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.     

Direct observations of freeze-etching processes of ice-embedded biomembranes by atomic force microscopy

We have fabricated a cryogenic atomic force microscope that is designed for structural investigation of freeze-fractured biological specimens. The apparatus is operated in liquid nitrogen gas at atmospheric pressure. Freeze-fracturing, freeze-etching and subsequent imaging are carried out in the same chamber, so that the surface topography of a fractured plane is easily visualized without ice contamination. A controlled superficial sublimation of volatile molecules allows us to obtain three-dimensional views of ultrastructures of biological membranes.     

Diastereoselective photochromism of a bisbenzothienylethene governed by steric as well as electronic interactions

Introduction of an asymmetric center to C-2 of one of the benzothiophene rings of bisbenzothienylperfluorocyclopentene results in a highly diastereoselective photochromic system. The stereogenic center bears a hydrogen atom, a methyl group, and a methoxymethoxy group. The steric as well as the electronic repulsions gave an 87-88% diastereomer excess in various solvents at room temperature with 80-85% conversion to the colored form. The enantioselective synthesis was also carried out. Upon photoirradiation in hexane, a change in optical rotation at 820 nm, where neither the open form nor the colored form absorbs light, was observed repeatedly.     

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).     

Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.     

Use of the organic crystal DAST for terahertz beam applications

We report the use of the organic crystal DAST as a freely propagating electromagnetic-wave sensor at terahertz (THz) frequency. We also report the result of using a DAST crystal as a mid-IR THz emitter. Compared with the optical rectification from our best ZnTe emitter, that obtained by use of DAST demonstrates a sixfold enhancement of radiation at 7-20 THz.     

A study on shielding gas contamination in laser welding of non-ferrous alloys

Laser welding of non-ferrous alloys is a high-productivity and cost-effective joining technology, which gained an undoubted interest especially in aerospace, chemical and medical industry, where high strength and corrosion resistant mechanical parts are required. Unfortunately some of the most used non-ferrous alloys are highly reactive with respect to the components of the environmental atmosphere: oxygen, nitrogen, hydrogen and humidity. This reactivity leads to the formation of porosities and to oxides and nitrides inclusion, which are responsible for a decrease of ductility and strength in welded joints.According to this a good shielding technique of the weld pool is of primary importance in order to obtain sound beads and reliable manufacturings. This paper deals with the opportunity of simulating the shielding gas behavior by means of Computational Fluid Dynamics software in order to understand the relationship among the outlet position, the shielding gas type and its flow rate.A simulation activity was carried out in order to evaluate the behavior of shielding gas concentration surrounding the weld pool. The simulated welding environment was simplified without considering the presence and the effect of the plasma plume. The main results concern the shielding gas contamination prediction with respect to the distance from the beam-material interaction zone.     

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.