Raman spectra of K2CuF4

The crystal structure of K₂CuF₄ has been studied by means of Raman scattering. The structure is found to belong to the space group D_4h⁵ rather than D_4h¹⁷ of K₂NiF₄ between 2 and 800 K because of the distortion arising from the “orbital ordering effect”.     

Photoreactive fluorinated polyimide protected by a tetrahydropyranyl group (THP) based on photo-induced acidolysis

A polyimide (6F-THP) with a tetrahydropyranyl group (THP) in its side chain has been synthesized. The THP group exhibits a high acidolysis rate in this polymer's film. This rate was faster than that of a tertbutoxycarbonyl group (t-BOC), which has been previously reported [1]. Furthermore, the deprotected fluorinated polyimide (6FDA-AHHFP) became soluble in an aqueous base due to the presence of a hydroxyl group attached to the phenyl group of the diamine segment. The polyimide thus provides high performance as a photopolymer when used in conjunction with a photoacid generator after the post-exposure baking process (PEB). The photoacid generators used in this study were p-nitrobenzyl-9,10-dimethoxyanthoracene-2-sulfonate (NBAS) and diphenyliodonium-9,10-dimethoxyanthoracene-2-sulfonate (DIAS). The quantum yields of photodissociation and photoacid generation were also measured. The photoacid-generating quantum yields closely corresponded to the photosensitivities of the photoreactive polyimide system. It was confirmed that the THP group was easily deprotected even in the 6F-THP film with p-toluenesulfonic acid as a model acid catalyst. The activation energy of the THP deprotection reaction was determined to be 12.8 kcal/mol (19.5 kcal/mol in the case of t-BOC). The relationships between the THP deprotecting rate constant (k_d) and acid molecular size and between k_d and polyimide structure were further investigated.     

A new effect of ultrasonication on the formation of BaTiO3 nanoparticles

A new effect of ultrasonic irradiation on the formation of BaTiO₃ particles was identified. Ultrasonication caused the aggregation of the original 5–10 nm BaTiO₃ particles in the same crystal axis and accelerated the formation of BaTiO₃ particles significantly. Furthermore, narrow size distribution was obtained for the aggregated particles under ultrasonic irradiation.     

First-principles calculations of migration energy of lithium ions in halides and chalcogenides

Migration of Li+ ions via the vacancy mechanism in LiX (X = F, Cl, Br, and I) with the rocksalt and hypothetical zinc blende structures and Li2X (X = O, S, Se, and Te) with the antifluorite structure has been investigated using first-principles projector augmented wave calculations with the generalized gradient approximation. The migration paths and energies, determined by the nudged-elastic-band method, are discussed on the basis of two idealized models: the rigid-sphere and charged-sphere models. The trajectories and energy profiles of the migration in these lithium compounds vary between these two models, depending on the anion species and crystal structure. The migration energies in LiX with both the rocksalt and hypothetical zinc blende structures show a tendency to decrease with increasing periodic number of the anion species in the periodic table. This is consistent with the widely accepted view that anion species with large ionic radii and high polarizabilities are favorable for good ionic conduction. In contrast, Li2O exhibits the lowest migration energy among Li2X compounds, although O is the smallest among the chalcogens, indicating that electrostatic attractive interactions play the dominant role in the inter-ion interactions in Li2O and, therefore, in the ion migration.     

Ultraviolet photolysis of urine for suppression of color quenching prior to liquid scintillation counting of tritium

In order to reduce the color quenching in the measurement of tritium in urine by liquid scintillation counting , UV irradiation was applied to decompose the organic substances in the sample. Urine was decolorized under UV irradiation in the presence of hydrogen peroxide. As a result, color quenching was considerably suppressed and higher counting efficiency of tritium was obtained. This UV treatment made it possible to increase the urine content in the sample from 2 to 40% (v/v) without significant decrease of counting efficiency. Either higher sensitivity or shorter analysis time was achieved in the tritium measurement by the augmentation of urine content. When the measurement time was 30 min, the detection limit of tritium defined as 3s was 0.03 Bq/ml. At the expense of some sensitivity (set at a detection limit of 0.3 Bq/ml), the measurement time was shortened to 0.5 min. These results will make a great improvement to routine tritium monitoring as well as to emergency monitoring in mass tritium exposure.      

Infrared vibrational autodetachment spectroscopy of microsolvated benzonitrile radical anions

Vibrational spectra of microsolvated benzonitrile radical anions (C6H5CN- -S; S = H2O and CH3OH) were measured by probing the electron detachment efficiency in the 3 microm region, representing resonance bands of autodetachment via OH stretching vibrations of the solvent molecules. The hydrogen-bonded OH band for both the cluster anions exhibited a large shift to the lower energy side with approximately 300 cm-1 compared to those for the corresponding neutral clusters. The solvent molecules are bound collinearly to the edge of the CN group of the benzonitrile anion in the cluster structures optimized with the density functional theory, in which the simulated vibrational energies are in good agreement with the observed band positions. Natural population analyses were performed for a qualitative implication in changes of solvent orientation upon electron attachment. Asymmetric band shapes depending on the vibrational modes are discussed with respect to dynamics of the autodetachment process from a theoretical aspect incorporated with density functional calculations.     

Insights into adsorption of uncharged macrocyclic complexes into a Nafion Film: Adsorption characteristics and analysis of tetraphenylporphyrine zinc(II)

Tetraphenylporphine zinc(II) (ZnTPP) was found to be adsorbed from its CH2Cl2 solution into a Nafion (Nf) film. The characteristics of the adsorption of ZnTPP into the Nf film were studied using a visible absorption spectroscopic technique. The initial rate (v0, mol cm(-2) s(-1)) for uptake of ZnTPP was saturated with increasing ZnTPP concentration (c0, M) in the solution. This kinetic profile was analyzed in terms of a Michaelis-Menten model considering preequilibrium of ZnTPP adsorption between the solution and the outer layer of the Nf film, followed by diffusion to an inner bulk region, giving a maximum diffusion reflux of v(max) = (2.2 +/- 0.2) x 10(-13) mol cm(-2) s(-1). This is different from the kinetics for the Nf/phthalocyanine zinc(II) (ZnPc) film, which gives a linear plot of v(0) vs c(0). This can be explained by the relatively slow diffusion of ZnTPP in the film compared to that of ZnPc because of steric factors: ZnTPP contains bulky tetraphenyl moieties attached perpendicular to a porphyrin ring, whereas ZnPc has higher planarity. The isotherm for the adsorption of ZnTPP into the Nf film was analyzed using a Langmuir isotherm equation, yielding an equilibrium constant of (3.6 +/- 1.1) x 10(6) M(-1) and a saturated amount of adsorbed ZnTPP of (1.8 +/- 0.1) x 10(-9) mol cm(-2), suggesting monolayer adsorption of ZnTPP on the hydrophobic polymer network interfacial with hydrophilic transport channels without significant intermolecular overlap. This is in contrast to the multilayer adsorption mode suggested for the ZnPc adsorption. The tetraphenyl moieties could prevent the stacking of ZnTPP for multilayer adsorption.