Isomer-selected photoreactions of gas-phase cluster ions

We have developed an apparatus for investigating isomer-selected photodissociation reactions by ion mobility spectrometry coupled with time-of-flight mass spectrometry. By using this apparatus we optimized ion intensities under isomer-separation condition for carbon cluster ions. Among ions having linear and cyclic isomers, we demonstrated dissociation of isomer-selected C₉ ⁺ ion at 355-nm photon irradiation. As a result we observed marked difference in the dissociation pathways between from linear isomer and from cyclic isomer. For the purpose of adopting this technique to metal-ligand cluster ions, we also investigated mobility spectrometry of vanadium metal ions with Ar, in addition to electronic state separation for free atomic ions.     

The electrochemical behavior of ad-atoms and their effect on hydrogen evolution: Part IV. Tin and lead ad-atoms on platinum

Hydrogen evolution on a platinum electrode decays against X_pt with the deposition of Sn ad-atoms and Pb ad-atoms in the same way as it decays with that of Ge ad-atoms, in which all of these ad-atoms occupy two platinum sites. In general the decay depends on the number of sites occupied by an atom of the ad-atom species.The potential ranges for oxygen adsorption by Sn ad-atoms and Pb ad-atoms are 0.45 to 1.24 V and 0.48 to 0.77 V, respectively, but the oxygen adsorbed by the latter ad-atoms is very small in amount.     

The electrochemical behavior of ad-atoms and their effect on hydrogen evolution: Part II. Arsenic ad-atoms on platinum

The state of an arsenic layer electrodeposited at various potentials on platinum electrodes has been examined electrochemically. The relation between the state and the electrocatalytic activity for hydrogen evolution has been investigated. The number of vacant sites have been found to increase with lowering of the deposition potential. The activity has been found to depend not on the amount of deposited arsenic but on the number of vacant sites. The difference in the effects of arsenic and of copper on hydrogen evolution is pointed out. This is attributed to the difference in the affinity of the ad-atoms for hydrogen.     

Senecicannabine,a new pyrrolizidine alkaloid from senecio cannabifolius

The structure of senecicannabine($\text{1}$), a new mcrocyclic pyrrolizidine alkaloid isolated from $\text{Senecio cannabifolius}$, has been established by chemical study and X-ray analysis.     

Micro-thermal analysis of thermal conductance distribution in advanced silicon nitrides

A micro-thermal analysis technique was applied to investigate advanced silicon nitride materials, which exhibit high thermal conductivity. Local thermal properties in the microstructure were evaluated, and the grain boundaries were observed to have lower thermal conductance than the Si₃N₄ grains. It was found that thermal conductance both in the grains and boundaries was lowered by the addition of the sintering aid Al₂O₃, which is soluble in Si₃N₄ grains. This indicates that high thermal conductivity in silicon nitride ceramics is achieved both by grain growth, leading to a reduction in boundary density, and by eliminating soluble elements in silicon nitride grains. This revised version was published online in August 2006 with corrections to the Cover Date.     

C-F Bond Formation for the Synthesis of Aryl Fluorides

A selection of carbon-fluorine bond-forming reactions is presented with particular focus on transition metal-mediated fluorination. A brief summary of conventional fluorination reactions is followed by a discussion of fluorination reactions mediated by palladium and silver. Investigations into the mechanism as well as the conceptual difficulty associated with transition metal-mediated carbon-fluorine bond formation are presented.     

LIGHT INDUCED FLUORESCENCE SPECTRAL CHANGES IN NATIVE PHYTOCHROME FROM Secale cereale L. AT LIQUID NITROGEN TEMPERATURE

Abstract— Fluorescence spectra of native rye phytochrome were determined under different light conditions at liquid nitrogen temperature. Fluorescence spectrum of the red-light-absorbing form (Pr) had a major peak at about 685 nm (14 600 cm⁻¹) and a broad sub-peak at about 515 nm (19 400 cm⁻¹). The peak height at 685 nm was reduced by irradiation with monochromatic light of 640 nm, and a new peak became obvious at about 702 nm (14250 cm⁻¹). This spectral change was almost completely reversed by subsequent irradiation with 700-nm light. Fluorescence spectrum of the photoequilibrium mixture of Pr and far-red-light absorbing form under continuous red light showed a sharp peak at about 685 nm having a peak height ca. 12% of Pr, and a broad sub-peak at about 508 nm (19 700 cm⁻¹). Light of 730 nm did not reduce the peak height at about 685 nm but induced a new shoulder at about 699 nm (14300 cm⁻¹). Monochromatic light of 640 and 700 nm given following the light of 730 nm could not reverse the spectral change at 699 nm induced by the irradiation with 730-nm light. Fluorescence spectrum of Pr in partially degraded phytochrome was similar to that in native phytochrome but the peak position in the red region was shifted by about 5 nm (100 cm⁻¹) to the blue.     

Vacuum fusion determination of micro-quantities of bulk gases in low carbon iron without an effect of surface gases

Summary Vacuum Fusion Determination of Micro-quantities of Bulk Gases in Low Carbon Iron Without an Effect of Surface Gases Micro-quantities of bulk and surface oxygen and hydrogen in low carbon iron was simultaneously determined by the surface-area-variation method using vacuum fusion analysis. Among the difference of three surface treatments, silicon carbide abrasive, electropolishing and hydrogen reduction methods, bulk oxygen and hydrogen were in agreement within their errors, however, surface oxygen and hydrogen were influenced from the surface treatments. Even in the case of electropolishing, which gave the smallest surface oxygen value, bulk oxygen less than 10g/g is needed to discriminate from the surface oxygen. Bulk hydrogen of 0.03g/g was determined without the effect of surface hydrogen in the hydrogen reduction treatment.     

Indomethacin sustained-release suppositories containing sugar ester in polyethylene glycol base

Indomethacin (IM) sustained-release suppositories were prepared by the fusion method using sugar ester and polyethylene glycol 4000 (PEG). The suppositories were evaluated by in vitro release testing, X-ray analysis and in vivo absorption testing in rabbits. X-ray analysis showed that IM was amorphous in PEG-base suppositories. In a release test, slow-release was obtained when the sugar ester content of a suppository was 60%. The IM plasma level following the administration of the suppository was well sustained in the absorption test. The main slow-release mechanism is considered to be the release of IM from the matrix composed of sugar ester and PEG, which is represented by the Higuchi equation. A good correlation between the release test and the absorption test was obtained. It is considered that the amorphous state of IM in this type of sustained-release suppository would enhance the release and absorption of IM in the rectum of the rabbit, whose rectal fluid volume is small.     

QUATERNARY STRUCTURE OF PEA PHYTOCHROME I DIMER STUDIED WITH SMALL-ANGLE X-RAY SCATTERING and ROTARY-SHADOWING ELECTRON MICROSCOPY

Abstract— The quaternary structure of pea phytochrome type I (PI) dimer in the red-light-absorbing form was studied by small-angle X-ray scattering (SAXS) technique and rotary-shadowing electron microscopy. Structural parameters for PI 114 kDa chromopeptide dimer and its tryptically digested N-terminal 59 kDa chromopeptide monomer, such as average electron density, molecular volume and the second moment of electron density distribution, were determined in terms of SAXS using the contrast variation method. Furthermore, by means of model simulation for the scattering profiles of the chromopeptides, most plausible structural models for both peptides were constructed. The distance between the chromophoric domains was estimated to be about 70 A in the resultant model for 114 kDa chromopeptide dimer. Furthermore, the model was consistent with the electron-micrographic images of both the intact PI dimer and the PI 114 kDa chromopeptide dimer, so that the N-terminal 7 kDa fragment did not significantly contribute the low-resolution images of the dimer.