and 473 nm for H- and J-bands, respectively) led to one fluorescence band at longer wavelength (723 nm). The direction of the emission transition dipole moment (μ _e) of individual rhombic microdomains, determined with an in situ optical microscope and a linear polarizer, was almost parallel to the major axis, which was also almost parallel to the direction of the absorption transition dipole moment of their J-bands. Their absorption and emission transition scheme was proposed.