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  • Analytical Chemistry and Spectroscopy  (2,321)
  • 2015-2019
  • 1990-1994  (1,518)
  • 1980-1984  (803)
  • 1940-1944
  • 1925-1929
  • 1993  (1,518)
  • 1983  (803)
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  • 2015-2019
  • 1990-1994  (1,518)
  • 1980-1984  (803)
  • 1940-1944
  • 1925-1929
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 7 (1993), S. 75-76 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 2
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 3
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    Journal of Chemometrics 7 (1993), S. 243-253 
    ISSN: 0886-9383
    Keywords: Orthogonal expansion ; Mapping ; Modelling ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we discuss the orthogonal expansion of data matrices and its application to mapping and modelling. Two new methods, modified optimal discriminant plane (MODP) for mapping and order Gram-Schmidt orthogonalization (OGSO) for modelling, are proposed and examples are given.
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  • 4
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 7 (1993) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 5
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    Journal of Chemometrics 7 (1993), S. 381-392 
    ISSN: 0886-9383
    Keywords: Factor analysis ; Kolmogorov-Smirnov test ; Non-parametric tests in factor analysis ; Non-parametric test for principal components ; Principal component analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Each eigenvector of the dispersion matrix [X]T [X] was shown to be a partial predictor of the original data matrix [X], the sum of the predictions from the individual principal components being equal to the expectance of [X]. By comparing the distributions of the members of two neighbouring predicted matrices, [X̃]1…i and [X̃]1…i+1 (i.e. the sums of the first i and i + 1 individual predictions respectively), it was shown that they should be indistinguishable provided that i is equal to or greater than the effective rank of [X], and significantly different otherwise. This was confirmed by analysing the visible absorption spectra of methyl orange and methyl red solutions as well as the Raman spectra of Na2SO4 and MgSO4 solutions. On the grounds of these findings, a non-parametric goodness-of-fit test for assessing the effective rank of [X] was proposed which proved to be comparatively conservative and more robust than most currently used tests.
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  • 6
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    Journal of Chemometrics 7 (1993), S. 369-379 
    ISSN: 0886-9383
    Keywords: Simulated annealing ; Constrained background bilinearization ; Calibration ; Two-way bilinear data ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Generalized simulated annealing (GSA) is an optimization technique for locating the global optimum. In this paper GSA was used as the optimization procedure in the constrained background bilinearization (CBBL) of two-way bilinear data in order to reduce the possibility of sinking into local optima. The behaviour of the algorithm and its comparison with the modified Powell algorithm were studied by simulations and real fluorescence excitation-emission data for organic dye mixtures.
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  • 7
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    Journal of Chemometrics 7 (1993), S. 439-445 
    ISSN: 0886-9383
    Keywords: Calibration ; Rank annihilation ; Residual bilinearization ; Three-way ; Trilinear ; Net analyte rank ; Second-order ; Generalized rank annihilation method (GRAM) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Through theoretical analysis and computer simulation, this short communication comments on the residual bilinearization (RBL) method and compares it with non-bilinear rank annihilation (NBRA) for the treatment of second-order calibration with non-bilinear data. It is found that these two methods are mathematically equivalent but have different noise propagation properties. The second-order advantage, namely quantitation in the presence of unknown interferences, can be carried over to non-bilinear data only if there exists a net analyte rank (NAR) for the analyte of interest.
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  • 8
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    Journal of Chemometrics 7 (1993), S. 495-526 
    ISSN: 0886-9383
    Keywords: Standard errors ; Eigenvalues ; PCA ; MLR ; GRAM ; Rank estimation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New expressions are derived for the standard errors in the eigenvalues of a cross-product matrix by the method of error propagation. Cross-product matrices frequently arise in multivariate data analysis, especially in principal component analysis (PCA). The derived standard errors account for the variability in the data as a result of measurement noise and are therefore essentially different from the standard errors developed in multivariate statistics. Those standard errors were derived in order to account for the finite number of observations on a fixed number of variables, the so-called sampling error. They can be used for making inferences about the population eigenvalues. Making inferences about the population eigenvalues is often not the purposes of PCA in physical sciences. This is particularly true if the measurements are performed on an analytical instrument that produces two-dimensional arrays for one chemical sample: the rows and columns of such a data matrix cannot be identified with observations on variables at all. However, PCA can still be used as a general data reduction technique, but now the effect of measurement noise on the standard errors in the eigenvalues has to be considered. The consequences for significance testing of the eigenvalues as well as the usefulness for error estimates for scores and loadings of PCA, multiple linear regression (MLR) and the generalized rank annihilation method (GRAM) are discussed. The adequacy of the derived expressions is tested by Monte Carlo simulations.
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  • 9
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    Journal of Chemometrics 7 (1993), S. 559-566 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 10
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    Journal of Chemometrics 7 (1993) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 11
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    Journal of Chemometrics 7 (1993), S. 61-73 
    ISSN: 0886-9383
    Keywords: Compression ; Multivariate analysis ; B-splines ; Maximum entropy ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For efficient handling of very large data arrays, pretreatment by compression is mandatory. In the present paper B-spline methods are described as good candidates for such data array compression. The mathematical relation between the maximum entropy method for compression of data tables and the B-spline of zeroth degree is described together with the generalization of B-spline compression to nth-order data array tables in matrix and tensor algebra.
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  • 12
    ISSN: 0886-9383
    Keywords: Factor analysis ; Window factor analysis ; Multicomponent analysis ; Ultraviolet spectroscopy ; Cu(II) complexes ; Ethylenediaminetetraacetic acid ; EDTA ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Window factor analysis (WFA) is a self-modeling chemometric technique for obtaining the concentration profiles of components from evolutionary processes such as chromotography, titration and reaction kinetics. By specifying the ‘window’, i.e. the region along the evolutionary axis indigenous to a component, the concentration profile of the component can be obtained without recourse to any information concerning the other components. Mathematical expressions required to perform such computations are derived. The method is applied to the investigation of copper(II) complexation with ethylenediaminetetraacetate (EDTA) by recording and factor analyzing the ultraviolet spectra of aqueous solutions containing a fixed amount of the disodium salt of EDTA and varying amounts of CuCl2. Evidence for four different species of EDTA is obtained. Clues concerning the stoichiometry of the species are garnered from the concentration profiles.
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  • 13
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    Journal of Chemometrics 7 (1993), S. 131-142 
    ISSN: 0886-9383
    Keywords: Classification ; Discriminant analysis ; Class modeling ; Specification limits ; Cross-validation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: There are many chemical products where product conformity is decided upon by qualitative human judgements of overall product quality. Nowadays, quantitative instrumentally determined quality parameters become available which are intended to replace such qualitative judgements by means of automatic decision rules using multivariate specification limits. Six classification methods to derive such limits are compared in terms of their power to predict corresponding human judgemets on overall color conformity of 17 dyestuffs based on historical quality data. Standard statistical classification methods turned out to be unacceptable for the routine generation of decision rules because of the frequent distinct suboptimality of their predictive power. Instead, a simple non-statistical classification method utilizing a priori knowledge about the underlying data structure yielded uniformly satisfactory decision rules.
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  • 14
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    Journal of Chemometrics 7 (1993), S. 153-163 
    ISSN: 0886-9383
    Keywords: Generalized inverse ; K-matrix analysis ; P-matrix analysis ; Least squares ; Principal component regression ; Partial least squares ; Continuum regression ; Beer's law ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper consists of two distinct but related parts. In the first part a geometric theory of generalized inverses is presented and a methodology based on this theory is developed and applied to solve the K-matrix and P-matrix forms of Beer's law. It is shown that most currently accepted and practiced methods for solving these forms of Beer's law are just special cases of this geometric theory of generalized inverses. In addition, this geometric theory is used to explain why the current methods work and why they fail.In the second part a general methodology that includes as special cases least squares, principal component regression, partial least squares 1 and 2, continuum regression plus a variety of other described and undescribed methodologies is presented and then applied to solve the P-matrix formulation of Beer's law. This general methodology, like the first, is also geometric in nature and relies on an understanding of projections.The main emphasis of this paper is one of perspective, which, if understood, provides the proper foundation for answering the general but extremely hard and possibly unanswerable question “what is the best method?”.
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  • 15
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    Journal of Chemometrics 7 (1993), S. 195-212 
    ISSN: 0886-9383
    Keywords: Calibration ; Non-linearity ; Principal components ; Stein estimate ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new regression method for non-linear near-infrared spectroscopic data is proposed. The technique is based on a model which is linear in the principal components and simple functions (squares and products) of them. Added variable plots are used to determine which squares and products to incorporate into the model. The regression coefficients are estimated by a Stein estimate which shrinks towards the estimate determined by the first several principal components and the selected non-linear terms. The technique is not computationally intensive and is appropriate for routine predictions of chemical concentrations. The method is tested on three data sets and in all cases gives more accurate predictions than does linear principal components regression.
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  • 16
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    Journal of Chemometrics 7 (1993), S. 227-242 
    ISSN: 0886-9383
    Keywords: Non-linear mapping ; Graphical methods ; SAR ; SPR ; Quality of representation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: From a review of the theoretical aspects of non-linear mapping and the different algorithms available in the literature, the methodological and practical problems linked to the use of this multivariate method in structure-activity and structure-property relationship studies are underlined. Useful tools for the graphical display of the outputs and the interpretation of the obtained clusters are presented. Statistical parameters estimating the quality of the graphical representation of each individual are also introduced. An example of application on a data matrix of 37 acaricides described by four physicochemical descriptors (π, F, R, MR) is presented.
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  • 17
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    Journal of Chemometrics 7 (1993), S. 291-304 
    ISSN: 0886-9383
    Keywords: Partial least squares ; Monte Carlo methods ; Cross validation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Partial least squares (PLS) regression is a commonly used statistical technique for performing multivariate calibration, especially in situations where there are more variables than samples. Choosing the number of factors to include in a model is a decision that all users of PLS must make, but is complicated by the large number of empirical tests available. In most instances predictive ability is the most desired property of a PLS model and so interest has centred on making this choice based on an internal validation process. A popular approach is the calculation of a cross-validated r2 to gauge how much variance in the dependent variable can be explained from leave-one-out predictions. Using Monte Carlo simulations for different sizes of data set, the influence of chance effects on the cross-validation process is investigated. The results are presented as tables of critical values which are compared against the values of cross-validated r2 obtained from the user's own data set. This gives a formal test for predictive ability of a PLS model with a given number of dimensions.
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  • 18
    ISSN: 0886-9383
    Keywords: Reaction kinetics ; Initial rate ; Kinetic order ; Response surface modelling ; Canonical analysis ; Organic synthesis ; Optimization ; Reaction mechanisms ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented by which it is possible to estimate the initial rate of chemical reactions when the experimental conditions are varied according to a response surface design. The method is intended as a complementary method for analysing data obtained from experiments in synthetic chemistry when the objective is to optimize the yield of the reaction.Data obtained by simulations have been used to develop the method. From the simulated reactions it is shown that sequential analysis of the chemical yield of the reaction makes it possible to estimate models which describe how the parameters of the response surface of the yield vary over time. The derivatives of these time functions of the response surface parameters can be used to define a rate function which describes how the variations in the experimental conditions influence the rate of the reaction.It is shown how such rate functions can be used to afford reasonable estimates of the initial rates of the reaction. The initial reaction rates thus estimated can be used to determine the kinetic order of the reactants and also to provide estimates of the activation energy of the reaction.A thorough discussion of how canonical analysis of the rate function may assist in the elucidation of reaction mechanisms is given.
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  • 19
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    Journal of Chemometrics 7 (1993), S. 427-438 
    ISSN: 0886-9383
    Keywords: Quality control ; Kerosene ; Variable reduction ; Cross-validation ; Variable selection ; Procrustes rotation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper deals with a typical question encountered in all industrial analytical laboratories: are all the tests performed in the laboratory to characterize the final product really necessary? In this work the cross-validation technique, Procrustes rotation techniques and statistical variable selection have been used to reduce the 26 initial British Petroleum and ASTM kerosene specification test to ten ‘essential’ ones. Statistical as well as chemical considerations were used to select the optimum subset of original variables to be retained from all the possible ones.
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  • 20
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    Journal of Chemometrics 7 (1993), S. 453-454 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 21
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    Journal of Chemometrics 7 (1993), S. 527-541 
    ISSN: 0886-9383
    Keywords: Principal component analysis ; Projection pursuit ; Simulated annealing algorithm ; Robust statistics ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Principal component analysis (PCA) is a widely used technique in chemometrics. The classical PCA method is, unfortunately, non-robust, since the variance is adopted as the objective function. In this paper, projection pursuit (PP) is used to carry out PCA with a criterion which is more robust than the variance. In addition, the generalized simulated annealing (GSA) algorithm is introduced as an optimization procedure in the process of PP calculation to guarantee the global optimum. The results for simulated data sets show that PCA via PP is resistant to the deviation of the error distribution from the normal one. The method is especially recommended for use in cases with possible outlier(s) existing in the data.
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  • 22
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    Journal of Chemometrics 7 (1993), S. 45-59 
    ISSN: 0886-9383
    Keywords: Partial least squares ; PLS algorithm ; Kernel ; Multivariate image analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fast and memory-saving PLS regression algorithm for matrices with large numbers of objects is presented. It is called the kernel algorithm for PLS. Long (meaning having many objects, N) matrices X (N × K) and Y (N × M) are condensed into a small (K × K) square ‘kernel’ matrix XTYYTX of size equal to the number of X-variables. Using this kernel matrix XTYYTX together with the small covariance matrices XTX (K × K), XTY (K × M) and YTY (M × M), it is possible to estimate all necessary parameters for a complete PLS regression solution with some statistical diagnostics. The new developments are presented in equation form. A comparison of consumed floating point operations is given for the kernel and the classical PLS algorithm. As appendices, a condensed matrix algebra version of the kernel algorithm is given together with the MATLAB code.
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    Journal of Chemometrics 7 (1993), S. 77-88 
    ISSN: 0886-9383
    Keywords: Direct trilinear decomposition method ; Curve resolution ; Trilinear data ; Similarity transformation ; Generalized rank annihilation method ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The direct trilinear decomposition method (DTDM) is an algorithm for performing quantitative curve resolution of three-dimensional data that follow the so-called trilinear model, e.g. chromatography-spectroscopy or emission-excitation fluorescence. Under certain coditions complex eigenvalues and eigenvectors emerge when the generalized eigenproblem is solved in DTDM. Previous publications never treated those cases. In this paper we show how similarity transformations can be used to eliminate the imaginary part of the complex eigenvalues and eigenvectors, thereby increasing the usefulness of DTDM in practical applications. The similarity transformation technique was first used by our laboratory to solve the similar problem in the generalized rank annihilation method (GRAM). Because unique elution profiles and spectra can be derived by using data matrices from three or more samples simultaneously, DTDM with similarity transformations is more efficient than GRAM in the case where there are many samples to be investigated.
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    Journal of Chemometrics 7 (1993), S. 143-148 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Chemometrics 7 (1993), S. 151-151 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 26
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    Journal of Chemometrics 7 (1993), S. 213-222 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of Chemometrics 7 (1993) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 28
    ISSN: 0886-9383
    Keywords: Multicomponent analysis ; Factor analysis ; Detection limit ; Local rank ; Zero-component region ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we redefine the term detection limit to embrace the inherent multivariate nature of samples, instrumental measurements and chemometrics resolution procedures. The so-called zero-component regions, i.e. parts with no chemical components eluting, are used as repeated analytical blanks to estimate a statistical multivariate detection limit for determining the number of chemical species in local regions of a single two-way chromatogram or a collection of synchronized one-way chromatograms. For two-way chromatography the detection limit is determined from the distribution of the first eigenvalues obtained from all possible combinations of spectra in the zero-component regions. The number of spectra in each calculation should correspond to the number included in the later examination of the local retention time regions. For one-way chromatography on a collection of samples with similar chemical components at varying concentrations the same procedure is used, with the samples taking the role of the spectra in two-way chromatography. The detection limit can be chosen at various confidence levels depending on whether false positive or negative detection of minor components is most critical. The results obtained from the zero-eigenvalue distribution are more robust than those obtained by a previously developed F-test.
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  • 29
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    Journal of Chemometrics 7 (1993), S. 447-452 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 30
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    Journal of Chemometrics 7 (1993), S. 477-494 
    ISSN: 0886-9383
    Keywords: Three-way principal components analysis ; Core matrix ; Body diagonalization ; Lower and upper bounds ; Simulation ; Soil contamination ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In contrast with conventional PCA, a direct superposition and joint interpretation of loading plots is not possible in three-way PCA, since there may be data variance which is described by unequal components of different modes. The contributions to variance of all possible combinations of components are described in the core matrix. Body diagonalization, which is achieved by appropriate rotation of component matrices, is an essential tool for simplifying the core matrix structure. The maximum degree of body diagonality which may be obtained from such transformations is analysed from both the mathematical and simulation viewpoints. It is shown that, at least in the average case, high degrees can be expected, which makes the procedure reasonable for many practical applications. Furthermore, simulation as well as theoretical derivation show that the success of body diagonality depends on the so-called polarity of the core array. The methodology is illustrated by a three-way data example from environmental chemistry.
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  • 31
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    Journal of Chemometrics 7 (1993), S. 551-557 
    ISSN: 0886-9383
    Keywords: Krylov sequence ; Partial least squares ; Polynomial regression ; Principal component regression ; R2 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: PLS1 regression is generally viewed as lying in between PCR and OLS regression. Proof is given that the coefficient of determination, R2, for a PLS multivariate calibration model is at least as high as that for a PCR model with the same number of components. It appears that PLS can be linked to a correlation-weighted polynomial regression of a constant response on the eigenvalues of the covariance matrix of the predictor variables.
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  • 32
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    Journal of Chemometrics 7 (1993), S. 1-14 
    ISSN: 0886-9383
    Keywords: Continuum regression ; Dynamic model identification ; Principal component regression ; Partial least squares regression ; Finite impulse response ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of continuum regression (CR) for the identification of finite impulse response (FIR) dynamic models is investigated. CR encompasses the methods of principal component regression (PCR), partial least squares (PLS) and multiple linear regression (MLR). PCR and MLR are at the two extremes of the continuum. In PCR and PLS, cross-validation is used to determine the optimum number of factors or ‘latent variables’ to retain in the regression model. CR allows one to vary the method in addition. Cross-validation then determines both the optimum method and the number of latent variables. The CR ‘prediction error surface’ - a function of the method and number of latent variables - is elucidated. The optimal model is defined as the minimum of this surface. Among the cases studied, the optimal model usually comes from the region of the continuum between PCR and PLS. Few derive from the region between PLS and MLR. It is also demonstrated that FIR models identified by CR have frequency domain properties similar to those identified by PCR.
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    Journal of Chemometrics 7 (1993) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 34
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    Journal of Chemometrics 7 (1993), S. 117-130 
    ISSN: 0886-9383
    Keywords: Calibration ; Rank annihilation ; Three-way ; Trilinear ; Bilinear ; Non-bilinear ; Net analyte signal ; MS/MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several multivariate methods are now available for the calibration of second-order or hyphenated instruments (e.g. GC/MS). When applied to bilinear data, it has been shown that calibration can be performed in the presence of unknown interferences - a significant advantage over first-order calibration. In this paper, non-bilinear rank annihilation (NBRA), a method which has the potential of handling, second-order non-bi-linear data, is studied through theoretical analysis and computer simulation. It is found that the second-order advantage can be carried over to non-bilinear data if a property defined as net analyte rank (NAR) holds for the analyte of interest. The net analyte signal (NAS) is defined accordingly for second-order calibration and the analogy to and difference from lower-order calibration are discussed. With NAS, some analytical figures of merit such as signal-to noise ratio, selectivity, sensitivity and limit of determination can be calculated for second order calibration. An application to MS/MS data is also given.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 36
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    Journal of Chemometrics 7 (1993), S. 177-193 
    ISSN: 0886-9383
    Keywords: Multivariate analysis ; Function space ; Coefficient space ; B-splines ; Compression ; PCA ; PLS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general framework for manipulating spectra as functions in traditional multivariate methods such as PCA and PLS is described. The functional representation is very convenient for compression, ensuring smoothness and continuity. There are two fundamentally different types of representations: (a) by functions and (b) by function coefficients. The use of coefficients is the most practical way of analysis.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 38
    ISSN: 0886-9383
    Keywords: Kalman filter ; Multivariate calibration ; Condition number ; Prediction error ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: The usefulness of the Kalman filter as an algorithm for calibration in a real system is shown. Results are compared with classical least squares and pure component calibration. The prediction of four priority pollutant chlorophenols in binary, ternary and quaternary mixtures was also carried out by Kalman filtering. The condition number, standard deviation and prediction error have been employed to choose the most suitable wavelength range. Comparison of the standard error of prediction in the validation set shows significant differences between the evaluated chlorophenols, the best results being obtained with Kalman multivariate calibration.
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  • 39
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    Journal of Chemometrics 7 (1993), S. 255-265 
    ISSN: 0886-9383
    Keywords: Multicomponent calibration ; Non-linearity ; Selectivity ; Wavelength selection ; Graphical diagnostics ; Outliers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Modern scanning infrared reflectance/absorption spectroscopes measure absorptions or reflectance at a sequence of around 1000 wavelengths. Training data may consist of 10-100 carefully designed sample mixtures whose true compositions are either known by formulation or accurately determined by wet chemistry. In future, one wishes to predict the true composition of a newly presented sample from its spectrum. Varying compositions of a mixture of three sugars in water are used for illustration of several different graphical techniques; the spectral measurements here are near-infrared (NIR) absorbances, but there is nothing exclusively infrared about the methodology. Graphs display the adequacy of a linear explanation of absorbance variability at each wavelength by wavelength linearity plots. These highlight regions of the spectrum where non-linearities and interaction effects are substantial. By selecting out these substantially non-linear regions, one can concentrate on linear formulae for prediction with resultant robust linear modelling. Such selections are further aided by plots which identify the component sugar for which each wavelength is most selective. Such plots offer rather natural pre-screening as an alternative or supplement to the wavelength selection method of Brown.We also display prediction diagnostics (R, Rx) which on a sample-by-sample basis may diagnose a particularly unusual presented spectrum. These diagnostics are shown to have predictive import for a validation data set.
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  • 40
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    Journal of Chemometrics 7 (1993), S. 305-340 
    ISSN: 0886-9383
    Keywords: Stem & leaf display ; Histogram ; Boxplot ; Quantile plot ; Scatterplot ; Regression ; Smoothing ; 3D rotation ; Scatterplot matrix ; OMEGA strategy ; Dimension reduction ; Stability of structure ; Resampling ; Interpretation of structure ; Prediction models ; Variables selection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Exploratory data analysis (EDA) is a toolbox of data manipulation methods for looking at data to see what they seem to say, i.e. one tries to let the data speak for themselves. In this way there is hope that the data will lead to indications about ‘models’ of relationships not expected a priori. In this respect EDA is a pre-step to confirmatory data analysis which delivers measures of how adequate a model is. In this tutorial the focus is on multivariate exploratory data analysis for quantitative data using linear methods for dimension reduction and prediction. Purely graphical multivariate tools such as 3D rotation and scatterplot matrices are discussed after having introduced the univariate and bivariate tools on which they are based. The main tasks of multivariate exploratory data analysis are identified as ‘search for structure’ by dimension reduction and ‘model selection’ by comparing predictive power. Resampling is used to support validity, and variables selection to improve interpretability.
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  • 41
    ISSN: 0886-9383
    Keywords: Curve resolution ; Multicomponent analysis ; Latent projections ; Local factor analysis ; Chlorophyll degradation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-performance liquid chromatography with diode array detection (HPLC--DAD) is used to characterize mixtures from chlorophyll a degradation experiments. Overlapping chromatographic peaks are resolved by means of the heuristic evolving latent projections (HELP) method. The HELP method is a self-modelling curve resolution method. No assumptions are made about spectral and/or chromatographic peak shape. In the first step the method establishes the real noise level in the data by use of the so-called zero-component regions. This information is used to reveal selective chromatographic information and the number of chemical species at every retention time in unresolved chromatographic peaks. Utilising the selective chromatographic regions in combination with the zero-concentration windows, unique resolution into concentration profiles and spectra of the pure chemical species is accomplished. HPLC-DAD data from six chlorophyll a degradation experiments were analysed. Consistent results were obtained even with very similar spectra for six or seven overlapping chemical components.
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  • 42
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    Journal of Chemometrics 7 (1993), S. 99-115 
    ISSN: 0886-9383
    Keywords: Classification ; Appreciation function ; Regularized discriminant analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Regularized discriminant analysis has proven to be a most effective classifier for problems where traditional classifiers fail because of a lack of sufficient training samples, as is often the case in highdimensional settings. However, it has been shown that the model selection procedure of regularized discriminant analysis, determining the degree of regularization, has some deficiencies associated with it. We propose a modified model selection procedure base on a new appreciation function. By means of an extensive simulation it was shown that the new model selection procedure performs better than the original one. We also propose that one of the control parameters of regularized discriminant analysis be allowed to take on negative values. This extension leads to an improved performance in certain situations. The results are confirmed using two chemical data sets.
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    Journal of Chemometrics 7 (1993), S. 149-150 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 44
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    Journal of Chemometrics 7 (1993), S. 165-176 
    ISSN: 0886-9383
    Keywords: Measurement error ; Outliers ; Environmental ; Quality control ; Multivariate kurtosis ; Generalized distance ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Environmental data are usually multivariate, with the variables conforming to some correlation structure. Occasionally, measurements which do not conform in structure or magnitude may occur in one or more variables. It is important (1) to characterize these discordancies in terms of the disturbed variables and the direction and magnitude of the anomalous error and (2) to associate each discordant observation with a specific cause of measurement error in order to prevent further mismeasurement. We describe a procedure for identifying suspected causes of discordant observations in otherwise multinormal data sets. Variables are assigned to groups, each of which is associated with a specific cause of measurement error. Discordant observations are identified with the generalized distance test or the multivariate kurtosis test. Suspected causes of measurement error are identified by repeating the tests with one of the groups of variables omitted in each analysis. The procedures are evaluated with simulated data sets having a correlation structure similar to that of a large environmental data set.
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    Journal of Chemometrics 7 (1993), S. 393-425 
    ISSN: 0886-9383
    Keywords: Preprocessing ; Closure ; Normalization ; Ratioing ; Constant sum transformation ; Constant length transformation ; Maximum value transformation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The geometric properties of three common object-preprocessing transformations (constant sum, or closure; constant length, or normalization; and maximum value, or ratioing) are investigated. An argument is made for using absolute values in the constant sum and maximum value transformations. In general, each transformation distorts the shape and dimensionality of patterns in the data: transformed data lie on (C-1)-dimensional surfaces in the original C-dimensional space. A data set that has been closed by one of these transformations can be reopened if a vector containing the constant sums, constant lengths or maximum values of the original objects was retained. Transformed data sets may be freely interconverted among these three transformations without the loss of information.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 7 (1993), S. 455-475 
    ISSN: 0886-9383
    Keywords: Biological activity ; Cross-validation ; Exchangeability ; Molecular descriptors ; Prediction ; Relationship ; Structure ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The two parts of this paper form a critique of a variety of statistical techniques of actual or potential use in quantitative structure-activity relationship (QSAR) studies and related fields. Part I explores the statistical thinking that is needed to underpin those techniques. Emphasis as placed on (a) the role of ‘exchangeability’ as an alternative to unrealistic statistical modelling and (b) the use of cross-validation to limit self-deception in the use of any particular technique. The problem of the almost unlimited range of molecular descriptors is seriously addressed. (Part II provides a concise critical review of methods-some well-established and some new.)
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    Journal of Chemometrics 7 (1993), S. 543-550 
    ISSN: 0886-9383
    Keywords: Fragment occurrence data ; Molecular similarity ; Similarity searching ; Standardization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Substructural fragment occurrence data are widely used as the basis for measures of inter-molecular structural similarity. This paper investigates the effect of standardization on the effectiveness of such measures using eight data sets for which both structural and biological activity data are available. Eight different standardization methods are studied and it is shown that there is no significant difference in the effectivenesses of the various methods; accordingly, any of them can be used for the calculation of intermolecular structural similarity.
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    Journal of High Resolution Chromatography 6 (1983), S. 36-37 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary column ; Cryogenic focusing ; On-column, pre-column trapping ; Volatile aroma compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 38-39 
    ISSN: 0935-6304
    Keywords: Gas chromatography-mass spectrometry (GC/MS) ; Capillary, fused silica ; Dihalogenated propanols ; Positional isomers ; Haloperoxidase ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 40-42 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary columns ; Splitless Injection ; Drug analysis ; Concentration dependence of retention values ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 20-26 
    ISSN: 0935-6304
    Keywords: Reversed-phase mode liquid chromatography ; Rekker's hydrophobic fragmental constant ; Calculation of concentration of organic modifier ; Prediction of retention time of phenols ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromatographic behavior of phenols in reversed-phase mode liquid chromatography differs from that of non-ionic compounds such as alkyl alcohols, alkylbenzenes, halogenated benzenes, polyaromatic hydrocarbons, and aromatic acids. Therefore, the retention times of 61 phenols were measured in a system of an octadecyl bonded silica gel and acetonitrile/water mixtures. The logarithm of the capacity ratio (log k') was found to be a linear function of the hydrophobicity (log P) in acidic acetonitrile/water mixtures. This result was applied to a different octadecyl bonded silica gel. Eight phenols were selected as standard compounds, and their log k' values were measured in 0.05 M phosphoric acid in 10 to 90% acetonitrile/water mixtures. An empirical polynomial relation was obtained between the concentration of acetonitrile and the slope of the log k' vs log P curve. Finally the capacity ratio of all phenols were calculated in given eluents by the equations derived from the measurements of standard compounds and the calculated log P values. The difference between predicted capacity ratios and measured ones was within 10%.
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    Journal of High Resolution Chromatography 6 (1983), S. 42-44 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Mg(NO3)2 .6H2O as stationary phase ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 45-46 
    ISSN: 0935-6304
    Keywords: Gel filtration of proteins ; Eluent parameters (pH and ionic strength) ; TSK-GEL G3000SW ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 64-67 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 60-63 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary column ; Cold silanization ; Medium polarity columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silane-coupling agents, commonly used for fiberglass reinforced plastics (FRP), were applied for deactivation of silanol sites in glass capillary columns prior to coating with mediumpolarity phases such as Carbowax and Superox. The columns, prepared in a two-stage process in the case of glass (acidic leaching and drying, dynamic cold silanization followed by static coating with the phase) or a one stage process in the case of fused silica, gave the best results when deactivation and hence wettability were induced by glycidoxypropyltrimethoxy silane.
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    Journal of High Resolution Chromatography 6 (1983), S. 72-76 
    ISSN: 0935-6304
    Keywords: Gas chromatography/mass spectrometry ; Capillary column, fused silica ; Long term precision ; Pollutant analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A test mixture containing 28 compounds plus their stable isotopically labeled analogs was analyzed on a daily basis for one month during a series of routine fused silica capillary column GC/MS analyses in order to establish the precision with which retention times and responses were produced. These long-term precision data were evaluated to determine how to best predict retention times and how to best reproduce quantification. Results clearly indicate that relative retention times should be calculated using the reference compound eluted most closely to the target compound and that quantification should be based on relative response using a chemically “similar” compound.
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  • 59
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Residue analysis ; Fenvalerate ; Fabric protectant ; Woolen cloth ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for the determination of fenvalerate (cyano(3-phenoxyphenyl)methyl 4-chloro-α-(1-methylethyl)-benzeneacetate) residues on woolen cloth. The fenvalerate was Soxhlet-extracted from the treated fabric with acetone for four hours at a reflux rate of six solvent exchanges per hour. The fenvalerate residue was determined by gas-liquid chromatography with a flame ionization detector. The results were quantitated by comparing integrator counts obtained from extracts of treated samples with those obtained from known standards. The method was sensitive to 0.00054% fenvalerate by weight. Recoveries from fabric treated with 0.00054% to 0.215% averaged 94.8%. The response of the detector was linear over a 400-fold range of fenvalerate concentrations.
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    Journal of High Resolution Chromatography 6 (1983), S. 273-274 
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    Keywords: Gas chromatography ; Solvent effect ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 275-277 
    ISSN: 0935-6304
    Keywords: Ion chromatography ; Low level ions detectable in highly caustic solutions ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 269-272 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Retention indices ; Specific retention volumes ; n-Alkanes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The choice of stationary phase for gas chromatography is dictated by the nature of the analytes. Polarity and selectivity are known to play an important role. This paper suggests equations for calculation of specific retention volumes of any compounds from their retention indices.
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    Journal of High Resolution Chromatography 6 (1983), S. 310-315 
    ISSN: 0935-6304
    Keywords: Micro-HPLC ; Gradient elution ; Epoxy resin oligomers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-performance micro packed fused-silica and open-tubular glass capillary columns were prepared and applied to separations of complex mixtures. Solvent-gradient elution proved quite useful for the separation of solutes with wide polarity. Instruments and some applications are described.
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    Journal of High Resolution Chromatography 6 (1983), S. 300-305 
    ISSN: 0935-6304
    Keywords: Fused silica capillary columns ; Flexibility ; Polyimide coating ; Cobalt-60 gamma radiation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five commercial varieties of uncoated fused silica capillary tubing used in high resolution gas chromatography were subjected to cobalt-60 gamma radiation. The advantages and superior performance of fused silica open tubular columns coated with OV-1 and subsequently immobilized or crosslinked in situ by radiation is reported in a previous paper in this Journal; however, in this investigation a loss in flexibility of irradiated capillaries was also noted. Quantitative measurements on flexibility were performed on specimens of irradiated fused silica capillaries, indicating that changes do indeed occur upon irradiation. Scanning electron micrographs also illustrate slight deterioration of the outer protective polyimide coating. Most surprisingly, it was also established that a variation does exist in the flexibility of the commercially available raw material studied.
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    Journal of High Resolution Chromatography 6 (1983), S. 306-309 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for separation of low amounts of DHETX m. s. from human plasma, based on extraction and determination by high performance liquid chromatography with fluorimetric detection.
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    Journal of High Resolution Chromatography 6 (1983), S. 348-358 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 366-370 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Fused silica capillary column ; Chiral phase ; Amino acid enantiomers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heliflex Chirasil-Val, a modified form of the original Chirasil-Val phase coated on fused silica capillary, has been investigated with regard to its resolution efficiency and the separation profile for various enantiomeric derivatives of amino acid. The best results could be obtained with TFA-Et derivatives by reason of the relatively low column temperature required.
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    Journal of High Resolution Chromatography 6 (1983), S. 383-385 
    ISSN: 0935-6304
    Keywords: Ion chromatography ; Indirect detection ; Water analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 386-387 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary columns ; On column injection ; Movable injector ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 388-389 
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    Keywords: Gas chromatography ; Fused silica capillary micro-packed columns ; Separation characteristics ; Application ; Separation of hydrocarbons ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 392-393 
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    Keywords: Gas chromatography ; Capillary columns ; Hydrogen carrier gas ; Pt-Ir tubing ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 390-391 
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    Keywords: Gas chromatography ; Dispersive interactions ; Inductive interactions ; Polycyclic aromatic hydrocarbons ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 394-396 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 396-396 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 399-400 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 77
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    Journal of High Resolution Chromatography 6 (1983), S. 419-421 
    ISSN: 0935-6304
    Keywords: GLC ; Solute escape ; Solvent effects ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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  • 78
    ISSN: 0935-6304
    Keywords: Thin layer chromatography, TLC ; Quantitation by TLC scanner ; Detection mode, fluorescence quenching ; Precision 1.8%, accuracy 2.7% ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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  • 79
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    Journal of High Resolution Chromatography 6 (1983), S. 451-451 
    ISSN: 0935-6304
    Keywords: High performance liquid chromatography, HPLC ; Electron-capture detector, ECD ; Extra-column broadening, ECB ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 567-568 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Solvent effect ; Headspace analysis ; Trace analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 569-570 
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    Keywords: Serially coupled capillary columns ; Window diagram ; Optimization ; Compressibility ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 571-572 
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    Keywords: Micro HPLC ; Bile acids ; Precolumn concentration ; Postcolumn reaction ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 573-574 
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    Keywords: Reversed phase HPLC ; Fluorimetric detection ; Fossil chlorins ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 581-583 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 577-580 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 575-576 
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    Keywords: Thin-film chromatography, HPTFC ; Separation on argentized silica gel ; Detection ; Scanning densitometry ; Lipids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 583-583 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 584-584 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 4-10 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Ion mobility detector ; Plasma chromatography ; Selective detection ; Quantitative analysis ; Halogenated compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An ion mobility detector that has been specifically developed for interfacing with capillary gas chromatography is investigated in the negative ion mode. Like the electron capture detector, to which this instrument is closely related, the ion mobility detector shows an enhanced response to low molecular weight halogenated compounds when a small quantity of oxygen is doped into the make-up gas flow. Under O2 doping conditions, the device can operate in a reactant ion monitoring mode responding universally to compounds capable of capturing thermal electrons and in a tunable selective product ion mode providing increased selectivity over that achieved by the ECD. At an oxygen concentration of 0.5%, minimum detectable amounts as low as 600 femtograms have been realized for carbon tetrachloride. Selectivity of chloro- versus bromo- compounds is demonstrated using a mixture of p-dichlorobenzene and p-dibromobenzene.
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    Journal of High Resolution Chromatography 6 (1983), S. 11-15 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass ; ECD ; Halocarbons in water, 0.1-10 ppb ; 0.5-2 μl injected on-column ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Interest in monitoring halogenated organics in drinking water and natural surface and ground water in the low ppb range continues to grow. There is a tendency to include still more volatile halocarbons, the trace determination of which is known to be rather demanding. This prompted us to re-examine the feasibility of large-volume direct aqueous injection onto capillary columns, coupled with ECD. A primary problem was to avoid simultaneous elution of water with halocarbons, since water suppresses the ground current of the ECD. The following measures contributed to the solution of this problem.Apolar, extremely inert, columns are required to elute water completely, and even before very light halocarbons. Their coatings have to be far thicker (≍ 5 mUm) than commonly employed thick films since they must permit isothermal analysis at a column temperature around 100°C in order to ensure rapid and complete elution of water. Finally, it is essential that sampling be carried out on-column for two reasons: diffusion of water vapor in the injector, resulting in delayed elution, is then eliminated, and peak distortion during splitless injection is avoided.Although we now know that persilylated columns with immobilized coatings withstand routine water injections, more longterm experience is needed to provide detailed recommendations for the handling of these columns.
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  • 92
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; Liquid crystal stationary phases ; para-Substituted cholesterol cinnamate ; Geometrical isomers (insect pheromones) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four para-substituted cholesterol cinnamates were synthesized and evaluated for utility as gas chromatograph (GC) liquid crystal stationary phases. The capability of the phases to separate olefinic geometrical isomers was found to be dependent on the position of the olefinic bond. When unsaturation occurred at positions four carbons or greater from the terminal methyl of the compounds investigated, the relative ability of the phases to separate geometrical isomers was p-Cl 〉 p-Me 〉 cholesterol cinnamate 〉 p-MeO derivative 〉 p-NO2. When unsaturation occurred at positions four carbons or less from the terminal methyl the relative ability of the para-derivatives of cholesterol cinnamate to separate geometrical isomers was reversed.
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    Journal of High Resolution Chromatography 6 (1983), S. 27-30 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; LSC with binary eluents ; Resolution in LSC ; Selectivity in LSC ; Adsorption LC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The recently derived general equation for the capacity ratio has been utilized to study the dependence of selectivity and resolution upon mobile phase composition. This equation accounts for differences in molecular size of solutes and solvents, and for the energetic heterogeneity of the adscrbent surface. Model calculations illustrating the influence of these factors on the selectivity and resolution are presented and discussed.
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    Journal of High Resolution Chromatography 6 (1983), S. 33-33 
    ISSN: 0935-6304
    Keywords: Liquid-liquid partition chromatography, HPLC ; Liquid-liquid distribution ; Nucleoside ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 34-35 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass ; Samples with varying water content ; Retention times correlated with water content ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 6 (1983), S. 51-52 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 54-54 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 6 (1983), S. 77-81 
    ISSN: 0935-6304
    Keywords: High performance thin-layer chromatography, HPTLC ; Fluorescence quantitation ; Scanning densitomery ; Resolution ; Signal-to-noise ratio ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conditions for maximizing resolution and signal-to-noise ratios in fluorescence scanning densitometry of separations obtained by high performance thin-layer chromatography are described. Resolution was found to be independent of most instrument parameters with a small decrease observed at wide slit widths. Signal was found to be markedly dependent on experimental parameters such as slit width, slit height, sensitivity setting, and the time constant of electronic filters. For recording chromatograms a slit width of 1.00 mm, a slit height slightly greater than the spot diameter, a low sensitivity setting (50 mV), electronic filtering, and a scan rate of 24 or 48 mm min-1 are commensurate with minimum recording time and maximum sample detectability without incurring a significant decrease in resolution.
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    Journal of High Resolution Chromatography 6 (1983), S. 203-208 
    ISSN: 0935-6304
    Keywords: Thin-layer chromatography, TLC ; Temperature effect on retention ; Martin's equation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study has been undertaken on the effect of temperature on retention characteristics in thin-layer chromatography (TLC) with low-volatility mobile phases (MP). It is shown that temperature variations in TLC in melts bring about variations in both the relative retention values and, in some cases, in the order of migration of the chromatographic zones across the layer. The variation in the capacity factor k' with temperature agrees well with Martin's equation. To explain the temperature dependence of Rf one must, in general, take into account the variations with temperature in both the partition coefficient and the phase ratio. To describe the variation in Rf with temperature in TLC with low-volatile MP one can use an approximate equation in which In Rf is a linear function of 1/T. The experiments indicate that temperature is a major factor in TLC in melts.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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