Sequential One‐Pot Addition of Excess Aryl‐Grignard Reagents and Electrophiles to O‐Alkyl Thioformates

The sequential addition of aromatic Grignard reagents to O‐alkyl thioformates proceeded to completion within 30 s to give aryl benzylic sulfanes in good yields. This reaction may begin with the nucleophilic attack of the Grignard reagent onto the carbon atom of the O‐alkyl thioformates, followed by the elimination of ROMgBr to generate aromatic thioaldehydes, which then react with a second molecule of the Grignard reagent at the sulfur atom to form arylsulfanyl benzylic Grignard reagents. To confirm the generation of aromatic thioaldehydes, the reaction between O‐alkyl thioformates and phenyl Grignard reagent was carried out in the presence of cyclopentadiene. As a result, hetero‐Diels–Alder adducts of the thioaldehyde and the diene were formed. The treatment of a mixture of the thioformate and phenyl Grignard reagent with iodine gave 1,2‐bis(phenylsulfanyl)‐1,2‐diphenyl ethane as a product, which indicated the formation of arylsulfanyl benzylic Grignard reagents in the reaction mixture. When electrophiles were added to the Grignard reagents that were generated in situ, four‐component coupling products, that is, O‐alkyl thioformates, two molecules of Grignard reagents, and electrophiles, were obtained in moderate‐to‐good yields. The use of silyl chloride or allylic bromides gave the adducts within 5 min, whereas the reaction with benzylic halides required more than 30 min. The addition to carbonyl compounds was complete within 1 min and the use of lithium bromide as an additive enhanced the yields of the four‐component coupling products. Finally, oxiranes and imines also participated in the coupling reaction.     

Preparations of polystyrene/aluminum hydroxide and polystyrene/alumina composite particles in an ionic liquid

Polystyrene (PS)/aluminum hydroxide (Al(OH)(3)) composite particles were successfully prepared by the sol-gel process of aluminum isopropoxide (Al(OPr(i))(3)) in a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) using ammonium hydroxide (NH(4)OH) as a catalyst in the presence of PS seed. Transmission electron microscopy observation of ultrathin cross-sections of the composite particles revealed that the composite particles had a core-shell morphology consisting of a PS core and a Al(OH)(3) shell having high crystallinity. The amount of secondary nucleated Al(OH)(3) could be reduced by dropwise addition of NH(4)OH. Moreover, PS/η-Al(2)O(3) composite particles were successfully prepared by heat treatment of PS/Al(OH)(3) at 300 °C in N(2) atmosphere, which is below the decomposition temperature of PS.     

Well-defined single-walled carbon nanotube fibers as quantum wires: Ballistic conduction over micrometer-length scales

We report quasi-ballistic conduction in single-walled carbon nanotube (SWNT) fibers at room temperature, with a measured mean free path of 1.0–2.6 μm. The dynamic submersion of vertical SWNT fibers into liquid mercury (Hg) electrode shows plateaus and steps indicative of quasi-ballistic electron transport. This response is described with a newly developed network model that uses surface impurities to simplify the parallel conducting channels. The quasi-ballistic SWNT fibers exhibit a resistance per unit length of 2.5–6.5 kΩ/μm and a mean free path exceeding 1 μm, a length longer than typical via dimensions in existing Si-chip technologies. These results highlight that SWNT fiber conductivity can be enhanced by increasing the metallic to semiconducting SWNT ratio and reducing the surface impurities.     

Unified neutron star EOSs and neutron star structures in RMF models

In the framework of the Thomas-Fermi approximation, we systematically study the EOSs and microscopic structures of neutron star matter in a vast density range with n_b ≈ 10⁻¹⁰-2 fm⁻³, where various covariant density functionals are adopted, i.e., those with nonlinear self couplings (NL3, PK1, TM1, GM1, MTVTC) and density-dependent couplings (DD-LZ1, DDME-X, PKDD, DD-ME2, DD2, TW99). It is found that the EOSs generally coincide with each other at n_b ≲ 10⁻⁴ fm⁻³ and 0.1 fm⁻³ ≲ n_b ≲ 0.3 fm⁻³, while in other density regions they are sensitive to the effective interactions between nucleons. By adopting functionals with a larger slope of symmetry energy L, the curvature parameter K_sym and neutron drip density generally increases, while the droplet size, proton number of nucleus, core-crust transition density, and onset density of non-spherical nuclei, decrease. All functionals predict neutron stars with maximum masses exceeding the two-solar-mass limit, while those of DD2, DD-LZ1, DD-ME2, and DDME-X predict optimum neutron star radii according to the observational constraints. Nevertheless, the corresponding skewness coefficients J are much larger than expected, while only the functionals MTVTC and TW99 meet the start-of-art constraints on J. More accurate measurements on the radius of PSR J0740 + 6620 and the maximum mass of neutron stars are thus essential to identify the functional that satisfies all constraints from nuclear physics and astrophysical observations. Approximate linear correlations between neutron stars' radii at M = 1.4M_⊙ and 2M_⊙, the slope L and curvature parameter K_sym of symmetry energy are observed as well, which are mainly attributed to the curvature-slope correlations in the functionals adopted here. The results presented here are applicable for investigations of the structures and evolutions of compact stars in a unified manner.     

Modal interaction in chaotic vibrations of a shallow double-curved shell-panel

Experimental results and analytical results are presented on chaotic vibrations of a shallow double-curved shell-panel subjected to gravity and periodic excitation. Modal interactions in the chaotic responses are discussed. The shell-panel with square boundary is simply supported for deflection. In-plane displacement at the boundary is elastically constrained. In the experiment, time histories of the chaotic responses at the spatial multiple positions of the shell-panel are measured for the inspection of modal interaction. In the analysis, the shallow shell-panel is assumed to have constant curvatures along to orthogonal directions and geometric initial imperfection. The Donnell-Mushtari-Vlasov type equation is used as governing equation with lateral inertia force. Assuming deflection with multiple modes of vibration, the governing equation is reduced to a set of nonlinear ordinary differential equations by the Bubnov-Galerkin procedure. Chaotic responses are integrated numerically. The chaotic responses, which are obtained by the experiment and the analysis, are inspected with the Fourier spectra, the Poincaré projections, the maximum Lyapunov exponents and the Lyapunov dimension. Contribution of modes of vibration to the chaotic responses is analyzed by the principal component analysis, i.e., Karhunen-Loève transformation.     

Silver nanosintering: a lead-free alternative to soldering

We propose a lead-free silver paste as a replacement for a high-temperature lead-rich solder used for electronics. The pastes tested here contain a small amount of solvent, but primarily consist of silver powder and alkoxide-passivated silver nanoparticles that undergo nanosintering when heated. The pastes were used to connect silicon diode chips to copper bases at 350°C in nitrogen ambient without external pressure. The resulting diode packages had electrical and thermal properties about equal to those with lead-solder joints. The mechanical strengths also were comparable to the lead joint. These properties make this nanosilver paste the first viable lead-free alternative to a lead solder.     

Environmental transmission electron microscopy observations of the growth of carbon nanotubes under nanotube-nanotube and nanotube-substrate interactions

The growth process of carbon nanotubes (CNTs) under CNT-CNT and CNT-substrate interactions has been observed directly by environmental transmission electron microscopy. Even a free standing CNT occasionally swings during the growth until it touches the substrate. In addition, we show that the growth direction of CNTs changes due to the interaction between CNTs.     

Enhanced deep ultraviolet emission from Si-doped AlxGa1-xN/AlN MQWs

Undoped and Si-doped AlGaN/AlN multiple quantum wells(MQWs) were grown on AlN/Sapphire templates by metalorganic phase vapor epitaxy.High-resolution x-ray diffraction measurements showed the high interface quality of the MQWs little affected by Si-doping.Room-temperature(RT) cathodoluminescence measurements demonstrated a significant enhancement of the RT deep ultraviolet emission at about 240 nm from the AlGaN/AlN MQWs by Si doping.The mechanism of the improved emission efficiency was that the Si-doping partially screens the internal electric field and thus leads to the increase of the overlap between electron and hole wavefunctions.Further theoretical simulation also supports the above results.