Surface reaction of alkynes and alkenes with H-Si(111): a density functional theory study

Recent experiments on the addition of alkene and alkyne molecules to H-terminated silicon surfaces have provided evidence for a surface chain reaction initiated at isolated Si dangling bonds and involving an intermediate carbon radical state, which, after abstraction of a hydrogen atom from a neighboring Si-H unit, transforms into a stable adsorbed species plus a new Si dangling bond. Using periodic density functional theory (DFT) calculations, together with an efficient method for determining reaction pathways, we have studied the initial steps of this chain reaction for a few different terminal alkynes and alkenes interacting with an isolated Si dangling bond on an otherwise H-saturated Si(111) surface. Calculated minimum energy pathways (MEPs) indicate that the chain mechanism is viable in the case of C(2)H(2), whereas for C(2)H(4) the stabilization of the intermediate state is so small and the barrier for H-abstraction so (relatively) large that the molecule is more likely to desorb than to form a stable adsorbed species. For phenylacetylene and styrene, stabilization of the intermediate state and decrease of the H-abstraction barrier take place. While a stable adsorbed species exists in both cases, the overall heat of adsorption is larger for the alkyne molecules.     

Total synthesis of leustroducsin B

A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O).     

Practical optical frequency measurement system around 1.5 μm based on an acetylene-stabilized laser-locked optical frequency comb

We have developed a practical and precise frequency measurement system at 1.5 μm telecommunication band. An electro-optic-modulator based optical frequency comb is phase-locked to a dither-free acetylene-stabilized laser to realize an optical frequency comb with frequency uncertainty of 10 kHz (5 × 10⁻¹¹) and the linewidth of 15 kHz. The present frequency comb can be also used as an optical frequency reference grid defined by ITU-T (International Telecommunication Union, Telecommunication Standardization Sector). Using the present frequency measurement system, we have demonstrated the first optical frequency measurement of ¹²C¹⁶O overtone absorption lines around 1.56 μm with the uncertainty of lower than 900 kHz.     

Synthesis of [60]fullerene-containing [2]rotaxanes using axle molecules bearing donor moiety

[2]Rotaxanes, consisting of a fullerene derivative bearing an electron-donating 1,5-dialkoxynaphthalene moiety and a macrocycle containing electron-deficient naphthalenetetracarboxylic diimide moieties, were first successfully synthesized and characterized.     

Localized solutions to the nonlinear wave equation for flexural motions of an elastic beam traveling in an air-filled tube

Steady-progressive-wave solutions are sought to the nonlinear wave equation derived previously [J. Fluids Struct. 16 (2002) 597] for flexural motions of an elastic beam traveling in an air-filled tube along its center axis at a subsonic speed. Fluid-structure interactions are taken into account through aerodynamic loading on the lateral surface of the beam subjected to small but finite deflection but end effects and viscous effects are neglected. Linear dispersion characteristics are first examined by exploiting the small ratio of the induced mass to the mass of the beam per unit length. Centered around the traveling speed of the beam, there exists such a narrow range of propagation velocity that the linear steady propagation is prohibited. In this range, it is revealed that some interesting nonlinear solutions exist. The periodic wavetrain is found to exist as the exact solution. Asymptotic analysis is then made by applying the method of multiple scales and the stationary nonlinear Schrödinger equation is derived for a complex amplitude. A monochromatic solution to this equation corresponds to the exact periodic solution. Imposing undisturbed boundary conditions at infinity, it is revealed that the localized solution exists as a result of balance between the linear instability and the nonlinearity. This solution is checked by solving the nonlinear equation numerically. It is further revealed that the amplitude-modulated wavetrain exists not only in the range of the velocity mentioned above but also outside of it.     

Genetic algorithm‐based wavelength selection method for spectral calibration

In this paper, we propose a genetic algorithm‐based wavelength selection (GAWLS) method for visible and near‐infrared (Vis/NIR) spectral calibration. The objective of GAWLS is to construct robust and predictive regression models by selecting informative wavelength regions. To demonstrate the ability of the proposed method, regression models for soil properties and sugar content of apples are constructed by using GAWLS and other variable selection methods. Copyright © 2010 John Wiley & Sons, Ltd.     

Near-infrared emission bands of Er-doped YAP and LSO crystals

The ground state absorption (GSA), photoluminescence (PL) and photoluminescence excitation (PLE) spectra for Er(1.0 at%):YAP and Er(0.5 at%):LSO were measured at room temperature. Based on the GSA spectra, the radiative transition rates and luminescence branch ratios of erbium ions were determined by the Judd-Ofelt (J-O) method. In the range of 1400-1700 nm Er(1.0 at%):YAP has intense absorption at 1509 nm (0.96×10⁻²⁰ cm²), which is almost two times larger than the peak absorption of Er(0.5 at%):LSO. From the PL and PLE spectra, four intense emission bands around 850 nm (⁴S_3/2→⁴I_13/2), 980 nm (⁴I_11/2→⁴I_15/2), 1230 nm (⁴S_3/2→⁴I_11/2) and 1520 nm (⁴I_13/2→⁴I_15/2) were observed. The stimulated emission cross-sections of the four bands were calculated by the Fuchtbauer-Ladenberg (F-L) equation. The results suggest that Er(1.0 at%):YAP has potential to realize laser oscillation at 858 nm because of the relatively large simulated emission cross-section (1.76×10⁻²⁰ cm²). The temperature dependences of the PL spectra for the two crystals were also investigated in the range of 290-12 K. The ∼1520 nm emission presents continuous increase with temperature, while the emissions around 850, 1230 and 980 nm firstly increase with temperature, then reach their own largest values at the transition temperatures (about 100 K), and finally decrease with temperature. These results were well interpreted by the temperature dependence of multi-phonon process.     

Curdlan as a Polymeric Starting Material to Access C6-Modified Glucose Derivatives

We evaluated the potential of a linear β-1,3-glucan (curdlan) as a starting material to access C6-modified glucose derivatives and found that 6-bromo-6-deoxyglucose, 6-azide-6-deoxyglucose, and 6-acetamido-6-deoxyglucose could be readily prepared from curdlan through its C6-selective and quantitative modifications and subsequent acid-catalyzed hydrolysis.     

On the volume and surface area of hyperbolic polyhedra

A truncated tetrahedron is a building block of hyperbolic 3-manifolds with totally geodesic boundary. We study the relation between the volume of a truncated tetrahedron and the area of its faces which form the boundary of manifolds.