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91.
Lewis SP Taylor NJ Piers WE Collins S 《Journal of the American Chemical Society》2003,125(48):14686-14687
Lewis acidic diborane 1 (J. Am. Chem. Soc. 1999, 121, 3244-3245) is highly effective for both proton- and cationogen-initiated isobutene polymerization in hydrocarbon media at low temperature. Reactions of diborane 1 with cumyl chloride and cumyl methyl ether were studied by variable-temperature 1H and 19F NMR spectroscopy. At low temperatures stable ion pairs 2a and 2b are formed; at higher temperatures these ion-pairs form phenyl-1,3,3-trimethylindan (3) with concomitant release of HCl to form 1 in the case of 2a or degradation of the anion (2b). Reaction between Ph3C-Cl and diborane 1 resulted in the generation of an ion-pair 4 consisting of the Ph3C cation very weakly associated with the chelated, mu-Cl counteranion as revealed by X-ray crystallography. 相似文献
92.
Grotjahn DB Collins LS Wolpert M Bikzhanova GA Lo HC Combs D Hubbard JL 《Journal of the American Chemical Society》2001,123(34):8260-8270
Using a series of Ir(I) and Rh(I) ketene complexes, conclusions about the structure and bonding of complexes of the fundamentally important ketene ligand class are reached. In a unique comparison of X-ray structures of the same metal fragment to ketenes in both the eta(2)-(C,C) and the eta(2)-(C,O) binding mode, the Ir-Cl bond distances in complexes of trans-Cl(Ir)[P(i-Pr)(3)](2) to phenylketene [4, eta(2)-(C,C)] and diphenylketene [2a, eta(2)-(C,O)] are 2.371(3) and 2.285(2) A, respectively. This would be consistent with greater trans influence of a ketene ligand bound to a metal through its C=C bond than one connected by its C=O bond. Back-bonding of Ir(I) and Rh(I) to diphenylketene was assessed using trans-Cl(M)[P(i-Pr)(3)](2)[eta(2)-(C,O)-diphenylketene] (2a and 2d). Most bond lengths and angles are identical, but slightly greater back-bonding by Ir(I) is suggested by the somewhat greater deformation of the ketene C=C=O system [C-C-O angles are 136.6(4) and 138.9(4) in the Ir and Rh cases 2a and 2d, respectively]. Syntheses of new labeled ketenes Ph(2)C=(13)C=O and Ph(2)C=C=(18)O and their Ir(I) and Rh(I) complexes are reported, along with the generation of an Ir(I) complex of PhCH=(13)C=O. The effects of isotopic substitution on infrared absorption data for ketene complexes are presented for the first time. Preliminary normal coordinate mode analysis allowed definitive assignment of absorptions ascribed to the C-O stretching frequencies of coordinated ketenes, which are near the absorptions for aromatic ring systems commonly found as substituents on ketenes. For free diphenylketene and four of its complexes and a phenylketene complex characterized by X-ray diffraction, the magnitude of the (13)C-(13)C coupling between the two ketene carbons is correlated to carbon-carbon bond distance. 相似文献
93.
Gabriela Ionita Petre Ionita Victor EM. Sahini Constantin Luca 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(3-4):269-271
The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin. 相似文献
94.
Dzik-Jurasz AS Wolber J Prock T Collins DJ Leach MO Rowland IJ 《Magnetic resonance imaging》2001,19(6):839-844
19F-MR-imaging has been used to quantitate albumin concentration in a phantom at 1.5 T. The experimentally derived relationship between albumin concentration and the T1 relaxation time of a fluorinated marker, tetrafluorosuccinic acid (TFSA) was used to calculate the albumin concentration from a quantitative 19F T1 map acquired using a gradient echo sequence. There was close correlation between calculated and actual BSA concentrations (r = 0.99, SE = 0.15). The potentially interfering effect of paramagnetic species on T1 relaxation times was also investigated. Relaxivity data show that albumin concentration measurements should be performed prior to any contrast agent administration. 相似文献
95.
A mapping approach for handling sloping interfaces in parabolic equation solutions is developed and tested. At each range, the medium is rigidly translated vertically so that a sloping interface becomes horizontal. To simplify the approach, the slope is assumed to be small and the extra terms that arise in the wave equation under the mapping are neglected. The effects of these terms can be approximately accounted for by applying a leading-order correction to the phase. The mapping introduces variations in topography, which are relatively easy to handle for the case of a pressure-release boundary condition. The accuracy of the approach is demonstrated for problems involving fluid sediments. The approach should also be accurate for problems involving elastic sediments and should be useful for solving three-dimensional problems involving variable topography. 相似文献
96.
Collins MD Schmidt H Siegmann WL 《The Journal of the Acoustical Society of America》2000,107(4):1964-1966
An energy-conserving spectral solution is derived and tested. A range-dependent medium is approximated by a sequence of range-independent regions. In each region, the acoustic field is represented in terms of the horizontal wave-number spectrum. A condition corresponding to energy conservation is derived for the vertical interfaces between regions. The accuracy of the approach is demonstrated for problems involving sloping ocean bottoms. The energy-conserving spectral solution is less efficient than the energy-conserving parabolic equation solution, but might be suitable for generalization to problems involving elastic bottoms. 相似文献
97.
Bradley K Jhi SH Collins PG Hone J Cohen ML Louie SG Zettl A 《Physical review letters》2000,85(20):4361-4364
The thermoelectric power (TEP) of single-walled carbon nanotubes (SWNTs) is extremely sensitive to gas exposure history. Samples exposed to air or oxygen have an always positive TEP, suggestive of holelike carriers. However, at fixed temperature the TEP crosses zero and becomes progressively more negative as the SWNTs are stripped of oxygen. The time constant for oxygen adsorption/desorption is strongly temperature dependent and ranges from seconds to many days, leading to apparently "variable" TEP for a given sample at a given temperature. The saturated TEP can be accounted for within a model of strong oxygen doping of the semiconducting nanotubes. 相似文献
98.
Progress in direct-drive inertial confinement fusion research at the
laboratory for laser energetics
R. L. McCrory D. D. Meyerhofer S. J. Loucks S. Skupsky R. Betti T. R. Boehly T. J.B. Collins R. S. Craxton J. A. Delettrez D. H. Edgell R. Epstein K. A. Fletcher C. Freeman J. A. Frenje V. Yu. Glebov V. N. Goncharov D. R. Harding I. V. Igumenshchev R. L. Keck J. D. Kilkenny J. P. Knauer C. K. Li J. Marciante J. A. Marozas F. J. Marshall A. V. Maximov P. W. McKenty S. F.B. Morse J. Myatt S. Padalino R. D. Petrasso P. B. Radha S. P. Regan T. C. Sangster F. H. Séguin W. Seka V. A. Smalyuk J. M. Soures C. Stoeckl B. Yaakobi J. D. Zuegel 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,44(2):233-238
Direct-drive inertial confinement fusion (ICF) is
expected to demonstrate high gain on the National Ignition Facility (NIF) in
the next decade and is a leading candidate for inertial fusion energy
production. The demonstration of high areal densities in hydrodynamically
scaled cryogenic DT or D2 implosions with neutron yields that are a
significant fraction of the “clean” 1-D predictions will validate the
ignition-equivalent direct-drive target performance on the OMEGA laser at
the Laboratory for Laser Energetics (LLE). This paper highlights the
recent experimental and theoretical progress leading toward achieving this
validation in the next few years.
The NIF will initially be configured for X-ray drive and with no beams
placed at the target equator to provide a symmetric irradiation of a
direct-drive capsule. LLE is developing the “polar-direct-drive” (PDD)
approach that repoints beams toward the target equator. Initial 2-D
simulations have shown ignition. A unique “Saturn-like” plastic ring
around the equator refracts the laser light incident near the equator toward
the target, improving the drive uniformity.
LLE is currently constructing the multibeam, 2.6-kJ/beam, petawatt laser
system OMEGA EP. Integrated fast-ignition experiments, combining the OMEGA
EP and OMEGA Laser Systems, will begin in FY08. 相似文献
99.
We report combinatorial molecular beam epitaxy synthesis and properties of a ternary epitaxial film of Co and Mn co-doped Ge grown on Ge (0 0 1) substrate. Structural effects were examined in situ by reflection high-energy electron diffraction and ex situ by microbeam X-ray diffraction techniques, and magnetic properties were probed by using magnetooptic Kerr effect. Ternary epitaxial phase diagrams have been studied for total doping concentrations up to 30 at.%, where regions of coherent epitaxy and rough disordered growth and those of near room temperature ferromagnetic ordering have been identified. 相似文献
100.
Diffusion of 111In/Cd impurity atoms was studied in Ga7Pt3 at the atomic level using the method of perturbed angular correlation of gamma rays (PAC). As in previous measurements on Ga7Pd3, probes were observed to occupy two inequivalent Ga-sublattices. Quadrupole interaction perturbation functions for each site exhibited damping at elevated temperatures that is attributed to nuclear relaxation caused by stochastic jumps of the probe atoms accompanied by reorientation of axes of the electric field gradient tensor. Fitted relaxation frequencies, proportional to mean jump frequencies of the probe, were thermally activated. Arrhenius plots revealed jump-frequency activation enthalpies of 0.94 (8) and 0.67 (4) eV for the two sites and frequency prefactors close to 1 THz. Results were similar to those found previously for Ga7Pd3, although jump frequencies are about 100 times lower in Ga7Pt3. 相似文献