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101.
102.
人工神经网络及其在分析化学中的应用 总被引:31,自引:1,他引:31
人工神经网络是一种新兴的计算方法,有着广阔的发展前途,目前在分析化学领域已经有了多方面的应用。本文简要介绍了人工神经网络的原理及其在分析化学中的应用。 相似文献
103.
I. Esteban-Díez 《Analytica chimica acta》2006,555(1):84-95
Orthogonal WAVElet correction (OWAVEC) is a pre-processing method aimed at simultaneously accomplishing two essential needs in multivariate calibration, signal correction and data compression, by combining the application of an orthogonal signal correction algorithm to remove information unrelated to a certain response with the great potential that wavelet analysis has shown for signal processing. In the previous version of the OWAVEC method, once the wavelet coefficients matrix had been computed from NIR spectra and deflated from irrelevant information in the orthogonalization step, effective data compression was achieved by selecting those largest correlation/variance wavelet coefficients serving as the basis for the development of a reliable regression model. This paper presents an evolution of the OWAVEC method, maintaining the first two stages in its application procedure (wavelet signal decomposition and direct orthogonalization) intact but incorporating genetic algorithms as a wavelet coefficients selection method to perform data compression and to improve the quality of the regression models developed later. Several specific applications dealing with diverse NIR regression problems are analyzed to evaluate the actual performance of the new OWAVEC method. Results provided by OWAVEC are also compared with those obtained with original data and with other orthogonal signal correction methods. 相似文献
104.
《Surface and interface analysis : SIA》2005,37(7):589-607
The accuracy of quantitative XPS analysis can be improved using predetermined transmission functions. Two different calibration methods are used for estimating the transmission function T(E) of a photoelectron spectrometer, applying a survey spectra approach (SSA) and a quantified peak‐area approach (QPA) to minimize the quantification error. For the SSA method, Au, Ag and Cu spectra measured with the Metrology Spectrometer II have been used. The new QPA method was built up from Au 4f, Au 4d, Au 4p3/2, Ag 3d, Ag 3p3/2, Cu 3p, Cu 2p3/2, Ge 3p and Ge 2p3/2 standard peak areas, applying adequate ionization cross‐sections and mean free path lengths for different pass energies (10 and 50 eV), lens modes (large area, large area XL, small area 150) and x‐ray sources (Al/Mg Twin and Al Mono). In the energy range 200–1500 eV a transmission function T(E) = a0 + b1E (where a0, b1 and b2 are variable parameters) was found to give an appropriate approximation for eight tested spectrometer settings, implementing the largest changes in the case of pass energy variations. Determination and application of the transmission functions were integrated in the XPS analysis software (UNIFIT 2004) and tested by means of an Ni90Cr10 alloy. The results demonstrate the practicability of the SSA and QPA methods, giving decreased errors of <8% in comparison with errors up to 38% obtained using Wagner's sensitivity factors. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
105.
The process of electron transport plays an essential role in the fundamental phenomena of life like photosynthesis, respiration and vision as well as in photoelectronic devices. However, the molecular mechanisms of the electron way and factors governing the transport rate in such systems are still unclear. Several groups have reported theoretical approaches for searching the mechanisms by using statistical mechanics, coherent dynamics and quantum mechanics. The current density vector inside the semiconducting layer is determined. In this paper we consider the problem of transport of electron promoted in the electrochemical cell constructed of two electrodes with the dye molecules immersed in. We describe the process of electron promotion by refractive light wave on the vacuum–semiconductor boundary as well as on the semiconducting electrode and the dye molecule layer in terms of extended phenomenological electrodynamics formalism. The results of our theoretical model show that such a theoretical approach will give more information on the mechanism of electron transport and will give insight in the determination of some electric features of materials. 相似文献
106.
The lattice model for equilibrium polymerization in a solvent proposed by Wheeler and Pfeuty is solved exactly on a Bethe lattice (core of a Caylay tree) with general coordination numberq. Earlier mean-field results are reobtained in the limitq, but the phase diagrams show deviations from them for finiteq. Whenq=2, our results turn into the solution of the one-dimensional problem. Although the model is solved directly, without the use of the correspondence between the equilibrium polymerization model and the diluten0 model, we verified that the latter model may also be solved on the Bethe lattice, its solution being identical to the direct solution in all parameter space. As observed in earlier studies of the puren0 vector model, the free energy is not always convex. We obtain the region of negative susceptibility for our solution and compare this result with mean field and renormalization group (-expansion) calculations. 相似文献
107.
Two different spectrofluorimetric methods for the determination of piroxicam (PX) in serum are presented and discussed. One of them is based on the use of three-way fluorescence data and multivariate calibration performed with parallel factor analysis (PARAFAC) and self-weighted alternating trilinear decomposition (SWATLD). This methodology exploits the so-called second-order advantage of the three-way data, allowing to obtain the concentration of the studied analyte in the presence of any number of uncalibrated (serum) components. The method was developed following two different procedures: internal standard addition and external calibration with standard solutions, which were compared and discussed. The second approach investigated is based on the combination of solid-phase extraction (SPE) and room temperature fluorimetry. Both methods here presented yield satisfactory results. The concentration range in which PX could be determined in serum was 1–10 μg ml−1. The limits of quantification for the experimental solutions using the chemometric approach were 0.09 μg ml−1 for the standard addition mode and 0.12 μg ml−1 using external calibration (both for PARAFAC and SWATLD algorithms). In the solid-surface fluorimetric method, the calibration graph was linear up to 0.22 μg ml−1 and the limit of quantification was 0.02 μg ml−1. 相似文献
108.
109.
Martí MP Pino J Boqué R Busto O Guasch J 《Analytical and bioanalytical chemistry》2005,382(2):440-443
The aromatic composition of sugar cane spirits and, in general, of alcoholic beverages, is mainly influenced by the ageing process in wood barrels. There are several factors that affect the quality of the final aged product, but the time of the storage in the barrel is perhaps the most important one. Ageing time must therefore be controlled in order to detect counterfeits; however, this parameter is very difficult to control and, at present, there is no analytical method available to determine it. We propose a quantitative method for determining the ageing time of sugar cane spirits in oak barrels by using an electronic nose based on coupling directly a headspace sampler to a mass spectrometer (HS-MS), and multivariate calibration. The method developed is simple and provides, in 5 min, the ageing time of spirits with an accuracy of about 1 month. 相似文献
110.
Investigation of carbon-13 nuclear magnetic resonance spectra-structure correlation based on novel atomic distance-edge (ADE) vector 总被引:1,自引:0,他引:1
A set of novel graph-theoretical parameters,called the atomic distance-edge (ADE) vector,was developed.Based on the connecting C-C bond number between central carbon atom and the other ones,various carbon atoms of alkanes were classified as four types,i.e.,type 1,2,3 and 4 for primary,secondary,ternary and quaternary carbon,respectively; and then four regression equations were obtained to link carbon-13 chemical shift (CS) of each type of atoms.Furthermore,these regression models were used to predict the carbon-13 nuclear magnetic resonance spectra of alkanes and it was found that the estimated CS were in agreement with the experimental results. 相似文献