Palladium-catalyzed C-H homocoupling of bromothiophene derivatives and synthetic application to well-defined oligothiophenes

Synthesis of oligothiophenes of well-defined structures that possess 2-8 thiophene units is performed with a new synthetic strategy involving C-H homocoupling of bromothiophenes and cross-coupling with organostannanes. Tolerance of the carbon-bromine bond to the palladium-catalyzed C-H homocoupling results in oligothiophenes bearing C-Br bonds at the terminal thiophene rings, which allow further transformation by the catalysis of a transition-metal complex.     

Reconstruction of Scalar Source Intensity Based on Sensor Signal in Turbulent Channel Flow

We consider a turbulent channel flow, where a scalar point source with a time-harmonic intensity releases a substance that can be modeled as a passive scalar. With the source location known, our objective is to estimate the time history of the source intensity based on sensor measurements at different locations downstream of the source by adopting an adjoint approach. It is shown that the proposed algorithm reproduces the original coherent sinusoidal wave of the scalar source accurately from the chaotic scalar signals measured by our sensors. By systematically changing the source-sensor distance and the pulsation frequency of the source, we clarify how these two factors affect the estimation accuracy. The proposed scheme is also applicable to estimation with multiple sensors. We demonstrate that increasing the number of sensors improves the estimation greatly when the scalar is released from a source away from the wall, where large-scale eddies dominate the scalar dispersion. In contrast, the estimation performance remains poor even with multiple sensors when the scalar source is located near the wall, where the source information is quickly lost due to the strong turbulence activity and the scalar diffusion in the near-wall region.     

High-yield boron nitride nanosheets from 'chemical blowing': towards practical applications in polymer composites

An improved 'chemical blowing' route presuming atmospheric-pressure pre-treatment and moderate heating rate of designated precursors was developed to synthesize ultra-thin boron nitride (BN) nanosheets with high yield and large lateral dimensions. The yield reached as high as 40 wt% with respect to raw materials (ammonia borane). The strong oxygen-related ultraviolet luminescence together with a blue emission of these BN nanosheets was then documented and analyzed. This implies potential applications in solid-state lighting, ultraviolet lasing and full-color luminescence. Mechanical strength of different polymeric composites with a small fraction of BN nanosheet fillers was dramatically increased by tens of per cent, while high transparency of composite materials was still maintained in the visible optical range. The increased yield and reduced cost of BN nanosheets should promote their wide practical applications in various composites.     

Coherent storage of photoexcited triplet states using 29Si nuclear spins in silicon

Pulsed electron paramagnetic resonance spectroscopy of the photoexcited, metastable triplet state of the oxygen-vacancy center in silicon reveals that the lifetime of the m(s)=±1 sublevels differs significantly from that of the m(s)=0 state. We exploit this significant difference in decay rates to the ground singlet state to achieve nearly ~100% electron-spin polarization within the triplet. We further demonstrate the transfer of a coherent state of the triplet electron spin to, and from, a hyperfine-coupled, nearest-neighbor (29)Si nuclear spin. We measure the coherence time of the (29)Si nuclear spin employed in this operation and find it to be unaffected by the presence of the triplet electron spin and equal to the bulk value measured by nuclear magnetic resonance.     

Luminescence of GaN single crystals prepared by heating a Ga melt in Na–N2 atmosphere

Colorless transparent prismatic crystals (0.5‐2.0 mm long) and hopper crystals (1.0‐2.5 mm long) of GaN were prepared by heating a Ga melt at 800°C in Na vapor under N₂ pressures of 7.0 MPa for 300 h. The photoluminescence (PL) spectrum of a prismatic crystal at 4 K showed the emission peaks of neutral donor‐bound exciton (D⁰‐X) and free exciton (X_A) at 3.472 eV and 3.478 eV, respectively, in the near band edge region. The full‐width at half‐maximum (FWHM) of (D⁰‐X) peak was 1.9 meV. The emission peaks of a donor–acceptor pair transition (D⁰‐A⁰) and its phonon replicas were observed in a lower energy range (2.9‐3.3 eV). The emission peaks of the D⁰‐A⁰ and phonon replicas were also observed in the cathodoluminescence (CL) spectrum at 20 K. The (D⁰‐X) PL peak of a hopper crystal at 4 K was at 3.474 eV (2.1 meV higher), having a FWHM of 6.1 meV which was over 3 times larger than that of the prismatic crystal. A strong broad band with a maximum intensity around 1.96 eV was observed for the hopper crystals in the CL spectrum at room temperature. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

氢化作用对低能电子束辐照下GaN发光演变的影响

结合氢在GaN中的扩散特性,运用阴极荧光（CL）谱,对氢化前后低能电子束辐照下GaN带边发光强度的演变进行了研究.实验发现,氢化前GaN在低能电子束辐照下带边发光强度呈现衰减的趋势,而氢化后带边发射强度先上升后衰减,而且氢化后的衰减比氢化前弱.1 h辐照过程中,氢化后GaN带边发光强度的变化比氢化前要小很多.另外,实验中发现经过氢化处理的GaN在辐照后20 h内没有观察到带边发射强度的恢复.研究表明氢原子在GaN中可以钝化缺陷来增强发光,但这种钝化缺陷的作用必须通过克服高的扩散势垒来实现,而低能电子束可以 关键词： 阴极荧光 低能电子束 氢化 演变     

Molecular Transformation to Pyrroles,Pentafulvenes, and Pyrrolopyridines by [2+2] Cycloaddition of Propargylamines with Tetracyanoethylene

In this paper, we describe an efficient and atom-economical synthesis of highly functionalized pyrroles, pentafulvenes, and pyrrolopyridines by [2+2] cycloaddition–retroelectrocyclization of N-substituted propargylamines with tetracyanoethylene, followed by the treatment of the resulting tetracyanobutadiene derivatives with silica gel. In this reaction, silica gel plays an important role to promote the intramolecular cyclization to afford the heterocyclic products from the tetracyanobutadiene intermediates. The products were obtained selectively depending on the substituent on the nitrogen atom of the starting propargylamines.     

Metal-ion complexation of imidazo[1,2-a]pyrazin-3(7H)-ones: continuous changes in absorption spectra of complexes depending on the Lewis acidity of the metal ion

The spectroscopic properties of metal-ion complexes of several imidazopyrazinone derivatives with Li⁺, Mg²⁺, Ca²⁺, Ba²⁺, Sc³⁺, and La³⁺ ions were studied. The spectral characteristics and the formation constants of the complexes changed continuously depending on the Lewis acidity of the metal ion, suggesting that the imidazopyrazinones can find application as indicators of Lewis acidity. In the case of bis-imidazopyrazinone derivatives, the complexation abilities were enhanced by chelate effects.