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1.
G. K. Hubler C. N. Waddell E. P. Donovan J. M. Zavada 《Optical and Quantum Electronics》1991,23(7):S883-S893
Precision reflection measurements were performed on GaAs/AlAs superlattices of the same composition but different layer spacings. Nonlinear-least-squares fits to the data were performed to a single layer. Measurements were extracted for the superlattice thickness, thickness of a disturbed interface layer between the superlattice and substrate, the uniformity in composition and/or spacing and the composition. It was demonstrated that these nondestructive measurements in the infrared region (3000 to 12 000 cm–1) in conjunction with a simple single layer model are capable of accurately yielding the above quantities with high precision. 相似文献
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The Milne-Thomson circle theorem is extended to give a simplegeneral expression for the image system in an elliptical cylinderintroduced into an otherwise specified unbounded potential flowwhich contains no singularities in the region to be occupiedby the ellipse. This image system is used to obtain an expressionfor the corresponding source-sink surface singularity distributionon the ellipse, thus providing new benchmark test cases forsource-sink solutions as obtained numerically by a panel method.Several typical examples are given to illustrate the generaltheoretical approach. 相似文献
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Abstract— All- trans - and 13- cis -14,15-dideuterioretinal were synthesized and their solution photochemistry examined. Quantum yields of trans → cis or cis → trans photoisomerization and the number and ratio of primary photoproducts, determined by high pressure liquid chromatographic analysis, are essentially identical to that of their corresponding retinal isomer. The C-14, C-15 carbon-hydrogen modes play no particularly important role in the deactivation of electronically excited linear polyenes related to retinal. 相似文献
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van Dongen PG 《Physical review. B, Condensed matter》1994,49(12):7904-7915
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Transient absorption spectra were recorded 15 ns to 6 μs following a 266 nm laser pulse for phenyl azide and for phenyl isocyanate in aerated acetonitrile and 3-methylpentane solutions. Transient spectra which are independent of concentration and of delay time, are essentially identical for phenyl azide and for phenyl isocyanate, except at higher energies where phenyl azide absorbs, and are assigned as that of triplet phenyl nitrene. Since there is no spectral evidence for a second species, phenyl nitrene is thought the chain propagator in the autocatalytic chain decomposition that occurs for phenyl azide and for phenyl isocyanate. 相似文献
9.
DeRider ML Wilkens SJ Waddell MJ Bretscher LE Weinhold F Raines RT Markley JL 《Journal of the American Chemical Society》2002,124(11):2497-2505
Collagen-like peptides of the type (Pro-Pro-Gly)(10) fold into stable triple helices. An electron-withdrawing substituent at the H(gamma)(3) ring position of the second proline residue stabilizes these triple helices. The aim of this study was to reveal the structural and energetic origins of this effect. The approach was to obtain experimental NMR data on model systems and to use these results to validate computational chemical analyses of these systems. The most striking effects of an electron-withdrawing substituent are on the ring pucker of the substituted proline (Pro(i)) and on the trans/cis ratio of the Xaa(i-1)-Pro(i) peptide bond. NMR experiments demonstrated that N-acetylproline methyl ester (AcProOMe) exists in both the C(gamma)-endo and C(gamma)-exo conformations (with the endo conformation slightly preferred), N-acetyl-4(R)-fluoroproline methyl ester (Ac-4R-FlpOMe) exists almost exclusively in the C(gamma)-exo conformation, and N-acetyl-4(S)-fluoroproline methyl ester (Ac-4S-FlpOMe) exists almost exclusively in the C(gamma)-endo conformation. In dioxane, the K(trans/cis) values for AcProOMe, Ac-4R-FlpOMe, and Ac-4S-FlpOMe are 3.0, 4.0, and 1.2, respectively. Density functional theory (DFT) calculations with the (hybrid) B3LYP method were in good agreement with the experimental data. Computational analysis with the natural bond orbital (NBO) paradigm shows that the pucker preference of the substituted prolyl ring is due to the gauche effect. The backbone torsional angles, phi and psi, were shown to correlate with ring pucker, which in turn correlates with the known phi and psi angles in collagen-like peptides. The difference in K(trans/cis) between AcProOMe and Ac-4R-FlpOMe is due to an n-->pi interaction associated with the Bürg-Dunitz trajectory. The decrease in K(trans/cis) for Ac-4S-FlpOMe can be explained by destabilization of the trans isomer because of unfavorable electronic and steric interactions. Analysis of the results herein along with the structures of collagen-like peptides has led to a theory that links collagen stability to the interplay between the pyrrolidine ring pucker, phi and psi torsional angles, and peptide bond trans/cis ratio of substituted proline residues. 相似文献
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