Molecular structures and hypochromism of two purinophanes

The structures of purinophane 1 and its higher homolog 2 were determined by X-ray crystallographic analysis. Hypochroism of 1 and 2 in various media reported.     

Unusual reactivity of (6,9)purinophanes due to stereoelectronic effect

[n](6,9)Purinophanes 2a–c were synthesized and their unusual reactivity toward nucleophiles was explained by the stereoelectronic effect in the fairly rigid tetrahedral intermediate.     

Detection of O(3P(J)) atoms formed by reaction, Al+O2--> AlO+O under crossed-beam condition

The vacuum ultraviolet laser-induced fluorescence technique was employed to detect the oxygen atoms formed by the reaction, Al+O(2)--> AlO+O. The measurements were carried out under the crossed-beam condition at 12.2 kJmol of collision energy. The relative populations of three spin-orbit states of O((3)P(J)) were determined to be 3.8, 1.0, and 0.2 for J=2, 1, and 0, respectively. They show nonstatistical populations, i.e., more population in O((3)P(2)) and less population in O((3)P(0)) than the statistical expectation. These populations were almost identical for two Al beam conditions where the relative concentrations of two spin-orbit states of Al, (2)P(1/2), and (2)P(3/2), are different. These results suggest that the reaction of Al with O(2) proceeds via an intermediate complex where the memory of the initial spin-orbit state is lost. Deviation from the statistical population of O((3)P(J)) implies the occurrence of the interaction among potential surfaces in the exit channel.     

Glycosides of Atractylodes lancea

Five sesquiterpenoid glycosides (two guaiane-type glycosides and three eudesmane-type glucosides) and a glucoside of an acetylene derivative were newly isolated from the water-soluble portion of the methanolic extract of Atractylodes lancea rhizome together with 26 known compounds. Their structures were characterized as atractyloside A 14-O-beta-D-fructofuranoside, (1S,4S,5S,7R,10S)-10,11,14-trihydroxyguai-3-one 11-O-beta-D-glucopyranoside, (5R,7R,10S)-isopterocarpolone beta-D-glucopyranoside, cis-atractyloside I, (2R,3R,5R,7R,10S)-atractyloside G 2-O-beta-D-glucopyranoside, and (2E,8E)-2,8-decadiene-4,6-diyne-1,10-diol 1-O-beta-D-glucopyranoside on the basis of chemical and spectroscopic investigation. The presence of six characteristic guaiane-type glucosides in both rhizomes of A. lancea and Atractylodes japonica suggested a close chemotaxonomic relationship between them.     

Nanometer‐sized polyradical particles: Organic magnetic dot array formed on a silicon microfabricated substrate

A magnetically active, purely organic dot array was formed by the selective deposition of polyradical nanoparticles on array‐like‐formed pits on a silicon substrate. The nanometer‐sized polyradical particles, poly(4‐methacryoyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl), were prepared by the emulsion polymerization of 4‐methacryloyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐acetoxyl followed by a deprotection reaction and oxidation in air. The size (diameter) and radical spin concentration of the polyradical nanoparticles were tunable between the polymerization and oxidation conditions. Electrochemical studies revealed the redox property of the polyradical nanoparticles. The magnetic response image of the polyradical nanoparticles was obtained by magnetic force microscopy, reflecting their radical spin concentrations. These results suggested a possible approach for the use of organic polyradical nanoparticles as organic magnetic dot arrays. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 521–530, 2007     

Observation of large arrays of plasma filaments in air breakdown by 1.5-MW 110-GHz gyrotron pulses

We report the observation of two-dimensional plasma filamentary arrays with more than 100 elements generated during breakdown of air at atmospheric pressure by a focused Gaussian beam from a 1.5-MW, 110-GHz gyrotron operating in 3-micros pulses. Each element is a plasma filament elongated in the electric field direction and regularly spaced about one-quarter wavelength apart in the plane perpendicular to the electric field. The development of the array is explained as a result of diffraction of the beam around the filaments, leading to the sequential generation of high intensity spots, at which new filaments are created, about a quarter wavelength upstream from each existing filament. Electromagnetic wave simulations corroborate this explanation and show very good correlation to the observed pattern of filaments.     

Solvent-coordinate free-energy landscape view of water-mediated ion-pair dissociation

Water-mediated ion-pair dissociation is studied by molecular dynamics simulations of NaCl in water. Multidimensional free-energy analysis clarifies the relation between two essential solvent coordinates: the water coordination number and water-bridge formation. These two are related in a complex way. Both are necessary to describe ion-pair dissociation. The mechanism constructed with both solvent variables clearly shows the individual roles. The water coordination number is critical for starting ion-pair dissociation. Water-bridge formation is also important because it increases the likelihood of ion-pair dissociation by reducing the dissociation free-energy barrier. Additional Ca–Cl and NH₄–Cl calculations show that these conclusions are unaffected by changes in the ion charge and shape. The present results will contribute to future explorations of many other molecular events such as surface water exchange and protein-ligand dissociation because the same mechanism is involved in such events.     

Non-fermi-liquid behavior in Sr2RuO4 with nonmagnetic impurities

We report that the quasi-two-dimensional Fermi-liquid behavior of the spin-triplet superconductor Sr2RuO4 breaks down in the vicinity of the critical impurity concentration for the onset of magnetic order induced by nonmagnetic Ti4+ impurities. The non-Fermi-liquid behavior is interpreted in terms of the two-dimensional antiferromagnetic fluctuations, which arise mainly from the nesting within one of the Fermi-surface sheets. We argue against the main role of such magnetic fluctuations in the pairing mechanism.     

Structural analysis of sonochemically prepared Au/Pd nanoparticles dispersed in porous silica matrix

Bimetallic Au/Pd nanoparticles supported on a silica matrix were prepared by an ultrasonic technique. The samples heat-treated at 100, 200, 300 and 400 degrees C were examined with techniques of XRD (X-ray diffraction), TEM and XAS (X-ray absorption spectrometry) for studying correlation between their structure and the catalytic activity of hydrogenation of cyclohexene. Even after the heat treatment at 400 degrees C, the particles were smaller than 20 nm and well dispersed in the matrix without agglomeration nor sintering. Results of the XRD, TEM and XAS indicated that the as-prepared particles have a core/shell structure of Au/Pd and transform into a random alloy at 300 degrees C. The catalysis seemed to be deactivated by alloying.