Palladium-catalyzed cycloheptatriene formation by [3+2+2] cocyclization of 2-substituted allylic alcohols and alkynes

Cycloheptatrienes were obtained by the reaction of 2-substituted allylic alcohols with alkynes in the presence of catalytic amounts of palladium complexes and p-toluenesulfonic acid.     

Significant differences in site of protonation and extent of fragmentations in chemical ionization and fast atom bombardment mass spectrometry of simple bifunctional compounds. A mechanistic implication for formation of protonated molecules

Chemical ionization (CI) and fast atom bombardment (FAB) mass spectra of simple bifunctional aromatic compounds were compared. Some significant differences were revealed with respect to the site of protonation and extent of fragmentations. Unlike conventional CI ionization, the protonated molecule formation by FAB could not be accounted for by ordinary proton transfer reactions in the gas phase. The observed ions under FAB conditions appear to be regulated by proton exchange reactions through frequent collisions in some particular region between the matrix and the gas phase.     

Low temperature synthesis and characterization of porous anatase TiO2 nanoparticles

An ethanol solution of Ti-peroxy compounds was prepared from the ethanol solution of titanium isopropoxide (Ti(O-iPr)4) and H2O2. Heating of the ethanol solution of the Ti-peroxy compounds at 348 K formed a Ti-peroxy gel, and heat treatment of the gel at 348 K for more than 6 h formed gels that consisted of anatase nanoparticles. The diameter of the anatase nanoparticles increased from 9 to 15 nm as the heating time increased from 6 to 48 h. According to the results of the N2 adsorption measurement, the anatase nanoparticles had micropores, and the specific surface area (SBET) was in the range of 254 to 438 m2/g. The particle size, lattice strain, specific surface area, and photocatalytic activity of the anatase nanoparticles can be regulated by the heating time of the Ti-peroxy gel at 348 K.     

Regioselective synthesis and biological activity of oxidized chitosan derivatives

Oxidized chitosan derivatives with various degrees of oxidation (DS, 0.1–1.0) were prepared by the treatment of chitosan with CrO₃/aq HClO₄ or by the oxidation of ­3‐O‐ and N‐protected chitosan with 30% aq H₂O₂/Na₂WO₄ followed by 3‐O‐ and N‐deprotection. The oxidized products were then N‐acetylated with Ac₂O in order to improve their water‐solubility. Although the oxidized chitosan derivative of DS 0.28 and the degree of N‐acetylation of chitosan (DA) 38% was insoluble in the pH 3–8 region, that of DS 0.26 and DA 76% was soluble in the neutral pH range. The newly‐prepared acetylated and oxidized chitosan derivatives were found to suppress the chemiluminescence response of inflammatory cells such as canine polymorphonuclear cells (PMNs). Analysis by the surface plasmon resonance method revealed that the bind and release behavior of PMNs to acetylated oxidized chitosan derivatives was similar to that against carboxymethylated chitosan derivatives. The amount of water‐soluble chitosan derivative bound to cytokine IL‐8 was found to be affected by the structural and electronic features of the chitosan substituents in the chitosan chain. Copyright © 2003 John Wiley & Sons, Ltd.     

Spectral analysis of Sr 3d XPS spectrum in Sr-containing hydroxyapatite

The Sr 3d X-ray photoelectron spectroscopy (XPS) spectrum of Sr-containing hydroxyapatite (SHAp) overlaps completely with the P 2p spectrum. Thus, the chemical state identification of Sr in SHAp is a challenging task. In this work, the Sr 3d spectrum was isolated from the overlapping spectra for analyzing the chemical state of Sr using a generic peak-fitting method. The SHAp layers containing various Sr concentrations were produced on a Ti substrate using a chemical treatment process with a calcium phosphate slurry that included Sr (NO₃)₂. The distribution of the constituent elements changed according to the Sr concentration, implying that the chemical state of Sr varied with concentration. The isolation of the Sr 3d XPS spectrum was conducted via spectral deconvolution using the P 2p spectrum corresponding to HAp. The isolated Sr 3d spectrum revealed that the chemical state of Sr was in SrO and Sr-substituted HAp states, and their ratio varied with the Sr concentration in the layer. The SrO to Sr-substituted HAp ratios affected the Sr ion releasing behavior from the SHAp layer, supporting the validity of the obtained analytical results.     

Interaction of highly charged ions with carbon-based materials using Kobe EBIS

Interaction of highly charged ions (HCIs) with surfaces produce various specific phenomena as a consequence of the potential energy that HCI possesses. In the present study, we have observed photon emission, structural, magnetic, and electronic modification on various carbon-based materials such as carbon nanotube by the impact of HCIs using an electron beam ion source named Kobe EBIS installed at the Kobe University. In order to study the potential effect, HCIs of Ar^q+ (q = 6–16) with the intensity of 0.1–1 nA are projected on the surface with a constant kinetic energy (16 keV). For photon emission measurements, we observed spatial and spectral distribution of visible light emission from the surface during irradiation with HCIs. On the other hand, the structural modification of multi-walled carbon nanotubes (MWCNTs) irradiated with HCIs has been analyzed using a transmission electron microscopy and Raman spectroscopy. Irradiation effects on the resistivity of single MWCNT supported on micrometer scale bridge pattern were also measured. We have also measured magnetic structure of highly oriented pyrolytic graphite irradiated with HCIs using electron spin resonance at low temperature. At the present paper, we will review our recent experimental results on the interaction of HCI with various carbon-based materials.     

Total deposition velocities and scavenging ratios of 7Be and 210Pb at Rokkasho, Japan

The atmospheric concentrations and deposition fluxes of ⁷Be and ²¹⁰Pb were observed biweekly in Rokkasho, Japan on the Pacific Ocean coast at the northern end of Honshu Island, from March 2000 to March 2006, to clarify their regional features. Seasonal variation pattern of atmospheric ⁷Be concentrations had double peaks, and that of ²¹⁰Pb had a single peak. Deposition fluxes of ⁷Be and ²¹⁰Pb showed the same patterns. The total deposition pattern of ⁷Be was similar to that commonly seen on the Pacific Ocean side of northern Honshu Island, while the pattern of ²¹⁰Pb was similar to that commonly seen on the Japan Sea side. The lack of high spine mountains windward in Rokkasho may be the cause of this ambiguity in the winter monsoon season. Total deposition velocities and scavenging ratios of ²¹⁰Pb were similar to those of ⁷Be from spring to fall, and showed that both nuclides had a similar removal process from the atmosphere. However, the scavenging ratios of ²¹⁰Pb were slightly larger than those of ⁷Be in winter, indicating different behaviors for both nuclides in the scavenging process. The scavenging ratios of both nuclides inversely correlated with precipitation rate, and the ratios in winter were larger than in the other seasons.     

Photoswitchable organocatalysis in acylation of alcohol using dithienylethene-linked azoles

Three novel dithienylethenes bearing azole derivatives were synthesized and found to undergo reversible photocyclization of the dithienylethene units upon alternate irradiation with UV and visible light. Among them, the dithienylethene-linked imidazole and N-phenylimidazole exhibited a relatively high organocatalytic activity for the acylation of 2-decanol with acetic anhydride, and the catalytic activity of the dithienylethene-linked imidazole could be switched by reversible photoinduced cyclization/cycloreversion of the dithienylethene unit.     

Application of simplified desorption method to study on sorption of americium(III) on bentonite

To elucidate the sorption behavior of americium(III) on bentonite, which is a mixture of montmorillonite clay, quartz and other minerals, simplified desorption experiments were applied to the solid phases collected after the sorption experiments. The sorption–desorption behavior was examined in the final pH range from 2 to 8. The desorption experiments revealed that most of the Am was sorbed on the montmorillonite moiety of the bentonite. The sorption of Am on montmorillonite was divided into two types: one was the “exchangeable” sorption, in which the sorbed Am was desorbed with a 1 M KCl aqueous solution, and the rest was the “unexchangeable” sorption. The exchangeable sorption was ion exchange of mostly Am³⁺. The unexchangeable sorption was the strong sorption of Am hydroxides. An accessory iron mineral, pyrite, might be involved in the Am sorption on bentonite at neutral pH.     

Semiempirical calculation of electronic spectra of organic compounds by using the improved method of new-γ electron repulsion integral. Part 2. Polycyclic aromatic hydrocarbons (PAHs)

Excitation energies of 123 polycyclic aromatic hydrocarbons were calculated by incorporating the improved method of new-γ for the two-center electron repulsion integral into two semiempirical molecular orbital methods (CNDO/S and INDO/S). This variable method well reproduced experimental excitation energies of them. The average error of the improvement is about 0.162 (CNDO/S) or 0.237 eV (INDO/S) though the average error without the improvement is about 0.541 (CNDO/S) or 0.536 eV (INDO/S). The improvement was useful for the calculations of other organic compounds including hetero atoms, such as organic dye.