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71.
William Kitching Maxwell Bullpitt David Doddrell William Adcock 《Magnetic resonance in chemistry : MRC》1974,6(5):289-292
The natural abundance, proton-decoupled carbon-13 spectra of 1-methylnaphthalene, 1-fluoronaphthalene, l-naphthonitrile and their 4-deutero analogues, as well as 2-naphthol and its 6-deutero analogue, have been recorded. Careful comparisons of the spectra of the deuterated and undeuterated compounds allow assignment, not only of the deuterated carbon, but also of the two ortho carbons (based on an upfield ‘two-bond’ deuterium isotope effect), as well as the two meta carbons (based on a significant J(CCCD) of ~1 Hz) which causes substantial broadening). In the 1-naphthyl compounds, significant coupling between the deuterium (at C4) and C5 allows assignment of this latter carbon. Thus, the consequences of the introduction of one deuterium atom, together with results from off-resonance noise decoupling, permits assignment of most of the spectra. Tentative, but very likely assignments of the few remaining signals, can be made on the bases of chemical shifts and compressional effects. This approach could allow indirect assignment of an aryl carbon to which direct attachment of deuterium is difficult, due to directive effects of an existing substituent. 相似文献
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The results of a linear multiple regression analysis indicate that the 19F SCS of 4-substituted bicyclo[2.2.2]oct-1-yl fluorides are essentially a manifestation of electric field and electronegativity effects. 相似文献
77.
Yan X MacLeod AM Gillespie WA Knippels GM Oepts D van Der Meer AF Seidel W 《Physical review letters》2000,85(16):3404-3407
Time-resolved measurements of the transverse electric field associated with relativistic electron bunches are presented. Using an ultrafast electro-optic sensor close to the electron beam, the longitudinal profile of the electric field was measured with subpicosecond time resolution and without time-reversal ambiguity. Results are shown for two cases: inside the vacuum beam line in the presence of wake fields, and in air behind a beryllium window, effectively probing the near-field transition radiation. Especially in the latter case, reconstruction of the longitudinal electron bunch shape is straightforward. 相似文献
78.
Kishani M. Ranatunga Charlotte Adcock Ian D. Kerr Graham R. Smith Mark S. P. Sansom 《Theoretical chemistry accounts》1999,101(1-3):97-102
The Poisson-Boltzmann equation was solved numerically for models of the pore regions of the Shaker K+ channel and of two glycoporins (LamB and ScrY) to yield electrostatic potential profiles along the pore axes. From these
potential profiles, single-channel current-voltage (I–V) relations were calculated. The importance of a proper treatment of the ionisation state of two rings of aspartate sidechains
at the mouth of the K+ channel pore emerged from such calculations. The calculated most likely state, in which only two of the eight aspartate sidechains
were deprotonated, yielded better agreement with experimental conductance data. An approximate calculation of single-channel
conductances based simply on pore geometry yielded very similar conductance values for the two glycoporins. This differed
from an␣experimentally determined conductance ratio of ScrY:LamB=10:1. Preliminary electrostatics calculations appeared to
reproduce the observed difference in conductance between the two glycoporins, confirming that single-channel conductance is
determined by electrostatic as well as geometric considerations.
Received: 25 May 1998 / Accepted: 4 August 1998 / Published online: 2 November 1998 相似文献
79.
C. G. Giribet M. C. Ruiz de Azúa S. B. Gmez E. L. Botek R. H. Contreras W. Adcock E. W. Della A. R. Krstic I. J. Lochert 《Journal of computational chemistry》1998,19(2):181-188
In the present work, the relationship between the large substituent effects on 3J(C1H) in 1-X-3-M-bicyclo[1.1.1]pentanes, I , and the polarizability of the bridgehead C3(SINGLE BOND)Mα bond is investigated. The existence of such a relationship is suggested by the finding that the effect of an electronegative substituent X on 3J(C1Mα) couplings in I (M=H) is due to a distortion of the C3(SINGLE BOND)H bond toward the C1 center, which enhances the Fermi contact interaction. If such distortion originates in an electrostatic effect, then in other members of this series it can be expected that the substituent effects on 3J(C1Mα) couplings should depend strongly on the C3(SINGLE BOND)Mα bond polarizability. Two approaches are followed. First, the ab initio CLOPPA-IPPP method is applied to study the C3(SINGLE BOND)Mα bond contribution to the molecular static polarizability tensor in I (M=H, F, CH3). Such bond polarizabilities are found to follow the same trend as calculated as well as experimentally determined substituent effects on 3J(C1Mα) couplings, which were measured as part of this work in I [X=H, Cl; M=F, CH3 and X=OCH3; M=Sn(CH3)3]. Second, 3J(C1Mα) couplings (M=H, CH3) are calculated at an ab initio level for X=H, F, and they are compared with those obtained in the parent compound (X=H) if the calculation is carried out in the presence of an inhomogeneous electric field. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 181–188, 1998 相似文献
80.
Adcock Ben Brugiapaglia Simone KingRoskamp Matthew 《Foundations of Computational Mathematics》2022,22(1):99-159
Foundations of Computational Mathematics - A signature result in compressed sensing is that Gaussian random sampling achieves stable and robust recovery of sparse vectors under optimal conditions... 相似文献