Molecular recognition by wall-assembling-type nanocavity in aqueous media

Steroid cyclophanes, each having a macrocyclic ring attached to four bile acid moieties via chiral lysine connectors, were synthesized, and the binding of the 2-naphthylphenylketone (guest) to the steroid cyclophanes in water was investigated. The circular dichroism spectra of the steroid cyclophane with cholic acid and L-lysine were significantly affected by the binding of the guest, and the induced circular dichroism based on the absorption of the achiral guest was also observed. The binding of the guest to the steroid cyclophane with cholic acids and D-lysines induced changes in the circular dichroism spectra with the opposite sign of the molecular ellipticities. An induced circular dichroism spectral change was not observed upon binding of the guest to the analogous host without OH sites. These results strongly suggest that the guest is conformationally fixed through hydrogen bonding between the carbonyl group of the guest and the steroidal hydroxyl group of the host. The assembly of only four steroid residues on the macrocyclic ring probably provided a hydrophobic nanocavity for hydrogen bonding.     

Purification and characterization of sea squirt alpha-N-acetylgalactosaminidase

Sea squirt alpha-N-acetylgalactosaminidase was purified to homogeneity. Its molecular weight was estimated to be approximately 160,000 by gel filtration and 40,000 by SDS-polyacrylamide gel electrophoresis (SDS-PAGE) under reducing condition. The chromatographic and electrophoretic behaviors indicated that the enzyme was composed of four subunits. The optimum pH of the enzyme reaction was about 4.0 at 37 degrees C, while the enzyme was stable in the range of pH 5.0 to 6.0 during 4 h preincubation at 37 degrees C. Although the enzyme (0.1 unit) was stable at 0 degrees C for 30 min in the presence of 7.5 mM metal ions (Al3+, Ba2+, Ca2+, K+, Mn2+, Pb2+, Sr2+, and Zn2+), almost 40% of the enzyme activity was lost in the presence of Cu2+, Hg2+, monoiodoacetic acid, and EDTA. The enzyme hydrolyzed aryl N-acetyl-alpha-D-galactosaminide as well as GalNAcalpha1(-->4GalNAcalpha1-->)n 4GalNAc-p-aminobenzoic acid ethyl ester (ABEE) (n = 1-4), but GalNAcalpha1-->4GalNAc-ABEE only scarcely. Furthermore, an allergenic pentasaccharitol ABEE derivative, GalNAcalpha1-->2Fucalpha1-->3(GalNAcbeta1-->4) GlcNAcbeta1-->2(3-acetoamido-3-deoxy)L-threose-ABEE, the minimum structural unit for the sea squirt allergenicity was hydrolyzed to 95 mol% for 72 h incubation with the enzyme. The enzyme could be utilized as a powerful tool for the structural analyses of the carbohydrate epitopes of the sea squirt allergen molecules.     

Coherency strains influence on martensitic transformation of γ-Fe particles in compressed Cu-Fe alloy single crystals

Single crystals of a Cu-Fe alloy, which contained spherical -Fe particles, were compressed up to shear strain of 0.17 in liquid nitrogen bath. In the process of straining the structural (optical and TEM) observations in as-deformed and post-deformation annealed samples were provided. The substructure of deformed samples was characterized by slightly developed cell structure and lack of distinct layer-like arrangements of dislocations. Three kinds of particles were found: coherent and semi-coherent f.c.c. -Fe and martensiticly transformed b.c.c. -Fe. The critical diameter for coherency loss was found to be 58 nm at the initial stage of deformation decreasing with strain to 50 nm. These values coincided with the theoretical estimations. It was suggested that relaxation of coherency strains around -Fe particles by the generation of interface dislocations might occur prior to the martensitic transformation. This assumption might explain the particle size dependency of martensitic transformation.     

Isotopic fractionation and profile evolution of a melting snowcover

Successive snow pits were dug intensively in a melting snowcover. Water was successfully separated from snow grains in the field for the first time. By measuring δ¹⁸O values of water and snow grain samples as well as comparing isotopic profiles, it is found that meltwater percolating down in snow develops quick and clear isotopic fractionation with snow grains, but exerts no clear impact on the δ¹⁸O profile of the snowcover through which the meltwater percolates.     

Effect of sorbed water on the electrical resistance of polysodium phosphate thin films

Measurements have been made of complex impedance and sorbed water of polysodium phosphate. The resistance and its activation energy decreases with an increase in the amount of sorbed water. The amount of sorbed water is strongly affected by the Na₂O/P₂O₅ mol ratio. The humidity dependence of the activation energy and the resistance is lowered by decreasing the average chain length of polysodium phosphate. This results in an increase in the amount of sorbed water. Especially, in low humidity conditions, the decrease in the resistance and the activation energy are achieved by increasing the concentration of the strongly acidic PO-H group. These improvements can not be achieved by increasing the Na₂O/P₂O₅ mol ratio. In a humid atmosphere, the resistance of the film, in which the Na₂O/P₂O₅ mol ratio is less than 0.8, is inversely proportional to the concentration of the strongly acidic PO-H group.     

Spectroscopic studies on the rare-earth vanadites

The nature of the V/1bO/1bV interaction of the perovskite type rare-earth vanadites were studied by spectroscopic methods. Infrared and ultraviolet analyses revealed that the V/1bO bond length became shorter and that the V/1bO bond strength increased, as a function of the atomic number of lanthanide elements in LnVO₃. Judging from the x-ray fluorescent spectra of oxygen-K_α, the energy level of O^2? (p_π) orbitals of the heavier rare-earth vanadites was lower than that of the lighter rare-earth vanadites.