917 resultados para d(x2-y2) is-wave superconductor
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10-Desbromoarborescidine A10-Desbromoarborescidine AABCD10-Desbromoarborescidine ADesbromoarborescidine ADesbromoarborescidine A NH2C=N C-CbzAcCOt-BuCO2EtBzDMAcMeSiCl3- The main constituent of Dracontomelum mangiferum B1, indoloquinolizidine alkaloid 10-Desbromoarborescidine A, has drawn great attention due to its calcium channel blocking activity. Its molecular structure is relatively simple compared with the other alkaloids of the same type, which has only one chiral center, albeit with four cycles A, B, C, and D. This compound is often used as a model target for exploring different strategies for the total synthesis of indole alkaloids. Nevertheless, so far there still lack practical and highly efficient methods for the asymmetric total synthesis of 10-Desbromoarborescidine A. Most of the current available methods rely on stoichiometric asymmetric synthesis for the construction of the chiral center. There is only one example reporting utilization of asymmetric catalysis, but with transition metal complex as the catalyst. Our retrosynthetic analysis shows that catalytic asymmetric reduction of imine could be used as the key step for the construction of the chiral center of Desbromoarborescidine A. Since in the previous studies our group has developed the asymmetric reduction of imines by trichlorosilane into a practical and highly efficient and enantioselective method using newly designed chiral organocatalysts, we hope to apply this method to develop a novel synthetic route for the total synthesis of Desbromoarborescidine A and its analogues in this study. According to the newly designed synthetic route, we first accomplished the synthesis of the key intermediates which was then examined for the critical asymmetric catalysis. The asymmetric reduction using the highly efficient organocatalysts, developed in our lab afforded high ee but poor yield. We tried different reaction conditions to improve the yield, but failed to get any good results. Simultaneously, to vertify the feasibility of the synthetic route we designed, we also tired to go through the route toward the racemic synthesis of Desbromoarborescidine A. But unfortunately, protection and deprotection proved to be big hurdles. All the different protection groups and different sequences of protection and deprotection we tried failed to get us through the designed synthetic sequence and furnish the final product. Most likely, the indole part is the culprit behind the failures.The NH group of the indole, no matter protected or not, may impact the catalytic asymmetric reduction of C-N double bond connected with 2-C. Additionally, the reduction product we designed contains an amino group in the -position of the indole, which may cause problems due to its instability. C-sulfenylation of enamines is a novel reaction discovered recently by our group, which has not been seen before in the literature. In this study, optimization of the reaction conditions and exploration of the substrate scope were further undertaken for this reaction, which reveal that a series of enamines with N-Cbz, Ac, COt-Bu, CO2Et protection groups could all undergo smooth C-sulfinylations with the comined use of sodium benzene sulphinate, DAMc and MeSiCl3, efficiently furnishing the -amino vinylsulfoxide products in high yield, affording a practical and highly efficient methods for synthesis of functional vinylsulfoxides.
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Breakup process of polyamide 6 (PA6) in polypropylene (PP) matrix under shear flow was online studied by using a Linkam CSS 450 stage equipped with optical microscopy. Both tip streaming and fracture breakup modes of PA6 droplets were observed in this study. It was reported that the droplet would break up by tip streaming model when the radio of the droplet phase viscosity to the matrix phase viscosity (n(r) = n(d)/n(m)) is smaller than 0.1 (Taylor, Proc R Soc London A 1934, 146, 501; Grace, Chem Eng Commun 1982, 14, 225; Bartok and Mason, J Colloid Sci 1959, 14, 13; Rumscheidt and Mason, J Colloid Sci 1961, 16, 238; de Bruijn, Chem Eng Sci 1993, 48, 277). However, the tip streaming model was observed even when the viscosity ratio was much greater than 0.1 (n(r) = 1.9). In this study for the tip streaming mode, small droplets were ruptured from the tip of the mother droplet. On the other hand, the mother droplet was broken into two or more daughter droplets with one or several satellite droplets between them for the fracture mode. It was found that PA6 droplet was much elongated at first, and then broke up via tip streaming or fracture to form daughter droplets or small satellite droplets with the shape of fiber or ellipse.
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Equilibrium geometries, vibrational frequencies and dissociation energies of hafnium dimer and trimer were studied by density functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, mPW1PW91 and PBE1PBE. The results indicate that singlet is the ground state both for hafnium dimer and for trimer. For hafnium dimer, the calculated bond distance is less sensitive to the methods used. Except at BHLYP level, the calculated vibrational frequency is comparable to the experimental value. For hafnium trimer, equilateral triangle with D-3h symmetry is slightly favored compared with isosceles triangle with C-2v, symmetry except at BHLYP level. This conclusion is in agreement with experiment in which the ground state of Hf-3 is fluxional and low-spin or closed shell is preferred.
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For the first time, we present the calculation of the nonlinear optical coefficient of the NdAl3(BO3)(4) (NAB) crystal from a systematic and quantitative standpoint. Based on the dielectric theory of complex crystals and the Levine bond charge model, the method of calculation of the second-order nonlinear optical tensor coefficients of complex crystals has been given systematically. The chemical bond parameters and linear and nonlinear susceptibilities of the NAB crystal have been calculated in detail, and the calculated value of d(11)(NAB) is -5.81 x 10(-9) esu, which agrees with the measured value of 4.06 x 10(-9) esu.
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A unified criterion is developed for initiation of non-cohesive sediment motion and inception of sheet flow under water waves over a horizontal bed of sediment based on presently available experimental data. The unified threshold criterion is of the single form, U-o = 2 pi C[1 + 5(T-R/T)(2)](-1/4), where U-o is the onset velocity of sediment motion or sheet flow, T is wave period, and C and T-R are the coefficients. It is found that for a given sediment, U-o initially increases sharply with wave period, then gradually approaches the maximum onset velocity U-o = 2 pi C and becomes independent of T when T is larger. The unified criterion can also be extended to define sediment initial motion and sheet flow under irregular waves provided the significant wave orbital velocity and period of irregular waves are introduced in this unified criterion.
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In order to realize fast development of the national economy in a healthy way and coordinate progress with whole society, the country has implemented the strategy of development of the western region. An important action of finishing this strategic task is to accelerate the highway construction in the western region, join the western region and places along the coast, the river, the border with goods and materials, technology, and personnel interchanges, and then drive development of the local economy.The western region was influenced by the Himalaya Tectonization in Cenozoic, and the crust rose and became the plateau. In the course of rising, rivers cut down sharply to form a lot of high mountains and gorges.Because of topography and geomorphology, bridges in the traffic construction in the alpine gorge area are needed. Rivers have characteristics of large flow, fast velocity and high and steep river valley, so building a pier in the river is not only very difficult, but also making the cost increase. At the same time, the impact that the pier is corroded and the bridge base that is drawn to be empty by flow are apt to cause destruction of the pier. For those reasons, suspending bridge and cable-stay bridge are usually adopted with the single and large span. For the large span bridge, the pier foundation could receive ten thousand and more vertical strength, bending moment and near kiloton horizontal thrust.Because bank slope in the alpine gorge district is cut deeply and unsettled big, natural stability is worse under endogenic and exogenic force. When bank slope bears heavy vertical strength, bending moment and horizontal thrust facing the river, it will inevitably make the balance state of rock and soil mass change, bridge bank slope deform, and even destroyed. So the key problem at the time of the large span's bridge construction in the alpine gorge area is how to make it stable.So based on the spot investigation, the Engineering Geology Analysis Method is very important to grasp the bank slope stability. It can provide the bank slope stability macroscopic ally and qualitatively, and reference to the indoor calculation. The Engineering Geology Analysis Method is that by way of analyzing and investigating terms of bank slope instability, stability development trend, the ancient rock slide and devolution in the site, stability comprehensive evaluation primarily, current and future stability of bank slope is gotten, realizing the intention to serving the concrete engineering.After the Engineering Geology Analysis Method is applied to project instances of BeiPan River Bridge and BaLin River Bridge, results are accord with bank slope actual conditions, which proves sites are suited to building bridges from site stability.we often meet bank slope stability issues in the traffic construction in the alpine gorge areao Before the evaluation of the bank slope stability, the engineering geological condition is investigated first. After that, the next exploration target and geology measures are decided. So, the Engineering Geology Analysis Method that the investigation of the engineering geological condition is the main content is quite important in practice. The other evaluations of the bank slope stability are based on it. Because foundation receives very heavy load, for the big span's bridge in the alpine gorge area, a long pile of the large diameter (D^0.8m) is usually selected. In order to reflect rock mass's deformation properties under rock-socketed pile function, the author has used the FLAG30 software for rock and soil mass and done many numerical simulations. By them, the author launches the further investigation on deformation properties of bank slope under different slope angle, pile length, diameter, elastic modulus, load, bank slope's structure, etc. Some conclusion meaningful to the design and produce are obtained.
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An Impressionistic piece. Dance of the Waves uses and expansive structure (A, A2, B, A2, Solos, D, C2, D). The piece is an atmospheric soundscape which evokes imagery of the ocean.
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Chemoprevention agents are an emerging new scientific area that holds out the promise of delaying or avoiding a number of common cancers. These new agents face significant scientific, regulatory, and economic barriers, however, which have limited investment in their research and development (R&D). These barriers include above-average clinical trial scales, lengthy time frames between discovery and Food and Drug Administration approval, liability risks (because they are given to healthy individuals), and a growing funding gap for early-stage candidates. The longer time frames and risks associated with chemoprevention also cause exclusivity time on core patents to be limited or subject to significant uncertainties. We conclude that chemoprevention uniquely challenges the structure of incentives embodied in the economic, regulatory, and patent policies for the biopharmaceutical industry. Many of these policy issues are illustrated by the recently Food and Drug Administration-approved preventive agents Gardasil and raloxifene. Our recommendations to increase R&D investment in chemoprevention agents include (a) increased data exclusivity times on new biological and chemical drugs to compensate for longer gestation periods and increasing R&D costs; chemoprevention is at the far end of the distribution in this regard; (b) policies such as early-stage research grants and clinical development tax credits targeted specifically to chemoprevention agents (these are policies that have been very successful in increasing R&D investment for orphan drugs); and (c) a no-fault liability insurance program like that currently in place for children's vaccines.
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2012 by Oxford University Press. All rights reserved.This article considers the determinants and effects of M&As in the pharmaceutical industry, with a particular focus on innovation and R&D productivity. As is the case in other industries, mergers in the pharmaceutical field are driven by a variety of company motives and conditions. These include defensive responses to industry shocks as well as more proactive rationales, such as economies of scale and scope, access to new technologies, and expansion to new markets. It is important to take account of firms' characteristics and motivations in evaluating merger performance, rather than using a broad aggregate brushstroke. Research to date on pharmaceuticals suggests considerable variation in both motivation and outcomes. From an antitrust policy standpoint, the larger horizontal mergers in pharmaceuticals have run into few challenges from regulatory authorities in the United States and the European Union, given the option to spin off competing therapeutic products to other drug firms.
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2005-2012 IEEE.Within industrial automation systems, three-dimensional (3-D) vision provides very useful feedback information in autonomous operation of various manufacturing equipment (e.g., industrial robots, material handling devices, assembly systems, and machine tools). The hardware performance in contemporary 3-D scanning devices is suitable for online utilization. However, the bottleneck is the lack of real-time algorithms for recognition of geometric primitives (e.g., planes and natural quadrics) from a scanned point cloud. One of the most important and the most frequent geometric primitive in various engineering tasks is plane. In this paper, we propose a new fast one-pass algorithm for recognition (segmentation and fitting) of planar segments from a point cloud. To effectively segment planar regions, we exploit the orthonormality of certain wavelets to polynomial function, as well as their sensitivity to abrupt changes. After segmentation of planar regions, we estimate the parameters of corresponding planes using standard fitting procedures. For point cloud structuring, a z-buffer algorithm with mesh triangles representation in barycentric coordinates is employed. The proposed recognition method is tested and experimentally validated in several real-world case studies.
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Accurate ab initio intermolecular potential energy surfaces (IPES) have been obtained for the first time for the ground electronic state of the C 2H2-Kr and C2H2-Xe van der Waals complexes. Extensive tests, including complete basis set and all-electron scalar relativistic results, support their calculation at the CCSD(T) level of theory, using small-core relativistic pseudopotentials for the rare-gas atoms and aug-cc-pVQZ basis sets extended with a set of 3s3p2d1f1g mid-bond functions. All results are corrected for the basis set superposition error. The importance of the scalar relativistic and rare-gas outer-core (n.1)d correlation effects is investigated. The calculated IPES, adjusted to analytical functions, are characterized by global minima corresponding to skew T-shaped geometries, in which the Jacobi vector positioning the rare-gas atom with respect to the center of mass of the C2H2 moiety corresponds to distances of 4.064 and 4.229, and angles of 65.22 and 68.67 for C 2H2-Kr and C2H2-Xe, respectively. The interaction energy of both complexes is estimated to be -151.88 (1.817 kJ mol-1) and -182.76 cm-1 (2.186 kJ mol-1), respectively. The evolution of the topology of the IPES as a function of the rare-gas atom, from He to Xe, is also discussed. 2012 Taylor and Francis.