409 resultados para Kobayashi Pseudodistance


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Pulse compression through filamentation in an argon-filled cell was experimentally demonstrated by using circularly and linearly polarized pulses. A 53 fs circularly polarized pulse was successfully compressed to 15 fs. By using circularly polarized pulse input, the broadened spectrum was much wider and the incident energy in the gas cell can be increased by more than 3/2 times. Much shorter pulse could be compressed by using circularly polarized pulse input. [GRAPHICS] The temporal profile of the compressed pulse (C) 2008 by Astro Ltd. Published exclusively by WILEY-VCH Verlag GmbH & Co. KGaA.

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Assessing the vulnerability of stocks to fishing practices in U.S. federal waters was recently highlighted by the National Marine Fisheries Service (NMFS), National Oceanic and Atmospheric Administration, as an important factor to consider when 1) identifying stocks that should be managed and protected under a fishery management plan; 2) grouping data-poor stocks into relevant management complexes; and 3) developing precautionary harvest control rules. To assist the regional fishery management councils in determining vulnerability, NMFS elected to use a modified version of a productivity and susceptibility analysis (PSA) because it can be based on qualitative data, has a history of use in other fisheries, and is recommended by several organizations as a reasonable approach for evaluating risk. A number of productivity and susceptibility attributes for a stock are used in a PSA and from these attributes, index scores and measures of uncertainty are computed and graphically displayed. To demonstrate the utility of the resulting vulnerability evaluation, we evaluated six U.S. fisheries targeting 162 stocks that exhibited varying degrees of productivity and susceptibility, and for which data quality varied. Overall, the PSA was capable of differentiating the vulnerability of stocks along the gradient of susceptibility and productivity indices, although fixed thresholds separating low-, moderate-, and highly vulnerable species were not observed. The PSA can be used as a flexible tool that can incorporate regional-specific information on fishery and management activity.

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Commercial and recreational deepwater (100-400 m) bottom-fishing in Hawaii targets a multispecies group of lutjanid snappers. Relatively little is known about the life history of these species. Research in Hawaii and elsewhere in the tropical Pacific suggests that most of the species are slow growing, long lived, and have a relatively high age at sexual maturity. Stock assessment is difficult because of the multispecies nature of the fishery. However, recent analysis of commercial fishery data indicates that some of the species may currently be overexploited. Research is underway to determine the efficacy of management measures such as minimum-size limit changes or seasonal and spatial fishery closures to maintain optimal spawning biomass.

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A packaging technique suited to applying MEMS strain sensors realized on a silicon chip to a steel flat surface is described. The method is based on adhesive bonding of the silicon chip rear surface on steel using two types of glue normally used for standard piezoresistive strain sensors (Mbond200/ 600), using direct wire bonding of the chip to a Printed Circuit Board, also fixed on steel. In order to protect the sensor from the external environment, and to improve the MEMS performance, the silicon chip is encapsulated with a metal cap hermetically sealed-off under vacuum condition with a vacuum adhesive in which the bonding wires are also protected from possible damage. In order to evaluate the mechanical coupling of the silicon chip with the bar and thestress transfer extent to the silicon surface, commercial strain sensors have been applied on the chip glued on a steel bar in alaboratory setup able to generate strain by inflection, yielding a stress transfer around 70% from steel to silicon. © 2008 IEEE.

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Karyological data on the lesser stripe-backed shrew, Sorex bedfordiae, were obtained from four specimens collected on Mt. Laojun, Lijiang District, Yunnan Province, China. Three of the four S. bedfordiae specimens had karyotypes consisting of 2n=26, NFa=4

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Cd in GaAs is an acceptor atom and has the largest atomic diameter among the four commonly-used group-II shallow acceptor impurities (Be, Mg, Zn and Cd). The activation energy of Cd (34.7 meV) is also the largest one in the above four impurities, When Cd is doped by ion implantation, the effects of lattice distortion are expected to be apparently different from those samples ion-implanted by acceptor impurities with smaller atomic diameter. In order to compensate the lattice expansion and simultaneously to adjust the crystal stoichiometry, dual incorporation of Cd and nitrogen (N) was carried out into GaAs, Ion implantation of Cd was made at room temperature, using three energies (400 keV, 210 keV, 110 keV) to establish a flat distribution, The spatial profile of N atoms was adjusted so as to match that of Cd ones, The concentration of Cd and N atoms, [Cd] and [N] varied between 1 x 10(16) cm(-3) and 1 x 10(20) cm(-3). Two type of samples, i.e., solely Cd+ ion-implanted and dually (Cd+ + N+) ion-implanted with [Cd] = [N] were prepared, For characterization, Hall effects and photoluminescence (PL) measurements were performed at room temperature and 2 K, respectively. Hall effects measurements revealed that for dually ion-implanted samples, the highest activation efficiency was similar to 40% for [Cd] (= [N])= 1 x 10(18) cm(-3). PL measurements indicated that [g-g] and [g-g](i) (i = 2, 3, alpha, beta,...), the emissions due to the multiple energy levels of acceptor-acceptor pairs are significantly suppressed by the incorporation of N atoms, For [Cd] = [N] greater than or equal to 1 x 10(19) cm(-3), a moderately deep emission denoted by (Cd, N) is formed at around 1.45-1.41 eV. PL measurements using a Ge detector indicated that (Cd, N) is increasingly red-shifted in energy and its intensity is enhanced with increasing [Cd] = [N], (Cd, N) becomes a dominant emission for [Cd] = [N] = 1 x 10(20) cm(-3). The steep reduction of net hole carrier concentration observed for [Cd]/[N] less than or equal to 1 was ascribed to the formation of (Cd, N) which is presumed to be a novel radiative complex center between acceptor and isoelectronic atoms in GaAs.

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过去十多年,世界手性药物市场需求迅速增长,手性制药工业的发展壮大,已经引起了各国政府、学术界,特别是企业界的高度重视。手性药物中含有大量的手性胺单元,因此研究高效构建手性胺结构单元的方法具有重要的意义和实用价值,而亚胺的不对称还原是合成手性胺最便捷的方法。 手性有机小分子路易斯碱催化三氯氢硅不对称还原亚胺是最近几年才发展起来的一类新的亚胺不对称还原方法。尽管在对映选择性和底物适用范围等方面已经获得了突破性的进展,但是,高性能的路易斯碱催化剂仅局限于N-甲酰氨基酸酰胺一种类型,而且其底物适用范围和催化活性仍不够理想。因此,发展新型催化剂很有必要。 手性硫氧化物作为手性诱导剂的应用已经有数十年的时间,广泛应用在不对称合成及天然产物的全合成中。理论上,硫氧结构单元也可以作为路易斯碱,对硅烷类试剂进行活化,而且硫氧键还有碳氧键难以比拟的先天优势,硫原子自带手性特征,在反应过程中,手性中心离反应位点更近,因此,从手性硫氧化合物出发,极有可能开发出新的高效手性路易斯碱催化剂。最近,Kobayashi和Khiar在亚胺的不对称烯丙基化反应中用手性亚砜活化烯丙基三氯硅烷,获得了较好的ee值,但反应中手性亚砜的用量都需要化学计量以上,因此还不能算做真正意义上的催化剂,进一步的文献调研也未见真正意义上的硫手性有机小分子催化剂。 本文首次成功将硫手性亚磺酰胺衍生物应用于催化三氯氢硅对亚胺的不对称还原,在经过对亚磺酰胺衍生物的多次结构优化,开发出了合成容易,催化活性和立体选择性都很优良,并且有着前所未有的底物普适性的新型手性路易斯碱催化剂。 我们首先尝试将商品化的20mol%叔丁基亚磺酰胺和对甲基亚磺酰胺直接用作催化剂催化三氯氢硅对亚胺的不对称还原,尽管仅获得中等的收率和很低的对映选择性,但证明我们的设计思路是可行的。在此基础上,我们以叔丁基亚磺酰胺为原料和基本骨架,设计合成了一系列的亚磺酰胺类催化剂,通过对催化剂的结构改造,发现当催化剂中存在较强酸性的酚羟基时,催化效果得到大幅提高。随着对催化剂的进一步结构优化,我们找到了一个结构简单,催化效果还不错的催化剂,经过反应条件优化以后,催化反应的收率最高能达到98%,对映选择性最高达93%,并且这个催化剂的底物适应范围比之前报道的催化剂都要广泛。针对酚羟基在催化剂中的重要作用,我们进行了仔细的机理研究后发现,在催化反应中,催化剂极有可能是通过双分子机理去活化三氯氢硅从而实现不对称催化的,而酚羟基的作用就是通过分子间氢键促进双分子催化剂与三氯氢硅的络合。受此启发,我们设计了一系列具有双齿结构的催化剂,通过对双齿催化剂的结构优化,最终筛选出了一个结构更加简单,但催化效果更好的双齿催化剂。10mol%该催化剂催化亚胺还原最高获得95%的收率和96%的ee值。这一结果也进一步验证了我们先前对催化剂机理的推测。 随后,我们还尝试将这些催化剂用于二级胺和芳香酮的直接还原胺化反应中,虽然能获得不错的收率,但对映选择性却很差,我们对反应条件进行了仔细的摸索,仍然没有获得突破。但这些实验为进一步研究二级胺和酮的不对称直接还原胺化反应奠定了良好的基础。 In the past decade, the rapid growth of the global chiral drug market and the significant development of the chiral pharmaceutical industry have attracted a great deal of attention from government, academia and enterprises. Chiral amine is an important structural motif of chiral drugs. Therefore, development of methods for the construction of this motif is of great importance. Catalytic enantioselective reduction of imines represents one of the most straightforward and efficient methods for the preparation of chiral amines. The chiral Lewis base organocatalysts promoted asymmetric reduction of imines by HSiCl3 has recently achieved significant advancements. Although big breakthroughs have been made in terms of substrate generality and enantioselectivity, the highly effective catalysts are limited to N-formyl amino acid amides, of which the efficiency and substrate scope remain unsatisfactory. Therefore, development of novel organocatalysts for this transformation is in great demand. Chiral sulfoxides have been well established as efficient and versatile stereocontrollers and have been extensively used in asymmetric synthesis and total synthesis of natural products. The S=O structural motif of sulfoxide could also behave as Lewis base activator for cholorsilane reagents, which, moreover, could be even better than caboxamide considering that the sulfur atom is chiral and thus the chirality center is closer to the reaction center. There exist great potentials that highly effective novel Lewis base organocatalysts could be developed starting from S-chiral sulfoxides. Recently, several S-chiral sulfoxides were reported by Kobayashi and Khiar to be used as Lewis base catalyst to activate allyltrichlorosilanes in asymmetric allylations and good enantioselectivities were obtained. However, these S-chiral sulfoxides were all used at a more than stoichiometric amount and were thus not authentically catalytic. A careful literature survey further revealed that there has been so far no S-chiral organocatalyst available. In this study, we, for the first time, successfully used S-chiral sulfinamides as Lewis base organocatalysts for the asymmetric reduction of ketimines by HSiCl3. After several rounds of structural optimization, we developed the first example of highly effective S-chiral organocatalysts, which promoted the asymmetric reduction of ketimines with trichlorosilane in high yield and excellent enantioselectivity with unprecedented substrate spectrum. In our initial practice, we examined 20mol% of the commercially available (R)-tert-butanesulfinamide and (S)-toluenesulfinamide as the catalyst in the hydrosilylation of ketimine. Although the product was only furnished in moderate yield and low ee, these results demonstrated that our strategy of catalyst design is on the right way. Next, starting from chiral tert-butanesulfinamide, we prepared a series of tert-butanesulfinamide derivatives via simple reductive amination and examined their catalytic efficiencies in the reduction of ketimine. We found that the catalyst bearing a phenolic hydroxyl group exhibited good reactivity and enantioselectivity. On the basis of which, we obtained a structurally simple and highly effective novel organocatalyst, affording the product in 98% yield and 93% ee under optimal reaction conditions. After careful exploration on the role of phenolic hydroxyl group in the catalyst, we speculated that two molecules of the catalyst be involved in the course of reaction, of which the assembly around the silicon center is facilitated by the intermolecular hydrogen bonding through the phenolic hydroxyl groups. Thus, we incorporated two units of sulfonamide into one molecular and prepared a new type of bissulfinamides organocatalysts and examined their catalytic efficiencies in the reduction of ketimine. After optimizing the structure of these catalysts, we finally obtained a novel organocatalyst which has even simpler molecular structure but showed better efficacies, 10mol% of which afforded up to 97% yield and 96% ee under optimal reaction conditions. These results further proved our speculation about the catalytic mechanism. We also examined the newly developed S-chiral organocatalysts in direct asymmetric reductive amination of secondary amines with aromatic ketone. The product was furnished in good yield but in low ee. No better results could be obtained despite our intense opimization efforts. Nevertheless, these experiments laid excellent foundations for eventual success.

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The Coulomb dissociation of the proton-rich nuclei Cl-31 was studied experimentally using Cl-31 beams at 58 MeV/nucleon with a lead target. The relative energy between the reaction products, S-30 and proton, was obtained. The first excited state in Cl-31 was observed which is relevant to the resonant capture of stellar S-30(p, gamma)Cl-31 reaction

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W-doped Fe2O3 films have been fabricated on polycrystalline alumina substrates by the RF magnetron sputtering method, and effects of annealing temperature on the NO2 sensing properties have been examined. The crystal structure of the obtained film changed from Fe3O4 to α-Fe2O3 after annealing at temperatures of 500 to 500°C in air. An increase in the annealing temperature increased the particle size, resulting in a decrease in the NO2-gas sensitivity. These results suggest that the NO2 sensitivity of W-doped Fe2O3 film depends on the particle size.

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With a newly synthesized poly(p-phenylene vinylene) (PPV) multiblock copolymer used in a triple-layer structure, efficient green light-emitting diodes with low driving voltage have been fabricated. The devices are turned on at 2.5 V, the brightness at 5 V is above 100 cd/m(2) and at 7 V is about 1650 cd/m(2), with an external quantum efficiency of about 1%. (C) 1998 Elsevier Science S.A. All rights reserved.