Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Computational Analysis Reveals a Critical Point Mutation in the N-Terminal Region of the Signaling Lymphocytic Activation Molecule Responsible for the Cross-Species Infection with Canine Distemper Virus

Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility.     

The kinetics of the light-induced defect creation in hydrogenated amorphous silicon – Stretched exponential relaxation

Our model for light-induced defect creation in hydrogenated amorphous silicon is applied to its kinetics, i.e., the growing curve of light-induced dangling bond density as a function of illumination time, which is fitted to a stretched exponential function. Two parameters β and τ involved in the function are estimated as functions of saturated dangling bond density in terms of our model. These are compared with two experimental results, i.e., our results obtained from ESR measurements and Shimakawa et al.’s results obtained from photoconductivity measurements. The saturated dangling bond density is also measured as a function of the generation rate of free carriers. The experimental results are compared with calculated results and discussed.     

Classical in-plane negative magnetoresistance and quantum positive magnetoresistance in undoped InSb thin films on GaAs (1 0 0) substrates

Magnetoresistance (MR) effects have been investigated in perpendicular and parallel magnetic fields at 300, 80 K and liquid He temperatures for undoped InSb thin films 0.1–2.3 μm thick grown on GaAs(1 0 0) substrates by MBE. At high temperatures, the intrinsic carriers show the parabolic negative MR observable only in magnetic fields parallel to the film. The skipping-orbit effect due to surface boundary scattering in the classical orbits in the plane vertical to the film has been argued to be responsible for the negative MR. At low temperatures (T=80 K), the transport is dominated by the two-dimensional (2D) electrons in the accumulation layers at the InSb/GaAs(1 0 0) hetero interface; MR is positive and shows a logarithmic increase with anisotropy between parallel and perpendicular field orientation, arising from the 2D weak anti-localization (WAL) that reflects the interplay between the spin-Zeeman effect and strong spin–orbit interaction caused by the asymmetric potential at the interface (Rashba term). The zero-field spin splitting energy of Δ₀13 meV, the electron effective mass of m^*0.10m₀ seven times of the band edge mass in bulk InSb and the effective g-factor of |g^*|15 in the accumulation layer have been inferred from fits of MR for the 0.1 μm thick film to the 2D WL theory.     

Characterization of metal binding properties of rhamnogalacturonan II from plant cell walls by size-exclusion HPLC/ICP-MS.

The binding properties of metal ions to a pectic polysaccharide, rhamnogalacturonan II (RG-II), from plant cell walls were analyzed by size-exclusion HPLC/ICP-MS. The dimeric RG-II borate complex (dRG-II-B) from sugar beet and red wine contained 0.8 - 1.1 mol/mol of B, 0.8 - 1.1 mol/mol of Ca, 0.1 - 0.3 mol/mol of Sr, and 0.03 - 0.07 mol/mol of Ba. The treatment of dRG-II-B with Sr2+, Ba2+, Pb2+ or La3+ exchanged the originally present Ca, Sr and Ba. In contrast, monomeric RG-II (mRG-II), which contained approximately 0.1 mol/mol of Ca, formed complexes with La3+, Eu3+, and Lu3+ added to the solution, but did not do so with Ca2+, Sr2+, Ba2+ and Pb2+. The HPLC/ICP-MS and HPLC/RI (refractive index detector) analysis of the partially hydrolyzed mRG-II that was treated with La3+ indicated that the side chains and backbone of mRG-II together form a lanthanoid binding site.     

Some remarks on projectively flat complex Finsler metrics

In this paper, we hall discuss the projective flatness of complex Finsler metrics by investigating the geometry of projective bundles associated with a holomorphic vector bundle.     

Interpretation of initial stage of 3C-SiC growth on Si(1 0 0) using dimethylsilane

The initial stage of cubic silicon carbide (3C-SiC) growth on a Si(0 0 1) surface using dimethylsilane (DMS) as a source gas was observed using scanning tunneling microscopy (STM) and reflection high-energy electron diffraction (RHEED). It was found that the dimer vacancies initially existing on the Si(0 0 1)-(2 × 1) surface were repaired by the Si atoms in DMS molecules, during the formation of the c(4 × 4) surface. From the STM measurement, nucleation of SiC was found to start when the Si surface was covered with the c(4 × 4) structure but before the appearance of SiC spots in the RHEED pattern. The growth mechanism of SiC islands was also discussed based on the results of RHEED, STM and temperature-programmed desorption (TPD).     

Compact directed acyclic word graphs for a sliding window

Suffix trees are a well-known and widely-studied data structure highly useful for string matching. The suffix tree of a string w can be constructed in O(n) time and space, where n denotes the length of w. Larsson achieved an efficient algorithm to maintain suffix trees for a sliding window. It contributes to prediction by partial matching (PPM) style statistical data compression scheme. Compact directed acyclic word graphs (CDAWGs) are a more space-economical data structure for indexing strings. In this paper we propose a linear-time algorithm to maintain CDAWGs for a sliding window.