Extensive quinoidal oligothiophenes with dicyanomethylene groups at terminal positions as highly amphoteric redox molecules

A series of highly extensive quinoidal oligothiophenes carrying a dicyanomethylene group at both terminal positions is synthesized. As the quinoidal structures extend, they have highly amphoteric abilities and show strong electronic absorptions in the visible to near-infrared region. The higher homologues, quinquethiophene and sexithiophene, exist as equilibrium mixtures with the biradical species.     

Asymmetric total synthesis of (+)-K01-0509 B: determination of absolute configuration

K01-0509 B is a novel natural product which contains a carbamoylated cyclic guanidine. Our asymmetric total synthesis features a Sharpless asymmetric epoxidation and a stereocontrolled construction of the cyclic guanidine via an asymmetric nitroaldol reaction, followed by intramolecular SN2 cyclization. These reactions allowed the cyclic guanidine and the adjacent hydroxy group to be assembled, facilitating the asymmetric total synthesis and determination of the absolute stereochemistry of K01-0509 B. [reaction: see text].     

Polypyrrole coating doped by molybdo-phosphate anions for corrosion prevention of carbon steels

The polypyrrole coating was prepared from phosphoric acid aqueous solution containing the hetero-polyanion and pyrrole monomer to make new coating for corrosion prevention of carbon steels. The coating thus formed in the phosphate acid solution was doped by and by . The coating was flexible enough to cover the steel homogeneously without cracks, although many cracks were observed on the coating formed in a neutral aqueous solution of Na₂MoO₂. The 5.1-μm-thick polypyrrole coating makes the steel maintain the passive state for 48 h in neutral 3.5 wt% NaCl solution at pH 5.3 and for 80 h in acidic 3.5 wt% NaCl solution at pH 1.9. The coating decreased the corrosion rate of the steel by 1/200 in the neutral NaCl solution and by 1/340 in the acidic NaCl solution, if compared with the rate of the bare steel. The dissolution current of the steel during the immersion remained at the level of the typical passive current in the respective solutions.     

Free vibration characteristics of double-walled carbon nanotubes embedded in an elastic medium

In this Letter, a theoretical analysis of the resonant vibration of double-walled carbon nanotubes (DWCNTs) and the DWCNTs embedded in an elastic medium is presented based on Euler-Bernoulli beam model and Winkler spring model. The vibration modes of DWCNTs are quite different from those of single-walled carbon nanotubes (SWCNTs). The resonant vibrations of DWCNTs are found to have in-phase and anti-phase modes, in which the deflections of the inner and outer nanotubes occur in the same and opposite directions, respectively. For the vibration of DWCNTs with the same harmonic numbers, the resonant frequencies of anti-phase mode are larger than the ones of in-phase mode. Moreover, influence of the surrounding medium on the resonant vibrations is investigated using the Winkler spring model. The results show that surrounding medium makes a strong impact on the vibration frequencies of in-phase mode, but little on those of anti-phase mode.     

Conformationally averaged score functions for electronic propagation in proteins

We explore the influence of conformational dynamics on protein-mediated electron donor-acceptor interactions. We introduce a thermally averaged score function to characterize electronic propagation from redox cofactors into the protein and solvent. The score function is explored for myoglobin at the extended-Hückel level, and the results are compared with those of simpler models. The conformationally averaged quantum results are consistent with the empirical analysis of the Pathways model. Notably, subtle effects of quantum interference among multiple coupling pathways that arise in static structures are largely averaged out when protein thermal motion is included. Propagation through bulk water near the single-protein interface decays rapidly with distance.     

Structural study of NO adsorbed on the reconstructed Pt(110)-(1 x 2) surface with X-ray photoelectron diffraction and near-edge X-ray absorption fine structure spectroscopy

The adsorption structure of NO on the reconstructed Pt(110)-(1 x 2) surface was studied with X-ray photoelectron spectroscopy (XPS), X-ray photoelectron diffraction (XPD), low-energy scanned-angle photoelectron diffraction (LESA-PD), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The experiments were performed at 180 K, where no surface lifting from (1 x 2) to (1 x 1) takes place after NO adsorption. XPS indicates that the (1 x 2) unit cell of the Pt(110) surface contains 1.5 NO molecules at the saturated coverage. XPD and LESA-PD analyses allow us to propose a structural model for the NO adlayer, where two-thirds of the NO molecules in the (1 x 2) unit cell are adsorbed on the atop site of the close-packed Pt rows (ridges) along the [10] direction with an inclined geometry and one-third of the NO molecules adsorb on the bridge site between the Pt ridges with an upright configuration. This model is supported by the N K-edge NEXAFS experiments and is consistent with the recently reported model based on the density functional theory (Orita, H.; Nakamura, I.; Fujitani, T. J. Phys. Chem. B 2005, 109, 10312).     

Contrast analysis of Shockley partial dislocations in 4H-SiC observed by synchrotron Berg–Barrett X-ray topography

Shockley partial dislocations in 4H-SiC were observed using monochromatic synchrotron X-ray topography with a grazing-incidence Bragg-case geometry, that is, Berg–Barrett topography. The contrast of partial dislocations at the edges of Shockley-type stacking faults is discussed in terms of whether they have C- or Si-core edge components, or screw components. The dissociated state of basal-plane dislocation is discussed on a basis of the stacking sequence for basal-planes in the 4H-SiC crystal structure. It is expected that the results obtained in this study will be useful for characterizing Shockley-type stacking faults in Berg–Barrett topography.     

Sonochemical immobilization of noble metal nanoparticles on the surface of maghemite: mechanism and morphological control of the products

Aqueous sample solutions containing noble metal ions (HAuCl₄, Na₂PdCl₄, H₂PtCl₆), polyethyleneglycol monostearate, and magnetic maghemite nanoparticles were irradiated with high power ultrasound. Analyses of the products showed that noble metal ions were reduced by the effects of ultrasound, and the formed noble metal nanoparticles were uniformly immobilized on the surface of the maghemite. The present “one pot process” significantly simplifies the immobilization of noble metal nanoparticles on the surface of supports, compared with the conventional impregnation method. The average diameter of immobilized Au was 7–13 nm, and the diameters of Pd and Pt were several nm. The diameters depended upon the concentration of polyethyleneglycol monostearate and the concentration of noble metal ions, but not upon the maghemite concentration, indicating the possibility of the morphological controls of the products by adjusting these preparation conditions. The measurements of the average diameters and the numbers of immobilized Au nanoparticles obtained under various conditions suggest that the nucleation of Au does not occur on the surface of maghemite, but it might occur in the homogeneous bulk solution.