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131.
Alfred D. French Anne‐Marie Kelterer Glenn P. Johnson Michael K. Dowd Christopher J. Cramer 《Journal of computational chemistry》2001,22(1):65-78
The HF/6‐31G* level of theory was used to calculate relaxed potential energy surfaces for 12 analogs of disaccharides. The analogs were made by replacing glucose with tetrahydropyran and fructose with 2‐methyltetrahydrofuran. Molecules had zero, one or two anomeric carbon atoms, and di‐axial, axial‐equatorial, and di‐equatorial linkages. Despite the absence of hydroxyl groups, the surfaces account well for conformations that are observed in crystals of the parent disaccharides. Thus, torsional energy and the simple bulk of ring structures are major factors in determining disaccharide conformation. The contour shapes around the global minima depend on the number of anomeric carbons involved in the linkage, while the presence of alternative minima that have relative energies less than 4 kcal/mol mostly requires equatorial bonds. However, molecules with two adjacent anomeric centers gave exceptions to these rules. Flexibility values related to a partition function show that the di‐axial trehalose analog is the most rigid. The di‐equatorial pseudodisaccharide analog with no anomeric centers is most flexible. Reproduction of these surfaces is proposed as a simple test of force fields for modeling carbohydrates. Also, these surfaces can be used in a simple hybrid method for calculating disaccharide energy surfaces. © 2000 John Wiley & Sons, Inc. * J Comput Chem 22: 65–78, 2001 相似文献
132.
133.
The transmission of ions through a conventional two-dimensional radiofrequency-only (rf) quadrupole has been studied for comparatively high operating pressures between 5 × 10?4 and 1 × 10?2 torr. Measurements of signals from mass-resolved analyte ions and total ion currents show that, provided the initial injection ion energy is low (1–30 eV), the ion transmission observed through a small aperture at the exit of the rf quadrupole first increases as the gas pressure increases, reaching a maximum at ? 8 × 10?3 torr before decreasing at higher pressures. This is in direct contrast to the expectations of classical scattering. This “collisional focusing” appears to be analogous to effects seen in three-dimensional ion traps. The collisional focusing increases with the mass of the ion (not mass-to-charge ratio) for masses up to at least 16,950 u. The collisional focusing of the ions is found to be accompanied by significant losses of axial kinetic energy. A Monte Carlo simulation of the energy loss process is reported that can provide agreement with the observed losses for reasonable collision cross-sections. The results suggest that operation of rf quadrupoles at relatively high pressure may find practical application in sampling ions from high (e.g., atmospheric) pressure ion sources. 相似文献
134.
Heidi M. French Mark J. Henderson A. Robert Hillman Eric Vieil 《Journal of Electroanalytical Chemistry》2001,500(1-2)
A combined electrochemical quartz crystal microbalance (EQCM) and probe beam deflection (PBD) instrument was used to monitor the mobile species transfers associated with the redox processes of thin (Γ100–150 nmol cm−2) α- and β-nickel hydroxide films exposed to aqueous LiOH solution. A comparison of the measured PBD signal with the predicted PBD profiles, calculated by temporal convolution analysis of the current and mass responses, enabled the contributions to redox switching of anion (OH−) and solvent (H2O) transfers to be discriminated quantitatively. The responses from the combined instrument are reconciled in terms of H+ deintercalation/intercalation within the nickel hydroxide structure as OH− ions enter/exit the film. Hydroxide ion movement is associated with a counterflux of water. Thin nickel hydroxide films show a gradual α→β phase transformation with continuous voltammetric cycling, especially when the films are exposed to high concentrations of electrolyte. α-Films are characterised by OH− transfers that dominate the H+ and H2O movements; β-films are characterised by an increased participation of water and protons to the exchange dynamics. 相似文献
135.
We describe a dispersion management methodology suitable for optimising lumped dispersion compensating schemes in heterogeneous terrestrial optical networks. The technique affords for a significant reduction in time expensive numerical simulations and is demonstrated to be effective for the transmission of 40 Gb/s DPSK in representative example networks made up of standard single-mode fibre. 相似文献
136.
Simon French 《The Journal of the Operational Research Society》1995,46(1):70-79
Any statistical analysis or decision analysis contains numerical inputs of which we are unsure. Some of our uncertainty arises from physical randomness which we can model in various ways, ideally through probability. Some uncertainty relates to judgemental estimates of quantities about which we may be unsure in many different respects. There are other uncertainties involved, however: some relate to ambiguity and imprecision of meaning; some relate to lack of clarity in the objectives which the analysis seeks to meet; some relate to the numerical accuracy of calculations. How should the uncertainty arising from ambiguity be modelled? Other uncertainties can also impact on an analysis. Why is the analysis being conducted? Are the objectives clear? 相似文献
137.
We report the fabrication of single mode SiC (silicon carbide) waveguides and the measurement of their propagation loss. By studying the effect of sidewalls scattering loss due to surface roughness and by reducing it, minimal propagation loss of 2.3 dB/cm for the TM polarization is measured in the visible at 0.633 μm. This loss can be used as a benchmark for further development of SiC microphotonic components and circuit for sensor systems in harsh environment. 相似文献
138.
Suhling K Siegel J Lanigan PM Lévêque-Fort S Webb SE Phillips D Davis DM French PM 《Optics letters》2004,29(6):584-586
We have developed a wide-field time-resolved imaging system to image quantitatively both the fluorescence lifetime and the rotational correlation time of a fluorophore. Using a polarization-resolved imager, we simultaneously image orthogonal polarization components of the fluorescence emission onto a time-gated intensified CCD. We demonstrate imaging of solvent viscosity variations through the rotational correlation time of fluorescein in a multiwell plate and apply this technique to probe the microviscosity in live cells. 相似文献
139.
As the sophistication of instruments that make fluorimetric measurements on samples in microplates has increased, so has the need for methods to validate instrumental performance. This paper describes a solid-state validation microplate that tests multiple aspects of fluorescence performance, including signal linearity, gain, noise, sensitivity, wavelength accuracy, and polarization stability. Both the operating principles and the validation of the validation microplate are discussed. 相似文献
140.