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71.
A binary mixture of particles interacting via long-ranged repulsive forces is studied in gravity by computer simulation and theory. The more repulsive A-particles create a depletion zone of less repulsive B-particles around them reminiscent to a bubble. Applying Archimedes' principle effectively to this bubble, an A-particle can be lifted in a fluid background of B-particles. This "depletion bubble" mechanism explains and predicts a brazil-nut effect where the heavier A-particles float on top of the lighter B-particles. It also implies an effective attraction of an A-particle towards a hard container bottom wall which leads to boundary layering of A-particles. Additionally, we have studied a periodic inversion of gravity causing perpetuous mutual penetration of the mixture in a slit geometry. In this nonequilibrium case of time-dependent gravity, the boundary layering persists. Our results are based on computer simulations and density functional theory of a two-dimensional binary mixture of colloidal repulsive dipoles. The predicted effects also occur for other long-ranged repulsive interactions and in three spatial dimensions. They are therefore verifiable in settling experiments on dipolar or charged colloidal mixtures as well as in charged granulates and dusty plasmas. 相似文献
72.
73.
With the development of high power ultrafast laser passively mode-locked by a semiconductor saturable absorber mirror (SESAM), the damage threshold and degeneration mechanism of the SESAM become more and more important. One way to reduce the maximum electric field inside the active part of the SESAM is the use of a dielectric coating on the top of the semiconductor structure. With Presnel formula, optical transfer matrix, and optical thin film theory, the electric field distribution and reflectance spectrum can be simulated. We introduce the design principles of SESAM including the dependence of reflectance spectrum on dielectric function of absorber, and investigate the dependences of the electric field distribution, modulation depth, reflectance spectrum, and the relative value of incident light power at the top quantum well of SESAM on the number of SiO2/Ta2O5 layers. 相似文献
74.
In this paper, we suggest the conditional test procedures for testing elliptical symmetry of multivariate distribution. The conditional tests are exactly valid if the symmetric center and the shape matrix are given and are asymptotically valid if they are unknowns to be estimated. The equivalence, in the large sample sense, between the conditional tests and their unconditional counterparts is established. The power behavior of the tests under global as well as local alternatives is investigated theoretically. A small simulation study is performed. 相似文献
75.
Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2] . The title compound has been prepared by the reaction of CuCl with WNCl3 in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH3CN)4]+ ions, which are arranged to form strands, and of anions [W4N4Cl14(CH3CN)2]2?, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W?N? W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands. 相似文献
76.
Streitwieser A Abu-Hasanyan F Neuhaus A Brown F 《The Journal of organic chemistry》1996,61(9):3151-3154
Ab initio calculations are presented for alkali metal derivatives of fluoro- and chlorobenzenes for comparison with previously determined experimental substitutent effects. Calculated substituent effects for one alkali metal are linearly related to those of another. (Difluorophenyl)lithiums show additivity of substituent effects calculated from (monofluorophenyl)lithiums but dichloro derivatives do not, an effect attributed to the higher polarizability of chlorine. meta- and para-fluoro substituents show excellent agreement with experiment. ortho-fluoro and chlorine substituents do not. These differences are rationalized. 相似文献
77.
K. Machner G. Kainz Eva Neuhaus H. Kathen A. Mührdel H. Pelzer und G. Kaim 《Fresenius' Journal of Analytical Chemistry》1958,162(6):441-445
Ohne Zusammenfassung 相似文献
78.
Hou L Shao H Zhang Y Li H Menon NK Neuhaus EB Brewer JM Byeon IJ Ray DG Vitek MP Iwashita T Makula RA Przybyla AB Zagorski MG 《Journal of the American Chemical Society》2004,126(7):1992-2005
The pathogenesis of Alzheimer's disease is characterized by the aggregation and fibrillation of the 40-residue A beta(1-40) and 42-residue A beta(1-42) peptides into amyloid plaques. The structural changes associated with the conversion of monomeric A beta peptide building blocks into multimeric fibrillar beta-strand aggregates remain unknown. Recently, we established that oxidation of the methionine-35 side chain to the sulfoxide (Met35(red) --> Met35(ox)) significantly impedes the rate of aggregation and fibrillation of the A beta peptide. To explore this effect at greater resolution, we carefully compared the (1)H, (15)N, and (13)C NMR chemical shifts of four A beta peptides that had the Met35 reduced or oxidized (A beta(1-40)Met35(red), A beta(1-40)Met35(ox), A beta(1-42)Met35(red), and A beta(1-42)Met35(ox)). With the use of a special disaggregation protocol, the highly aggregation prone A beta peptides could be studied at higher, millimolar concentrations (as required by NMR) in aqueous solution at neutral pH, remaining largely monomeric at 5 degrees C as determined by sedimentation equilibrium studies. The NOE, amide-NH temperature coefficients, and chemical shift indices of the (1)H alpha, (13)C alpha, and (13)C beta established that the four peptides are largely random, extended chain structures, with the Met35(ox) reducing the propensity for beta-strand structure at two hydrophobic regions (Leu17-Ala21 and Ile31-Val36), and turn- or bendlike structures at Asp7-Glu11 and Phe20-Ser26. Additional NMR studies monitoring changes that occur during aging at 37 degrees C established that, along with a gradual loss of signal/noise, the Met35(ox) significantly hindered upfield chemical shift movements of the 2H NMR signals for the His6, His13, and His14 side chains. Taken together, the present NMR studies demonstrate that the Met35(red) --> Met35(ox) conversion prevents aggregation by reducing both hydrophobic and electrostatic association and that the A beta(1-40)Met35(red), A beta(1-40)Met35(ox), A beta(1-42)Met35(red), and A beta(1-42)Met35(ox) peptides may associate differently, through specific, sharp changes in structure during the initial stages of aggregation. 相似文献
79.
A new efficient synthesis of m-xylylene 1 is reported. The diradical 1 was trapped in argon matrices at 10 K and characterized by IR, UV-vis, and EPR spectroscopy. The syntheses reported before only allowed generation of 1 in organic glasses, and the spectroscopic identification was limited to fluorescence and EPR spectroscopy. Diradical 1 proved to be highly photolabile, and irradiation results in the formation of three isomeric hydrocarbons 7, 9, and 11 which could be identified by comparison of their IR spectra with the results of DFT calculations. 相似文献
80.
Burger BV Petersen WG Ewig BT Neuhaus J Tribe GD Spies HS Burger WJ 《Journal of chromatography. A》2008,1186(1-2):245-253
Using gas chromatography with flame ionization detection and electroantennographic detection in parallel (GC-FID/EAD), the active constituents of the sex attractant of male dung beetles of Kheper bonellii were located in the gas chromatogram of an extract of the secretion. These constituents were identified as propanoic acid, butanoic acid, indole, 3-methylindole (skatole) and methyl cis-cascarillate (methyl cis-2-2'-hexylcyclopropylacetate) by, inter alia, GC-MS, (1)H and (13)C NMR analysis, and synthesis. These compounds elicited EAD responses in male as well as female antennae. Racemic methyl cis-cascarillate was synthesized for comparison with the natural methyl ester. Enantioselective GC-FID/EAD using a capillary column coated with OV-1701-OH containing 10% heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-beta-cyclodextrin showed that the natural compound co-eluted with the first-eluting enantiomer of the racemic methyl cis-cascarillate, which was the only enantiomer that elicited EAD responses in the antennae of male and female K. bonellii. The absolute configuration of this enantiomer was established by a stereoselective synthesis, which gave methyl (R,R)-cascarillate [methyl (1'R,2'R)-2-2'-hexylcyclopropylacetate] in an enantiomeric excess of 69%. 相似文献