Formation of microcrystalline structure in a-Si:H films prepared by RF sputtering

Formation of microcrystalline structure in a-Si:H films prepared by RF sputtering has been investigated by TEM and FT-IR. The Films deposited in pure H₂ have grain-like structure and tend to crystallize with increasing the gas pressure, while the films deposited in Ar containing 10 % H₂ usually become amorphous. With increasing input power and the gas pressure, however, the latter films tend to have amorphous-microcrystalline mixed structure, and corresponding to this structural change, shift of optical absorption edge to lower energy and decreases of resistivity and activation energy of its temperature dependence are observed.     

A Practical Synthesis of 4′-Methylbiphenyl-2-carbonitrile as a Key Intermediate of Angiotensin II Antagonists

A new and practical synthesis of 4′-methylbiphenyl-2-carbonitrile, a key intermediate of angiotensin II antagonists is described. The key step is Pdcatalyzed dehydrogenation of the compound 6, which proceeds selectively by utilizing hydrogen acceptor such as maleic diester or oxygen.     

Nondestructive high-resolution solid-state NMR of rotating thin films at the magic-angle

We present a new approach to nondestructive magic-angle spinning (MAS) nuclear magnetic resonance (NMR) for thin films. In this scheme, the sample put on the top of a rotor is spun using the conventional MAS system, and the NMR signals are detected with an additional coil. Stable spinning of disk-shaped samples with diameters of 7 mm and 12 mm at 14.2 and 7 kHz are feasible. We present 7Li MAS NMR experiments of a thin-film sample of LiCoO2 with a thickness of 200 nm. Taking advantage of the nondestructive feature of the experiment, we also demonstrate ex situ experiments, by tracing conformation change upon annealing for various durations. This approach opens the door for in situ MAS NMR of thin-film devices as well.     

Relaxation of green fluorescent protein chromophore anion observed by photodissociation in an electrostatic storage ring

The gas-phase absorption properties of the green fluorescent protein chromophore anion were studied using an electrostatic storage ring. The time sequence of neutral particles produced by photodissociation was detected following laser irradiation. The lifetimes of the photo-absorbed ions depended on their storage time in an ion trap before injection into the storage ring. The lifetime increased with the storage time and saturated, indicating a change in the population of rovibrationally excited states with respect to the storage time. Photodissociation neutral spectrum of the relaxed ions measured as a function of the laser wavelength was characterized by a narrow asymmetric shape, which was in good agreement with the photo fragment ion action spectrum reported recently.     

平行于异材界面的三维椭圆平片裂纹分析

讨论了拉伸载荷作用下平行于两相材料界面的椭圆平片裂纹问题．首先,使用有限部积分概念和两相材料界面完全接合时的点力基本解导出了一组以裂纹表面位移差为未知函数的超奇异积分方程组．该组方程表明,此时三种裂纹模型同时存在;其次,在数值求解该组方程的过程中,未知函数裂纹表面位移差被近似为位移差的基本密度函数与多项式之积．基本密度函数反映了裂纹前沿应力奇性性态;最后,以拉伸载荷为例,讨论了椭圆平片裂纹与界面的距离、裂纹形状比和不同材料组合对应力强度因子的影响,并以图表形式给出。     

Structural properties of GaAs nanostructures formed by a supply of intense As4 flux in droplet epitaxy

We investigated detailed structural properties of GaAs nanostructures formed by a supply of intense As₄ flux to Ga droplets. Scanning electron microscopy (SEM) and cross-sectional transmission electron microscopy (TEM) revealed that whisker-like nanostructures had formed on the truncated cone-shaped bases after crystallization. Moreover, electron energy loss spectroscopy in scanning transmission electron microscopy (STEM-EELS) revealed that elemental Ga atoms remained inside the nanostructures while outside, some had crystallized into GaAs. These findings suggest that crystallization started at the edges of the droplets and the GaAs grew upward along the periphery of the droplets until the droplets were completely covered with crystallized GaAs.     

Iron-Catalyzed Biomimetic Dimerization of Tryptophan-Containing Peptides

Biomimetic oxidative dimerization of tryptophan derivatives in aqueous media with oxygen as a bulk oxidant catalyzed by an iron octacarboxy phthalocyanine complex was established. The discovery of the extremely active iron catalyst enables aerobic enzyme-mimetic oxidation to be performed in a flask. This method was applicable to the oxidative dimerization of a wide range of tryptophan derivatives, including various dipeptides and oligopeptides, with remarkable functional-group tolerance without the protection of the amino acid residues. Furthermore, oxidative dimerization of tryptophan derivatives bearing dioxopiperazine units enabled the convergent total synthesis of five natural pyrroloindole compounds and unnatural congeners. The established chemical method provides facile access to a broad range of dimerized peptides with a unique scaffold to link two turn structures, which will serve as a powerful tool to create new small- and medium-sized-molecules as drug candidates.     

Reactions of benzeneselenyl and benzenesulfenyl chlorides with syn‐ and anti‐9,9′‐bibenzonorbornenylidenes

Reaction of syn‐9,9′‐bibenzonorbornenylidene (1a) with benzeneselenyl chloride produced vic‐dichloride (4) exclusively, which corresponds to the cis‐addition product of 1a with molecular chlorine, with retention of the original alkene configuration. Moreover, the reaction of anti‐9,9′‐bibenzonorbornenylidene (1b) with benzeneselenyl chloride gave the same vic‐dichloride (4) exclusively with inversion of the original alkene configuration. No expected benzeneselenyl chloride adducts were formed in both cases. On the other hand, reactions of 1a and 1b with benzenesulfenyl chloride only resulted in the syn–anti isomerization of the alkenes without any adduct formation. Mechanisms of these reactions are discussed in some detail. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:625–629, 2001