229 research outputs found
Is Hyperconjugation Responsible For The Gauche Effect In 1-Fluoropropane And Other 2-Substituted-1-Fluoroethanes?
The energies and geometries of a series of 2-substituted-1-fluoroethanes were computed at the MP2/6-311++G**(6D)//MP2/6-31+G* level of theory for both the maxima and minima of the rotation about the C-C bond. The results did not support the predictions of a hyperconjugative model, that both 1,2-difluoroethane and 1-chloro-2-fluoroethane would strongly prefer a gauche conformation, and that 1-fluoro-2-silylethane would strongly prefer an anti conformation. The existence of competing electrostatic interactions between the fluorine and the substituents at C-2 was indicated by the detailed geometries of the gauche conformers and by the calculated sensitivity of the gauche-anti energy differences to the presence of a polar solvent. However, Fourier analyses of the torsional potential energies were wholly consistent with hyperconjugative electron donation into the C-F sigma* orbital contributing to the conformational preferences of these 1-fluoroethanes. Fourier analyses also showed that hyperconjugation contributes to the small variations in C-C and C-F bond lengths and in fluorine atomic charges that were computed. The torsional potential energies, variations in geometry and atomic charge, and sensitivity to solvent were all in accord with the expected ranking of hyperconjugative electron donating ability of bonds to carbon, C-Si \u3e C-H \u3e C-C \u3e C-Cl \u3e C-F
Measuring surface-area-to-volume ratios in soft porous materials using laser-polarized xenon interphase exchange NMR
We demonstrate a minimally invasive nuclear magnetic resonance (NMR)
technique that enables determination of the surface-area-to-volume ratio (S/V)
of soft porous materials from measurements of the diffusive exchange of
laser-polarized 129Xe between gas in the pore space and 129Xe dissolved in the
solid phase. We apply this NMR technique to porous polymer samples and find
approximate agreement with destructive stereological measurements of S/V
obtained with optical confocal microscopy. Potential applications of
laser-polarized xenon interphase exchange NMR include measurements of in vivo
lung function in humans and characterization of gas chromatography columns.Comment: 14 pages of text, 4 figure
Channel Capacities for Different Antenna Arrays with Various Transmitting Angles in Tunnels
[[abstract]]This paper focuses on the research of channel capacity of multiple-input multipleoutput
(MIMO) system with different transmitting angles in straight and curvy tunnels.Araytracing
technique is developed to calculate channel frequency responses for tunnels, and the
channel frequency response is further used to calculate corresponding channel capacity. The
channel capacities are calculated based on the realistic environment. The channel capacities
of MIMO long term evolution system using spatial and polar antenna arrays by different
transmitting angles are computed. Numerical results show that, The channel capacity for
transmitting angle at 15◦ is largest compared to the other angles in the tunnels. Moreover,
the channel capacity of polar array is better than that of spatial array both in the straight and
curvy tunnels. Besides, the channel capacity for the tunnels with traffic is larger than that
without traffic. Finally, it isworth noting that in these cases the presentwork provides not only
comparative information but also quantitative information on the performance reduction.[[notice]]補正完畢[[incitationindex]]SC
Segregated tunneling-percolation model for transport nonuniversality
We propose a theory of the origin of transport nonuniversality in disordered
insulating-conducting compounds based on the interplay between microstructure
and tunneling processes between metallic grains dispersed in the insulating
host. We show that if the metallic phase is arranged in quasi-one dimensional
chains of conducting grains, then the distribution function of the chain
conductivities g has a power-law divergence for g -> 0 leading to nonuniversal
values of the transport critical exponent t. We evaluate the critical exponent
t by Monte Carlo calculations on a cubic lattice and show that our model can
describe universal as well nonuniversal behavior of transport depending on the
value of few microstructural parameters. Such segregated tunneling-percolation
model can describe the microstructure of a quite vast class of materials known
as thick-film resistors which display universal or nonuniversal values of t
depending on the composition.Comment: 8 pages, 5 figures (Phys. Rev. B - 1 August 2003)(fig1 replaced
Diagnostic findings in sinonasal aspergillosis in dogs in the United Kingdom: 475 cases (2011–2021)
Objectives: To describe the diagnostic tests used and their comparative performance in dogs diagnosed with sinonasal aspergillosis in the United Kingdom. A secondary objective was to describe the signalment, clinical findings and common clinicopathologic abnormalities in sinonasal aspergillosis. Materials and Methods: A multi‐centre retrospective survey was performed involving 23 referral centres in the United Kingdom to identify dogs diagnosed with sinonasal aspergillosis from January 2011 to December 2021. Dogs were included if fungal plaques were seen during rhinoscopy or if ancillary testing (via histopathology, culture, cytology, serology or PCR) was positive and other differential diagnoses were excluded. Results: A total of 662 cases were entered into the database across the 23 referral centres. Four hundred and seventy‐five cases met the study inclusion criteria. Of these, 419 dogs had fungal plaques and compatible clinical signs. Fungal plaques were not seen in 56 dogs with turbinate destruction that had compatible clinical signs and a positive ancillary test result. Ancillary diagnostics were performed in 312 of 419 (74%) dogs with observed fungal plaques permitting calculation of sensitivity of cytology as 67%, fungal culture 59%, histopathology 47% and PCR 71%. Clinical Significance: The sensitivities of ancillary diagnostics in this study were lower than previously reported challenging the clinical utility of such tests in sinonasal aspergillosis. Treatment and management decisions should be based on a combination of diagnostics including imaging findings, visual inspection, and ancillary testing, rather than ancillary tests alone
Diagnostic findings in sinonasal aspergillosis in dogs in the United Kingdom: 475 cases (2011-2021).
ObjectivesTo describe the diagnostic tests used and their comparative performance in dogs diagnosed with sinonasal aspergillosis in the United Kingdom. A secondary objective was to describe the signalment, clinical findings and common clinicopathologic abnormalities in sinonasal aspergillosis.Materials and methodsA multi-centre retrospective survey was performed involving 23 referral centres in the United Kingdom to identify dogs diagnosed with sinonasal aspergillosis from January 2011 to December 2021. Dogs were included if fungal plaques were seen during rhinoscopy or if ancillary testing (via histopathology, culture, cytology, serology or PCR) was positive and other differential diagnoses were excluded.ResultsA total of 662 cases were entered into the database across the 23 referral centres. Four hundred and seventy-five cases met the study inclusion criteria. Of these, 419 dogs had fungal plaques and compatible clinical signs. Fungal plaques were not seen in 56 dogs with turbinate destruction that had compatible clinical signs and a positive ancillary test result. Ancillary diagnostics were performed in 312 of 419 (74%) dogs with observed fungal plaques permitting calculation of sensitivity of cytology as 67%, fungal culture 59%, histopathology 47% and PCR 71%.Clinical significanceThe sensitivities of ancillary diagnostics in this study were lower than previously reported challenging the clinical utility of such tests in sinonasal aspergillosis. Treatment and management decisions should be based on a combination of diagnostics including imaging findings, visual inspection, and ancillary testing, rather than ancillary tests alone
Calculations Predict That Carbon Tunneling Allows the Degenerate Cope Rearrangement of Semibullvalene to Occur Rapidly at Cryogenic Temperatures
Article on calculations predicting that carbon tunneling allows the degenerate cope rearrangement of semibullvalene to occur rapidly at cryogenic temperatures
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