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61.
We use molecular simulation to calculate the nucleation free energy barrier for the freezing of a 456 atom gold cluster over a range of temperatures. The results show that the embryo of the solid cluster grows at the vapor-surface interface for all temperatures studied and that the usual classical nucleation model, with the embryo growing in the core of the cluster, is unable to predict the shape of the free energy barrier. We use a simple partial wetting model that treats the crystal as a lens-shaped nucleus at the liquid-vapor interface and find that the line tension plays an important role in the freezing of gold nanoparticles. 相似文献
62.
We examine the metastable liquid phase of a supercooled gold nanocluster by studying the free energy landscape using the largest solidlike embryo as an order parameter. Just below freezing, the free energy exhibits a local minimum at small embryo sizes and a maximum at a larger critical embryo size. At T=660 K the free energy becomes a monotonically decreasing function of the order parameter as the liquid phase becomes unstable, indicating that we have reached a limit of stability. In contrast to the mean-field theory predictions for a spinodal, the size of the critical embryo remains finite as the limit of stability is approached. We also calculate the rate of nucleation, independently from our free energy calculations, and observe a rapid increase in its temperature dependence when the free energy barrier is on the order of kT. We suggest that this supports the idea that freezing becomes a barrierless process at low temperatures. 相似文献
63.
Jeffrey A. Pfefferkorn Daniel M. Bowles William Kissel David C. Boyles Chulho Choi Scott D. Larsen Yuntao Song Kuai-Lin Sun Steven R. Miller Bharat K. Trivedi 《Tetrahedron》2007,63(34):8124-8134
This paper describes the development of an efficient and scalable second generation synthesis of novel, pyrrole-based HMG-CoA reductase inhibitors. Compound 1 was identified as part of a discovery program aimed at finding improved treatments for hypercholesterolemia. Herein, we describe an efficient synthesis of its highly functionalized pyrrole core followed by attachment of the 3,5-dihydroxyhexanoic acid side chain via ylide olefination chemistry. 相似文献
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Patel SM de la Fuente M Ke S Guimarães AM Oliyide AO Ji X Stapleton P Osbourn A Pan Y Bowles DJ Davis BG Schatzlein A Yang M 《Chemical communications (Cambridge, England)》2011,47(38):10569-10571
Glycosylated analogues of novobiocin, discovered using a broad library of enzymes, have 100-fold improved activity against breast, brain, pancreatic, lung and ovarian cancers and ablated associated off-target activity leading to an up to 2.7 × 10(4) fold increase in selectivity. 相似文献
67.
M. Vos V.A. Sashin C. Bowles A.S. Kheifets E. Weigold 《Journal of Physics and Chemistry of Solids》2004,65(12):2035-2039
Electron momentum spectroscopy is often used to determine the spectral function of materials. It relies on the determination of the scattering angle of electrons with extremely high precision. In practice, it is important to calibrate these angles, and hence the momentum scales. Here we describe a method to do so and show how minor misalignments affect the measured momentum densities of Li2O. Using the same procedure we further calibrated the momentum scale by measuring the spectral momentum density along a Brillouin zone boundary of a Si single crystal. 相似文献
68.
Jaffe JS Simonet F Roberts PL Bowles AE 《The Journal of the Acoustical Society of America》2007,121(1):158-165
The Florida manatee (Trichechus manatus latirostris) is an endangered sirenian. At present, its adult population (approximately 2200) seems stable, but tenuous. Manatee-boat collisions are a significant proportion (approximately 25%) of mortalities. Here, the potential use of active sonar for detecting manatees by quantifying sonic reflectivity is explored. In order to estimate reflectivity two methods were used. One method measured live reflections from captive animals using a carefully calibrated acoustic and co-registered optical system. The other method consisted of the analysis of animal tissue in order to obtain estimates of the sound speed and density and to predict reflectivity. The impedance measurement predicts that for a lateral view, the tissue reflectivity is close to 0.13, with a critical grazing angle of 28 degrees. Data measured from live animals indicate that substantial reflections can be recorded, however in many instances observed "empirical target strengths" were less than an experimentally dependent -48-dB threshold. Conclusions favor the hypothesis that the animals reflect substantial amounts of sound; however, the reflections can often be specular, and therefore impractical for observation by a manatee detection sonar operating at 171 kHz. 相似文献
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W. Prandtl A. Brukl L. Pauling H. N. Mc Coy Ida Noddack J. K. Marsh L. Holleck W. Noddack G. Urbain F. Bourion G. Jantsch H. Albers H. Grubitsch P. W. Selwood J. A. C. Bowles H. M. Partridge H. C. Fogg L. Hess H. H. Williard N. K. Tang E. A. Werner C. James H. C. Holden A. J. Grant J. P. Bonardi Leonid Kuhlberg und F. M. Semiakin 《Fresenius' Journal of Analytical Chemistry》1938,113(3-4):121-135
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