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11.
Extraction of quantitative information from large sets of sequential time-series spectra (two-dimensional, 2D, data) using a curve-fitting procedure is investigated. The difference between any experimental spectrum and any curve-fitted spectrum is constructed in a least-squares manner and the Pearson VII model is selected as the general band-shape function for the infrared absorbance spectra. The starting point for the curve-fitting procedure is a 2D peak map. Next, an interior spectrum from the 2D array is chosen, initial guesses of the band parameters are provided by an initialization scheme, and curve fitting is performed. Once optimal values of the Pearson VII model band parameters are obtained from the starting spectrum in the 2D array, these are then used as reasonable and judicious initial guesses for subsequent curve fitting of the neighboring spectra in the time series. This increases computational efficiency enormously. By adjusting the band center positions for moving bands, and re-optimizing each subsequent curve-fitting calculation to account for changing band shapes, the entire 2D array is rapidly and efficiently modeled. A 2D experimental spectroscopic time-series array from a homogeneous rhodium-catalyzed hydroformylation reaction was successfully curve fitted in this manner. The procedure holds considerable promise for the curve fitting of massive time-series spectroscopic data, such as that arising from on-line process monitoring of expensive value-added specialty chemical and pharmaceutical syntheses. 相似文献
12.
Two useful numerical methods using ultraviolet (UV) and circular dichroism (CD) spectroscopies are proposed to determine enantiomeric excess (e.e). An algorithm is also proposed to generate self-consistent pure R and S enantiomer reference spectra. After all pure reference spectra are generated, a simulated annealing algorithm is applied to minimize the mismatch between the experimental spectra and the spectra after a least-squares fit. Optimal factors for R and S enantiomers are then used to determine e.e. The ultraviolet-circular dichroism (UV-CD) method uses the combined UV and CD spectra in a composite form, while the high-performance liquid chromatography (HPLC)-CD method only employs the CD spectra with the total concentrations of R plus S enantiomers provided by HPLC using a non-chiral stationary phase. Both methods were successfully tested on mixtures with known composition and then applied to real experimental data (unknown compositions). Compared with the UV-CD method, the results show that excellent results are more readily obtained using the HPLC-CD method. With the systems studied, the latter usually provided outstanding estimations of e.e with low error percentages. 相似文献
13.
Brian D. Garland Irene J. Beyerlein Linda S. Schadler 《Composites Science and Technology》2001,61(16):4209-2480
Recent experimental work (Narayanan S, Schadler LS. Mechanisms of kink band formation in graphite/epoxy compsites: a micromechanical experimental study. Comp Sci Technol 1999; 59:2201-13) suggests that kink bands in unidirectional continuous carbon fiber reinforced polymer composites initiate from damage zones formed under axial compressive loads. A damage zone consists of a cluster of locally crushed fibers and broken fibers, that are often fractured at an angle, θ > 0°, normal to the fiber axis. Typically, under compressive loads, fiber breaks in damage zones form roughly along a plane at an angle φ, normal to the fiber axis. These damage zones produce stress concentrations which can lead to instabilities in the nearby fiber and matrix and initiate microbuckling and kink bands. This paper extends a micromechanical influence function technique based on earlier shear lag fiber composite models. Our modified technique calculates the fiber axial and matrix shear stress concentrations due to multiple angled and crushed fibers in arbitrary configurations. Modeling reveals that angled or ‘shear’ breaks (θ > 0°) can lead to higher shear stress concentrations in the matrix than transverse breaks (θ=0°). Also we find that the damage zone is more likely to form at an angle φ, which is greater than that of its individual fiber breaks, θ. When φ is slightly greater than θ, the shear stress in the surrounding matrix regions within the damage zone achieves a maximum, potentially weakening the matrix and interface and consequently leading to kink band formation. Monte Carlo simulations incorporating this stress analysis predict that the initiation and propagation of crushed and angled breaks progress roughly along an angle, φ ≈ 17° in a linear elastic system. When possible, our model results are compared to strain measurements of fiber composites under compression obtained by Narayanan and Schadler using micro-Raman spectroscopy (MRS). 相似文献
14.
Since the increase in the use of computers as learning tools, there have been many scales developed that can measure various aspects of ‘computer attitude’. The aim of this study is to examine the relevance of a number of these scales and determine whether they are still appropriate for use today. Four computer attitude scales, which are used widely, are assessed. It was found that the scales are reliable. However, the degree of predictive validity for each scale varied and the various underlying constructs appear to reflect different aspects of attitude. In addition, these constructs had changed since the original creation of the scales. This suggests that the traditional style of computer attitude scale is no longer as relevant as when first developed, and judicious selection and care need to be exercised over their use and the interpretation of findings. 相似文献
15.
S.A. Moya M. Vidal G. Abarca C. Martinez V. Guerchais H. Le Bozec M.T. Garland S. Rodriguez P. Aguirre 《Inorganic chemistry communications》2010,13(12):1519-1521
The synthesis and characterization of new ruthenium(II) carbonyl complexes containing polypyridine and triphenylphosphine ligands is reported. Crystallographic information obtained for the trans-PPh3-[Ru(biq)(PPh3)2(CO)]Cl2 complex (biq = 2,2’-biquinoline) reveals five-coordination on the metal. The complexes were studied as catalysts in hydrogen transfer reactions in basic solution. Turnover frequencies in the 2250-817 h-1 range were determined in 1 hour of reaction with a substrate/catalysts ratio of 830. 相似文献
16.
17.
Garland S.J. Guttag J.V. Horning J.J. 《IEEE transactions on pattern analysis and machine intelligence》1990,16(9):1044-1057
The checkability designed into the LSL (Larch shared language) is described, and two tools that help perform the checking are discussed. LP (the Larch power) is the principal debugging tool. Its design and development have been motivated primarily by work on LSL, but it also has other uses (e.g. reasoning about circuits and concurrent algorithms). Because of these other uses, and because they also tend to use LP to analyze Larch interface specifications, the authors have tried not to make LP too LSL-specific. Instead, they have chosen to build a second tool, LSLC (the LSL checker), to serve as a front-end to LP. LSLC checks the syntax and static semantics of LSL specifications and generates LP proof obligations from their claims. These proof obligations fall into three categories: consistency (that a specification does not contradict itself), theory containment (that a specification has intended consequences), and relative completeness (that a set of operators is adequately defined). An extended example illustrating how LP is used to debug LSL specifications is presented 相似文献
18.
A sensitive and specific assay for recombinant interleukin-2 (rIL-2) in human serum is described. The assay is based on a sequential sandwich immunobioassay that uses a microtiter plate coated with anti-rIL-2 monoclonal antibody (specific for recombinant human IL-2) to capture rIL-2 from serum, and an IL-2 dependent T-cell line that proliferates in a dose-dependent fashion. The lower limit of quantitation of the assay is 2 units/mL (1 unit = approximately 50 pg) using 0.1 mL of serum and the calibration curves ranged from 2 to 50 units/mL. Data are reported on the sensitivity, precision, reproducibility, and specificity of the assay; the stability of rIL-2 in serum; and the recovery of rIL-2 from serum. We also report on the use of the procedure to assay clinical samples from patients with AIDS undergoing treatment with rIL-2. 相似文献
19.
20.
ML Curtin SK Davidsen HR Heyman RB Garland GS Sheppard AS Florjancic L Xu GM Carrera DH Steinman JA Trautmann DH Albert TJ Magoc P Tapang DA Rhein RG Conway G Luo JF Denissen KC Marsh DW Morgan JB Summers 《Canadian Metallurgical Quarterly》1998,41(1):74-95
Studies conducted with the goal of discovering a second-generation platelet-activating factor (PAF) antagonist have identified a novel class of potent and orally active antagonists which have high aqueous solubility and long duration of action in animal models. The compounds arose from the combination of the lipophilic indole portion of Abbott's first-generation PAF antagonist ABT-299 (2) with the methylimidazopyridine heterocycle moiety of British Biotechnology's BB-882 (1) and possess the positive attributes of both of these clinical candidates. Structure-activity relationship (SAR) studies indicated that modification of the indole and benzoyl spacer of lead compound 7b gave analogues that were more potent, longer-lived, and bioavailable and resulted in the identification of 1-(N, N-dimethylcarbamoyl)-4-ethynyl-3-[3-fluoro-4-[(1H-2-methylimidazo[4,5-c] pyrid-1-yl)methyl]benzoyl]indole hydrochloride (ABT-491, 22 m.HCl) which has been evaluated extensively and is currently in clinical development. 相似文献