摘要:

AbstractThe use of recursive filtering techniques for parameter estimation in a variety of areas is reviewed. In particular, the Kalman filter algorithm is described, along with several variations, including square‐root,UDUTand information filters. The solution to parameter estimation problems is discussed for both linear and non‐linear models. Applications described include calibration, curve resolution in spectroscopy, chromatography, electrochemistry, kinetic analysis and process monitor

ISSN:0886-9383    

DOI:10.1002/cem.1180040203

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

摘要:

AbstractThe design of an experiment for the determination of binding parameters in the association between a ligand and a macromolecule with two groups of non‐interacting binding sites is proposed. In the Gauss–Newton non‐linear least squares treatment the standard deviation of each parameter is given as the product of two terms: one depending on the experimental error and the other, the diagonal element of the dispersion matrix, depending only on the independent variables of the system. In order to reach an optimal experimental design, these diagonal elements of the information matrix have to be minimized. In our approach this is achieved by searching those values of the independent variable which maximize the determinant of the information matrix. Furthermore, the limits of validity of the model are deduced from an analysis of the diagonal elements of the information matrix obtained under optimal condi

ISSN:0886-9383    

DOI:10.1002/cem.1180040204

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

摘要:

AbstractThe partial least squares–residual bilinearization (PLS–RBL) approach to background correction presented in Part 1 of this work is demonstrated with an example from HPLC with diode array detection. Data are also evaluated with generalized rank annihilation factor analysis (GRAFA) and results are compa

ISSN:0886-9383    

DOI:10.1002/cem.1180040205

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

摘要:

AbstractWhen constructing diagnostic systems or using knowledge‐based systems, e.g. in analytical chemistry, features of different type and character, represented by numbers, trajectories or linguistic variables such as intensities or colours, must be considered. To find neighbourhoods or to fill in missing values, the notion of similarity is of essential importance. The paper presents a new fuzzy‐set‐theory‐based approach to quantifying similarity and provides a system of rules to be implemented into the diagnostic part of the knowledge base to

ISSN:0886-9383    

DOI:10.1002/cem.1180040206

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

摘要:

AbstractSome well‐established ideas from classical covariance stabilization and shrinkage estimation are extended to the context of physical mixtures through the use of a model developed by Burdick and Rayens. A cross‐validation techique is proposed and associated computational issues are addressed. The methodology is evaluated in the context of real polychlorinated biphenyl d

ISSN:0886-9383    

DOI:10.1002/cem.1180040207

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

摘要:

AbstractIn this paper a criterion is described for the construction of experimental designs for the evaluation of calibration models in analytical chemistry. The proposed criterion seeks a compromise between theD‐optimal designs for estimating the parameters of different polynomial models. A computer algorithm is presented for a sequential construction of experimental designs using the optimality criterion. The performance of the optimality criterion and the computer algorithm is elaborated for the problem of discrimination between a first‐ to a third‐degree polynomial for the calibration of analytical methods. An experimental design consisting of replicate measurements at five distinct levels equally spaced over the calibration range proved a good sol

ISSN:0886-9383    

DOI:10.1002/cem.1180040208

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

摘要:

AbstractIf in two data tablesXandYobjects are characterized by the same variables (measured at different occasions), then looking for common latent features should be more appropriate than choosing latent features inXandYseparately (e.g. as in canonical correlation or PLS). The procedure to be proposed here is a slight modification of the method of linear characteristics (according to De Groot and Li) by disclaiming the assumption of equal inner‐block covariance matrices. In order to find weights defining a latent feature with maximal correlation betweenXandY, a system of non‐linear equations has to be solved. The procedure is applied to the investigation of heavy metal concentrations in different human tiss

ISSN:0886-9383    

DOI:10.1002/cem.1180040209

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

ISSN:0886-9383    

DOI:10.1002/cem.1180040210

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

ISSN:0886-9383    

DOI:10.1002/cem.1180040211

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY

ISSN:0886-9383    

DOI:10.1002/cem.1180040202

出版商:John Wiley&Sons, Ltd.    

年代:1990

数据来源: WILEY