Interaction of bathocuproine with metals (Ca, Mg, Al, Ag, and Au) studied by density functional theory

Electronic structure of the interface between a bathocuproine (BCP) molecule and metal surface was studied by density functional theory. The bond energy of BCP with metal surface increased with decreasing work function of metals, that is, Au, Ag, Al, Mg, and Ca in this order. The charge transfer also increased with decreasing metal work function. It was analyzed that the Fermi level and the lowest unoccupied molecular orbital of BCP are composed of both BCP and metal orbital component, and electron transport properties across the BCP and metal is discussed based on these analyses.     

Packing manner of graft copolymers with rigid‐rod main chains and amorphous‐crystalline diblock copolymers as side chains

We have investigated the morphology and packing manner of graft copolymers consisting of rigid‐rod‐like poly(γ‐benzyl L ‐glutamate) (PBLG) main chains and grafted diblock copolymers of amorphous poly(propylene glycol) (PPG) and crystalline poly(ethylene glycol) (PEG). The results of differential scanning calorimetry and wide‐angle X‐ray scattering measurements for graft copolymers with higher side‐chain volume fractions suggest that the rodlike main chains and crystallized PEG chains exist in segregated domains. Small‐angle X‐ray scattering profiles for these samples show diffraction intensity maxima accompanied by higher order peaks, the positions of which suggest the formation of an ordered layered structure. From these observations, the graft copolymers are estimated to form repeated layered structure consisting of segregated PBLG, PPG, and PEG layers. A proposed model for molecular packing of the graft copolymers is consistent with the experimental observation that the repeating distance for the layered structure decreases with an increase in the volume fraction of side chains. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1904–1912, 2002     

Melt rheology of hyperbranched‐polystyrene synthesized with multisite macromonomer

Melt rheological behaviors of hyperbranched‐polystyrene (PS) copolymerized by dendric macromonomer technique are presented. The time–temperature superposition principle was applicable to the hyperbranched‐PS. The branched‐PS showed slightly lower zero‐shear viscosity in comparison with linear PS regardless of a presence of a number of branches expected from the dendric macromonomer technique. Although the influence of use of multimethacryloyl macromonomer in the polymerization process was marginal for linear viscoelastic regime, nonlinear shear and uniaxial elongational flows showed distinct differences between linear and branched‐PS. The strain dependence of the damping function became weak as increase of macromonomer content. The branched‐PS exhibited the growing elongational viscosity function comparing with linear PS. This prominent effect on the elongational flow behavior can be explained by the molecular architecture of the branched‐PS. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2226–2237, 2009     

Whole field spatial frequency analysis of double-or multiple-exposed PIV images

Speckle Velocimetry or high-image density PIV gives a velocity vector map of a twodimensional flow field by point-by-point spatial frequency analysis of local pattern at an interrogation spot in a double- or a multiple-exposed image of laser speckle or pseudo-speckle pattern generated by pulsed laser-light-sheet illuminations of a plane in the flow densely seeded with fine particles. The whole field spatial frequency analysis of the double- or multiple-exposed PIV image gives more useful information of the flow field. Optical Fourier transform is a conventional technique not only for the local spatial frequency analysis but for the whole field analysis. Filtering of spatial frequency is one of the typical techniques for the latter which can reconstruct a velocity contour or a component velocity contour map of the flow. Fundamentally this technique is a simple and efficient analogue method to get more information in the velocity field analysis of the flow than a digital image processing, but in practical applications the measurement is restricted to simple flows because of optical noise and low spatial resolution. In order to improve the technique, the fundamental characteristics of the filtering and the noise yielded in the filtering process must be investigated. Meanwhile, wavelet analysis can also be applied to the whole field spatial frequency analysis of PIV image. In this paper the filtering technique is examined by numerical convolution integral, and the results obtained are compared with ones obtained by the wavelet analysis.     

Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol

A persistent dialkylsilanone was synthesized by the dehydrobromination of a dialkylbromosilanol with tris(trimethylsilyl)silyl potassium in solution at ?80 °C: It was characterized by NMR and IR spectroscopy, and was tested in several reactions. In ²⁹Si NMR spectrum in [D₈]toluene, the signal due to the unsaturated silicon nuclei was observed at 128.7 ppm. Reactions of the dialkylsilanone with water and mesitonitrile oxide gave a silanediol and a [2+3] cycloadduct, respectively. The silanone remains intact in [D₈]toluene below ?80 °C for at least two days, while it undergoes unprecedented isomerization to give a siloxysilene by means of 1,3‐silyl migration at higher temperatures.     

The synthetic and biological studies of discorhabdins and related compounds

Various analogues of the marine alkaloids, discorhabdins, have been synthesized. The strategy contains spirocyclization with phenyliodine(III) bis(trifluoroacetate) (PIFA), oxidative fragmentation of the β-amino alcohols with the hypervalent iodine reagent C(6)F(5)I(OCOCF(3))(2), the detosylation and dehydrogenation reaction of the pyrroloiminoquinone unit in the presence of a catalytic amount of NaN(3) and the bridged ether synthesis with HBr-AcOH as the key reactions. All the synthesized compounds were evaluated by in vitro MTT assay for cytotoxic activity against the human colon cancer cell line HCT-116. Furthermore, the discorhabdin A oxa analogues were also evaluated against four kinds of tumor model cells, a human colon cancer cell line (WiDr), a human prostate cancer cell line (DU-145) and murine leukemia cell lines (P388 and L1210). For the identification of the target, discorhabdin A and the discorhabdin A oxa analogue were evaluated by an HCC panel assay. In the test, discorhabdins could have a novel mode of action with the tumor cells.     

The existence of a 2‐factor in K1, n‐free graphs with large connectivity and large edge‐connectivity

In this article, we study the existence of a 2‐factor in a K_{1, n}‐free graph. Sumner [J London Math Soc 13 (1976), 351–359] proved that for n?4, an (n?1)‐connected K_{1, n}‐free graph of even order has a 1‐factor. On the other hand, for every pair of integers m and n with m?n?4, there exist infinitely many (n?2)‐connected K_{1, n}‐free graphs of even order and minimum degree at least m which have no 1‐factor. This implies that the connectivity condition of Sumner's result is sharp, and we cannot guarantee the existence of a 1‐factor by imposing a large minimum degree. On the other hand, Ota and Tokuda [J Graph Theory 22 (1996), 59–64] proved that for n?3, every K_{1, n}‐free graph of minimum degree at least 2n?2 has a 2‐factor, regardless of its connectivity. They also gave examples showing that their minimum degree condition is sharp. But all of them have bridges. These suggest that the effects of connectivity, edge‐connectivity and minimum degree to the existence of a 2‐factor in a K_{1, n}‐free graph are more complicated than those to the existence of a 1‐factor. In this article, we clarify these effects by giving sharp minimum degree conditions for a K_{1, n}‐free graph with a given connectivity or edge‐connectivity to have a 2‐factor. Copyright © 2010 Wiley Periodicals, Inc. J Graph Theory 68:77‐89, 2011