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991.
The application of a new method to the multivariate analysis of incomplete data sets is described. The new method, called maximum likelihood principal component analysis (MLPCA), is analogous to conventional principal component analysis (PCA), but incorporates measurement error variance information in the decomposition of multivariate data. Missing measurements can be handled in a reliable and simple manner by assigning large measurement uncertainties to them. The problem of missing data is pervasive in chemistry, and MLPCA is applied to three sets of experimental data to illustrate its utility. For exploratory data analysis, a data set from the analysis of archeological artifacts is used to show that the principal components extracted by MLPCA retain much of the original information even when a significant number of measurements are missing. Maximum likelihood projections of censored data can often preserve original clusters among the samples and can, through the propagation of error, indicate which samples are likely to be projected erroneously. To demonstrate its utility in modeling applications, MLPCA is also applied in the development of a model for chromatographic retention based on a data set which is only 80% complete. MLPCA can predict missing values and assign error estimates to these points. Finally, the problem of calibration transfer between instruments can be regarded as a missing data problem in which entire spectra are missing on the ‘slave’ instrument. Using NIR spectra obtained from two instruments, it is shown that spectra on the slave instrument can be predicted from a small subset of calibration transfer samples even if a different wavelength range is employed. Concentration prediction errors obtained by this approach were comparable to cross-validation errors obtained for the slave instrument when all spectra were available. 相似文献
992.
O. V. Shishkin 《Russian Chemical Bulletin》1997,46(9):1510-1512
The molecular geometries and inversion barriers of the rings in 2-oxo-1,2,3,4-tetrahydropyridine and its alkyl-substituted
(Me, Et, Pri, or But) and phenyl-substituted derivatives were calculated by the molecular mechanics method. The introduction of substituents has
no substantial effect on the equilibrium conformation of the heterocycle (a distorted sofa). For 4-alkyl- and 3-alkyl-substituted
derivatives (except for 4-Me and 4-Et derivatives), an axial orientation of the alkyl group is more favorable. The phenyl
substituents have equatorial and axial orientations at postions 4 and 3, respectively.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1584–1586, September, 1997. 相似文献
993.
毛细管电泳是一种高效、简便的分离方法,已被用于生物、环境及临床等试样的分离及分析[1].检测技术在毛细管电泳中占有重要的地位,目前,在柱紫外可见及荧光检测是两种广为接受的检测方法,但其检测灵敏度仅为10-5~10-6mol/L[2].电感耦合等离子体光谱(ICP-AES/MS)是一种灵敏的元素选择性的分析方法,已被广泛地用于各种试样中元素分析.近年来,该方法作为色谱及毛细管电泳的检测器,被用于元素的形态分析[3].在毛细管电泳(CE)与ICP光谱连用技术中,挑战性的工作是设计一种能把CE与ICP相连的接口.目前已有几种接口… 相似文献
994.
Moni Chauhan Claude Chuit Robert J. P. Corriu Catherine Rey Jean-Paul Declercq Antoine Dubourg 《Journal of organometallic chemistry》1996,510(1-2):173-179
The X-ray structure analysis of bis(8-dimethylamino-l-naphthyl)phenylphosphane (3) and of the corresponding sulphide 4 has revealed hexacoordination at phosphorus in both cases, the N … P separations being less than the sum of the van der Waal radii. Furthermore, in both cases the overall geometry corresponds to a distorted bicapped tetrahedron. The optimum geometry calculated for 4 via the
program developed by Autodesk (MM + method) suggests that the structure of the molecule is a function not only of steric requirements but also of electronic effects. 相似文献
995.
在氩气氛中,合成子SrMgF4:xEu,yTb复合氟化物磷光体,该体系中Eu^3+和Eu^2+共存,随共掺入Tb浓度的增加,Eu^3+的荧光发射强度降低,Eu^3+的发光增强,并且Eu^2+的ESR信号增强,认为Eu^3+和Tb3+之间存在的电荷迁移,即Eu^3+Tb^3+→Eu^2++Tb^4+,通过半量手段研究了这一电荷迁移反应的平衡常数。 相似文献
996.
997.
A simple and accurate digestion method using nitric acid, perchloric acid and hydrogen peroxide has been developed for use in trace analysis for heavy metals in vegetables by differential pulse anodic stripping voltammetry. The recovery of the metals from the samples is lower if the hydrogen peroxide is omitted from the digestion mixture. Standard reference materials have been analysed satisfactorily by this method. 相似文献
998.
Riccardo d'Agostino Vincenzo Colaprico Francesco Cramarossa 《Plasma Chemistry and Plasma Processing》1981,1(4):365-375
The spectroscopic emission intensities from excited F atoms in SF6-O2 discharges at 1 torr have been correlated to the densities of atoms in their ground electronic state by measuring the excitation efficiencies of the electrons in the energy range 11 to 17 eV with a method which essentially consists in the analysis of the emission of Ar or N2, added as actinometer gases to the discharge mixtures. The general applicability of the method has been tested by a direct titration of F atoms with chlorine. The spectroscopic analysis has allowed the determination of useful information on the trends of both the electron densities and their energies as a function of the oxygen percent in the feed. 相似文献
999.
1000.
Analyte transfer from the matrix in a thin layer distillation (TLD) cell and its subsequent measurement were investigated in a flow injection configuration. We designed the cell such that the donor and acceptor streams flowed in parallel channels separated by a thin dividing wall. The matrix transfer process involved room-temperature distillation of the analyte into the headspace of the TLD cell and its subsequent condensation/uptake by a concurrently flowing acceptor stream. There are no membranes; hence there are no membrane-related problems. The TLD system design was optimized with respect to its dimensions and operational parameters. Throughput and sensitivity were compared with a conventional pervaporation flow injection (PFI) system for ammonia and five different amines. For the higher molecular mass amines, the TLD approach provided comparable or superior performance. The TLD technique should be an attractive approach for online analysis of volatile chemical species in ‘dirty’ samples, especially for volatile analytes of higher molecular mass. 相似文献