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  • Analytical Chemistry and Spectroscopy  (2,281)
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  • 1
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 6 (1992) 
    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
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    Journal of Chemometrics 6 (1992), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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  • 3
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    Journal of Chemometrics 6 (1992), S. 63-64 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 4
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    Journal of Chemometrics 6 (1992), S. 65-83 
    ISSN: 0886-9383
    Keywords: Trilinear decomposition ; Receptor modeling ; Source identification ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In many cases, monitoring data for ambient airborne particles can be organized in the form of a three-way data table with one way for chemical species, one for sampling periods and one for sites. A direct trilinear decomposition followed by a matrix reconstruction (DTDMR) is developed to analyze such a data table as a whole. The three-way data set is composed into three two-way matrices by a direct trilinear decomposition (DTD). The column vectors of each of the matrices are called ‘source profiles’, ‘emission patterns’ and ‘site coefficients’ respectively. Particulate sources are identified by examining both their source profiles and emission patterns. After the sources have been identified, emission patterns and site coefficients are used to produce a three-way matrix that gives estimates of mass contributions of sources to the samples collected at every site in every period. By simulation study, not only has the method been verified, but a good indicator has been found that shows the number of factors (i.e. sources) in the system. Unlike other receptor models, DTDMR does not require source profile data and does not involve trial-and-error procedures. Since DTDMR identifies sources based on variations in two dimensions, it has a higher potential to distinguish two sources that have similar chemical compositions. The DTDMR model has provided excellent results with simulated data and has been applied in a real world three-way data set.
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  • 5
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    Journal of Chemometrics 6 (1992), S. 113-116 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 6
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    Journal of Chemometrics 6 (1992), S. 117-118 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 7
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    Journal of Chemometrics 6 (1992), S. 151-161 
    ISSN: 0886-9383
    Keywords: NIR spectroscopy ; Wavelength selection ; Interaction effects ; Multicomponent mixtures ; Partial least squares ; Generalized least squares ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Modern scanning (near-)infrared reflectance/absorption (NIR) spectroscopes measure the absorptions or reflectances at a sequence of around 1000 wavelengths. Training data may consist of 10-100 carefully designed sample mixtures for which the true composition of the mixture is either known by formulation or accurately determined by wet chemistry. In future one wishes to predict the true composition from the spectrum. In this paper we compare a simple wavelength selection approach with methods which retain all the wavelengths. It offers a powerful yet simple technique for choosing those wavelengths that are specific to each pure component as against the other components (including the medium) for the varying compositions. In the presence of a defined range of ingredients in thus chooses wavelengths which are highly selective for each particular component. It has the added advantage of selecting wavelengths which are little effected by interaction effects and consequent non-linearities.The calibration data used consist of 125 observations of three sugars, each varying at five levels in a full 53 design. The validation set consists of 21 further samples specially selected to have compositions outside the range of the training sample. The selection methods perform much better on this prediction set than methods which retain all the wavelengths, 700 in this case. The leave-one-out cross-validation internal to the calibration data would point to the opposite finding and suggests that such crossvalidations may be overly flattering to techniques such as partial least squares and may encourage overfitting. After selection, simple straightforward least squares methods may be used, eschewing the need for ‘shrinkage’ methods such as partial least squares or ridge regression.
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  • 8
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    Journal of Chemometrics 6 (1992), S. 247-255 
    ISSN: 0886-9383
    Keywords: Analysis of variance ; Assumptions ; Graphics ; Models ; Validation of model ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The computer has made it possible to scrutinize data rapidly by means of graphics. This should be done prior to the application of any model to the data, since the model must be validated before using it as a means of analyzing the data. The procedure is illustrated in terms of two examples of real experimental data.
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  • 9
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    Journal of Chemometrics 6 (1992), S. 284-285 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 10
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    Journal of Chemometrics 6 (1992), S. 307-334 
    ISSN: 0886-9383
    Keywords: Non-linear PLS ; Quadratic regression ; Non-linear models ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We treat here an extension of linear PLS regression to include regression on quadratic PLS components. The quadratic regression can be viewed as a natural extention of linear PLS regression to quadratic PLS according to the H-principle of mathematical modelling. The numerical implementation is treated in detail. It is shown that this approach can be used for models with large numbers of variables. Some modelling strategies are discussed depending on the purpose of the modelling. Applications of this approach are treated.
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  • 11
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    Journal of Chemometrics 6 (1992), S. 357-357 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 12
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    Journal of Chemometrics 6 (1992) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 13
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    Journal of Chemometrics 6 (1992), S. 29-40 
    ISSN: 0886-9383
    Keywords: Factor analysis ; Window factor analysis ; Multicomponent analysis ; Flow injection analysis ; Self-modeling curve resolution ; Bismuth chloride complexes ; 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 method for extracting the concentration profiles of individual components from evolutionary processes such as flow injection, chromatography, titrations and reaction kinetics. The method takes advantage of the fact that each component lies in a specific region along the evolutionary axis, called the window. Theoretical equations are derived. The method is used to extract the concentration profiles and spectra of seven bismuth species from data obtained by Gemperline and Hamilton, who injected bismuth perchlorate into a flowing stream of hydrochloric acid.
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  • 14
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    Journal of Chemometrics 6 (1992), S. 57-62 
    ISSN: 0886-9383
    Keywords: Closure ; Baseline ; Mean centering ; Rank ; Exploratory data analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes an investigation into the relationship of closure, a baseline offset and mean centering to the interpretation of matrix rank. The equivalence of a certain type of closure to a constant baseline (i.e. a simple numerical offset which may vary between response channels but is constant over all samples) is demonstrated. A systematic approach to the interpretation of the rank of a matrix is given.
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  • 15
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    Journal of Chemometrics 6 (1992), S. 97-102 
    ISSN: 0886-9383
    Keywords: Between-group variances ; Canonical variate criterion ; Eigenvalues ; Eigenvectors ; Orthogonal projection ; Within-group variance ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Canonical variate analysis is the appropriate descriptive technique for multivariate data which have an a priori group structure, but problems arise with this technique when there are more variables than within-group degrees of freedom because of singularity of matrices. In such cases it is shown through illustrative examples that principal component analysis is a viable substitute provided that the principal components are ranked according to the canonical variate criterion (ratio- of between- to within-group variances) rather than the usual criterion of total variance. This ranking can also be used to select components for subsequent discriminant analysis.
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  • 16
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    Journal of Chemometrics 6 (1992) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 17
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    Journal of Chemometrics 6 (1992), S. 119-133 
    ISSN: 0886-9383
    Keywords: Mass spectra ; Classification ; Structure description ; Fragmentation ; Ion series ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to investigate correlations between the functionality of compounds and the classification of their mass spectra, low-resolution spectra of monofunctional compounds have been classified by four supervised classification methods. The new classes are characterized by structural features and the correlation between functionality and classification is explained by fragmentation rules. Systematic misclassifications show that low-resolution mass spectra alone are not suitable for reliable identification of functionality.
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  • 18
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    Journal of Chemometrics 6 (1992), S. 163-175 
    ISSN: 0886-9383
    Keywords: Multiple-correspondence analysis ; Starch granule description ; Image analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raw starch is composed botanically of characteristic granules of various sizes and shapes, so that each kind of starch may be characterized by the population of its granules. In the present study ten commercial starch species were studied: wheat, rice, manioc, potato, arrowroot, amylomaize, normal maize, waxy maize and two different banana species. Six variables measuring the size and shape of granules were obtained by image analysis. The objective was to find a method to describe and compare the granule populations of the ten species. For such a study, multiple-correspondence analysis (MCA) was applied. MCA makes it possible to draw similarity maps of categories and objects. For each starch species the frequency distributions (histograms) of the six variables were assessed and each granule was characterized by its species and the classes of histograms to which it belonged. MCA was applied to the granule table and a description of the histogram classes and the granules was obtained. From the variables description a general typology of the granules was deduced. The similarity maps showed considerable scatter of the granules for all species except rice. A particular species could therefore not be identified by a single granule, but the granule distribution seemed to be characteristic. MCA was an appropriate method to analyse these data because it points out non-linear relationships between quantitative and qualitative variables.
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  • 19
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    Journal of Chemometrics 6 (1992), S. 177-188 
    ISSN: 0886-9383
    Keywords: PLS ; Prediction error ; Background constituents ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modification of a technique proposed by Lorber and Kowalski for the estimation of prediction errors is presented. The method is applied to five data sets. The results show that for some data sets the estimated prediction errors are close to the actual prediction errors for samples within the calibration range, while samples outside the calibration range must be background corrected before quantification of the prediction error.
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  • 20
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    Journal of Chemometrics 6 (1992), S. 189-198 
    ISSN: 0886-9383
    Keywords: Robust regression ; Partial least squares ; QSAR ; Perturbation study ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A robust partial least squares (PLS) regression algorithm is developed. This is achieved by substitution of the univariate regression steps in the iterative PLS2 algorithm by a robust alternative. The angle between loading vectors from both perturbed and unperturbed solutions is used as a measure of robustness. By means of a perturbation study on a structure-activity data set, it is demonstrated that the stability of the robust method is superior to standard PLS.
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  • 21
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 22
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    Journal of Chemometrics 6 (1992) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 23
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    Journal of Chemometrics 6 (1992), S. 267-281 
    ISSN: 0886-9383
    Keywords: Genetic algorithms ; Feature selection ; Multivariate analysis ; Optimization methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Genetic algorithms have been created as an optimization strategy to be used especially when complex response surfaces do not allow the use of better-known methods (simplex, experimental design techniques, etc.). This paper shows that these algorithms, conveniently modified, can also be a valuable tool in solving the feature selection problem. The subsets of variables selected by genetic algorithms are generally more efficient than those obtained by classical methods of feature selection, since they can produce a better result by using a lower number of features.
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  • 24
    ISSN: 0886-9383
    Keywords: Derivatization reaction ; Factorial design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of nucleophiles have been successfully identified and quantified using the Kröhnke reaction with 2,3-diphenyl derivatives of quinolizinium salts. Optimization of the reaction conditions by means of a mathematical model involving analysis of the response surface has led to a better understanding of the factors exerting an influence on the above reaction.The parameters chosen were temperature, reaction time, base concentration, water concentration and nucleophile concentration. The reaction was developed in polar aprotic solvents (acetone, acetonitrile). To facilitate the nucleophilic attack, the presence of an organic base (triethylamine) was necessary, although concentrations in excess of 0·15M did not alter the development of the reaction. Since pharmaceutical solutions are often aqueous, the influence of water on the reaction was studied. Low water volumes have no significant influence on the opening of the quinolizinium ring by the nucleophilic reagent. However, when the water proportion exceeded that of the organic solvent, the fluorescence intensity was lower than expected. Development of the fluorescent reaction product was first detected 5 min after the reaction started. The fluorescence intensity reached its optimum value after 138 min.
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    Journal of Chemometrics 6 (1992), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 26
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    Journal of Chemometrics 6 (1992), S. 85-96 
    ISSN: 0886-9383
    Keywords: Optimization ; Calibration ; Simulated annealing ; Experimental design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper utilizes variable step size generalized simulated annealing (VSGSA) to design multicomponent calibration samples for spectroscopic data. VSGSA is an optimization procedure which is capable of converging to exact positions of global optima located on multidimensional continuous functions. On the basis of analysis sample response vectors, optimally designed calibration concentration matrices are obtained assuming knowledge of components present. The complexity of response surfaces established by the optimization criteria is described.
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  • 27
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    Journal of Chemometrics 6 (1992), S. 103-111 
    ISSN: 0886-9383
    Keywords: Mean centering ; Preprocessing ; Multivariate calibration ; Error propagation ; Principal component regression (PCR) ; Partial least squares (PLS) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Traditionally, one form of preprocessing in multivariate calibration methods such as principal component regression and partial least squares is mean centering the independent variables (responses) and the dependent variables (concentrations). However, upon examination of the statistical issue of error propagation in multivariate calibration, it was found that mean centering is not advised for some data structures. In this paper it is shown that for response data which (i) vary linearly with concentration, (ii) have no baseline (when there is a component with a non-zero response that does not change in concentration) and (iii) have no closure in the concentrations (for each sample the concentrations of all components add to a constant, e.g. 100%) it is better not to mean center the calibration data. That is, the prediction errors as evaluated by a root mean square error statistic will be smaller for a model made with the raw data than a model made with mean-centered data. With simulated data relative improvements ranging from 1% to 13% were observed depending on the amount of error in the calibration concentrations and responses.
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    Journal of Chemometrics 6 (1992), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 29
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    Journal of Chemometrics 6 (1992), S. 135-150 
    ISSN: 0886-9383
    Keywords: 2D surface ; Multivariate analysis ; Non-congruent ; Unfolding ; Folding ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of latent variable projection for analysis of non-congruent 2D surfaces is presented. We give a formal description of the folding/unfolding process. A simulated 2D oscillator evolving in time is studied in detail to illustrate interpretation aspects of the method.
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    Journal of Chemometrics 6 (1992), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 6 (1992), S. 199-216 
    ISSN: 0886-9383
    Keywords: MARS ; Splines ; Multivariate calibration ; Non-linear ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This tutorial paper presents a simplified view of one of the more recently published multivariate calibration methods particularly suited to dealing with non-linear data sets. The method is referred to as MARS and stands for multivariate adaptive regression splines. Simple examples are provided to explain the workings of the method.
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    Journal of Chemometrics 6 (1992), S. 228-228 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 6 (1992), S. 229-229 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 34
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    Journal of Chemometrics 6 (1992), S. 231-246 
    ISSN: 0886-9383
    Keywords: Integration methods ; Taylor series method ; Optimization methods ; Kinetic mechanisms ; Kinetic determinations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general equation to derive kinetic models up to any order is given. This equation greatly facilitates the application of the Taylor series method to the integration of kinetic models up to very high orders. When dealing with non-stiff models, computing time is always reduced by increasing the integration order, at least up to the 20th order. When the model is stiff, the integration order should be optimized; however, a twelfth order is recommended to integrate weakly stiff models. The use of an algorithm which permits the immediate calculation of the integration step size required to maintain a given accuracy leads to further reductions in computing time. When implemented as recommended here, a high-order Taylor series method is more rapid and accurate than Runge-Kutta and predictor-corrector methods and can be advantageously used in combination with optimization methods to perform mechanism studies and in multicomponent kinetic determinations.
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  • 35
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 36
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    Journal of Chemometrics 6 (1992), S. 289-305 
    ISSN: 0886-9383
    Keywords: Chemical structure database ; Conformational searching ; Similarity searching ; Substructure searching ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents a review of the rapid developments that have taken place over the last few years for the searching of databases of three-dimensional (3D) molecules. The geometric arrangement of the atoms in a 3D molecule is described by an interatomic distance matrix. This is a form of labelled graph that can thus be searched using the subgraph-isomorphism algorithms that are widely used for searching databases of two-dimensional (2D) molecules. Several in-house and commercial systems have been developed for 3D database searching that are based on such techniques. These systems are reviewed and their effectiveness demonstrated by examples of their use in the discovery of novel, biologically active molecules. Current systems represent a molecule by one or a small number of low-energy conformations and there is hence much interest in the development of representational techniques and searching algorithms that account for the full set of geometric arrangements that can be adopted by a flexible molecule.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 38
    ISSN: 0886-9383
    Keywords: GOLPE ; PLS ; Regression ; SDEP ; Variable selection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure called GOLPE is suggested in order to detect those variables which increase the predictivity of PLS models. The procedure is based on evaluating the predictive power of a number of PLS models built by different combinations of variables selected according to a factorial design strategy. Examples are given of the efficiency of this variable selection procedure, which shows how these predictive PLS models are better than those obtained by all variables and better than the corresponding ordinary regression models.
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  • 39
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    Journal of Chemometrics 6 (1992), S. 11-28 
    ISSN: 0886-9383
    Keywords: Three-way PLS ; PARAFAC ; Unfolding ; Validatory tools ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The methods PARAFAC and three-way PLS are compared with respect to their ability to predict reversed-phase retention values. Special attention is paid to simple validatory tools, the meaning and use of which are explained.
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  • 40
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    Journal of Chemometrics 6 (1992), S. 41-56 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The principal properties, here called the ρ-scales, of peat have been calculated on the basis of chemical analysis. The scales were derived from quantitative contents of carbohydrates, Klason lignin, amino acids, amino sugars and conventional chemical peat measurements. The variation in the chemical parameters was compressed using principal component analysis (PCA). Partial least squares (PLS) regression was used for prediction of botanical, microbial, physical and dewatering data. A rapid estimation of the scales has been made from near-infrared (NIR) spectroscopy and offers, indirectly, rapidly obtainable, chemically interpretable, biological information. A reduced scale based on carbohydrate data was also tested. The ρ-scales offer an interface between different areas of peat research. Strategies are outlined for the selection of a subset of chemical measurements among the variables used for characterization. A multivariate strategy based on these ideas is discussed.
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  • 41
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    Journal of Chemometrics 6 (1992) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 42
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    Journal of Chemometrics 6 (1992), S. 217-225 
    ISSN: 0886-9383
    Keywords: Principal component regression ; Calibration ; Optimality ; Principal component selection ; Quantitative structure-activity relationship ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Principal components (PCs) for principal component regression (PCR) have historically been selected from the top down for a reliable predictive model. That is, the PCs are arranged in a list starting with the most informative (PC associated with the largest singular value) and proceeding to the least informative (PC associated with the smallest singular value). PCs are then chosen starting at the top of this list. This paper discusses an alternative procedure of treating PC selection as an optimization problem. Specifically, without any regard to the ordering, the optimal subset of PCs for an acceptable predictive model is desired. Five data sets are analyzed using the conventional and alternative approaches. Two data sets are spectroscopic in nature, two data sets deal with quantitative structure-activity relationships (QSARs) and one data set is concerned with modeling. All five data sets confirm that selection of a subset without consideration to order secures the best results with PCR. One data set is also compared using partial least squares 1.
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  • 43
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    Journal of Chemometrics 6 (1992), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 44
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    Journal of Chemometrics 6 (1992), S. 257-266 
    ISSN: 0886-9383
    Keywords: Principal factor analysis ; Factor analysis ; Eigenvalue analysis ; Multivariate analysis ; Weighted factor analysis ; Procrustean analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two approximate methods for weighted principal components analysis (WPCA) were devised and tested in numerical experiments using either empirical variances (obtained from replicated data) or assumed variances (derived from unreplicated data). In the first (‘spherical’) approximation each data vector was assigned a weight proportional to the geometrical mean of its variances in all dimensions. The arithmetical mean of variances was used instead in the other approximation. Both the numerical experiments with artificial data containing random errors of various kinds (constant, proportional, constant plus proportional, Poisson) and the analysis of two sets of Raman spectra clearly indicated the necessity of introducing statistical weights. The spherical approximation was found to be slightly better than the arithmetical one. The application of statistical weighting was found to improve the performance of PCA in estimation problems.
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  • 45
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 46
    ISSN: 0886-9383
    Keywords: Predictive ability ; Regression ; PLS ; SDEP ; Cross-validation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The standard deviation of prediction errors (SDEP) is used to evaluate and compare the predictive ability of some regression models, namely MLR, ACE and linear and non-linear PLS, the last being the best one. The parameter is determined by a cross-validation approach as an average of several runs obtained on forming groups in a random way. The variation in SDEP with the number of latent variables in PLS is also discussed.
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  • 47
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    Journal of High Resolution Chromatography 5 (1982), S. 311-320 
    ISSN: 0935-6304
    Keywords: Chromatography theory, GC and LC ; Chromatography plate concept, “theoretical” and “discontinuous” ; Partial differential contributions ; Variance addition rule ; Theoretical band shapes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown theorectically that the classical formula for calculating the theoretical plate number from squared first central moment, tms2, and second central moment, σ2, according to ntheor = tms2/σ2 is valid only when the capacity ratio, k approaches infinity. The general relation between the classical experimental HETP value, H = L/nmtheor, and the underlying true theoretical plate height, ΔL, is found to be\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm H' = }\frac{{{\rm L(\sigma ')}^{\rm 2} }}{{\overline {\rm t}_{{\rm ms}}^{\rm 2} }}{\rm = }\frac{{{\rm 2}\overline {\rm D} _{\rm m} }}{{\overline {\rm u} }}{\rm + }\overline {\rm k} \frac{{{\rm 2}\overline {\rm D} _{\rm s} }}{{\overline {\rm u} }}{\rm + \Delta L}\frac{{\overline {\rm k} }}{{{\rm 1 + }\overline {\rm k} }} $$\end{document} when (σ′)2 is the total column contribution to band broadening, L is the column length, Dm is the average diffusion coefficient of the sample component in the mobile phase, Ds is its value in the stationary phase, and u is the average linear velocity of the mobile phase. The mobile phase displacement, as well as the mass exchange process, is assumed to be continuous, but the application of the plate concept conditions leads to a mass balance equation that can be interpreted as belonging to a modified discontinuous plate model. The contributions 2Dm/u and k 2 Ds/u from longitudinal sample diffusion in the mobile and stationary phases, respectively, are consistent with the assumption that the processes are statistically independent, although the common solution technique of the differential equations does not take full account of this independence.
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    Journal of High Resolution Chromatography 5 (1982) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 49
    ISSN: 0935-6304
    Keywords: Thin-layer chromatography, TLC ; Binary solvent mixtures ; New solvent polarity ranking ; Optimization ; Window diagram ; Cluster center ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ΔRf, the separation between a pair of compounds on a thin layer chromatographic plate, can be predicted as a function of solvent composition for certain binary systems. This allows the prediction of optimum solvent composition for separating a mixture of compounds by thin layer chromatography. A new solvent polarity ranking, based on calculation of ΔRf is described.
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    Journal of High Resolution Chromatography 5 (1982), S. 382-384 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Trapping by active charcoal ; Thermal desorption system ; Microwave oven ; 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 5 (1982), S. 3-12 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 52
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    Journal of High Resolution Chromatography 5 (1982), S. 31-37 
    ISSN: 0935-6304
    Keywords: Gas-liquid chromatography ; Plasma determination ; Midazolam ; Pharmacokinetic study ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A sensitive gas liquid chromatographic (GLC) assay was developed for plasma determinations of 8-chloro-6-(2′ -fluorophenyl)-1-methyl-4H-imidazo[1,5 α][1,4]benzodiazepine (compound I) and its hydroxymethylimidazo metabolite (compound II). The internal standards used were 8-chloro-6-(2′ -chlorophenyl)-1 -methyl-4H-imidazo[1,5 α][1,4]benzodiazepine (compound VI) and 7-chloro-5-(2′ -fluorophenyl)-1, 3-dihydro-1-(hydroxyethyl)-2H-1,4-benzodiazepin-2-one (compound VII) for compounds I and II, respectively. Following extraction, and silylation for compound II, compounds I and II were analyzed by GLC using a glass column packed with 5% OV-101 on Gas-Chrom Q, and a 63Ni electron-capture detector. The GLC method was validated by a CI-GC/MS technique. The detection limit of the assay is approximately 4-5 ng/ml for compound I and 3 ng/ml for compound II. The method was used in comparative pharmacokinetic studies of the distribution of the two compounds in arterial and venous blood.
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    Journal of High Resolution Chromatography 5 (1982), S. 50-51 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass, fused silica ; Connection ; 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 5 (1982), S. 58-58 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 55
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, fused silica ; Effluent splitter ; Selective detectors: NPD, Hall™ electrolytic conductivity detector ; Chloro- and chloronitroanilines ; POTW sludge extracts ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simultaneous detection with a 700-A Hall™ and an NPD detector is an effective technique for characterizing chloro-and chloronitroanilines in highly complex Publicly Owned Water Treatment Works (POTW) sludges. The utilization of a modified Varian effluent splitter and a SE-54 fused silica capillary column permitted the detection of mid-picogram quantities of the polar chloroanilines without sacrificing peak shape. The response of the Hall™ detector in the halogen mode was roughly proportional to the number of chlorine atoms present, while the response of the Hall™ in the nitrogen mode and the NPD was less predictably influenced by the presence of one or more nitro groups. When combined with retention time data, the ratio of the NPD response to the Hall™ response has been found to substantiate the presence of chloro- and chloronitroanilines in sludge extracts.
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    Journal of High Resolution Chromatography 5 (1982), S. 98-99 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass ; Polyaromatic hydrocarbons ; Airborn Particulates ; Aircraft turbines ; 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 5 (1982), S. 106-107 
    ISSN: 0935-6304
    Keywords: RM values in HPTLC ; A-ring derivatives of 5α-cholestane ; trans-Decalin derivatives as reference compounds ; ΔRM values for C/D rings and side chain in 5α-cholestanes ; 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 5 (1982), S. 113-113 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 59
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass ; High temperature silylation ; C2-C6 fatty acids ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 5 (1982), S. 134-138 
    ISSN: 0935-6304
    Keywords: Thin-layer chromatography ; Reversed phases ; Preloading with solvent vapors ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromatographic behavior of some hydrocarbons and some of their nitro derivates after preconditioning with solvent vapors has been investigated. After preloading with cyclohexane or hexane an improved separation of some sample pairs is observed. Furthermore, inversion of Rf values takes place. The preloading of the reversed-phase plates permits utilization of mobile phase with higher water content, thus leading to a significant shortening of developing time.
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    Journal of High Resolution Chromatography 5 (1982), S. 150-150 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 62
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    Journal of High Resolution Chromatography 5 (1982), S. 139-142 
    ISSN: 0935-6304
    Keywords: Thin-layer chromatography, TLC ; TLC with mixed mobile phases ; Adsorption chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Considerations of TLC process optimization have been based on the thermodynamic theory of adsorption from multicomponent solvents using experimental and theoretical RM1, 2 = f (Φ1) relationships. It was found that a relationship exists between the Az parameter (log k1,2∞ where k1,2∞ is the partition coefficient of the substance chromatographed) of the above theory and pKa values of substances as well as the solubility parameter δ of the mobile phase components. Analysis of the Az values of substances shows that a slight variation therein is associated with lower selectivity of chromatographic separation.
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    Journal of High Resolution Chromatography 5 (1982), S. 206-207 
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    Keywords: Gas chromatography ; Capillary, glass ; cis, trans, positional isomers of C22 esters separated on OV-73 ; Numerous arguments favor nonpolar columns ; 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 5 (1982), S. 213-214 
    ISSN: 0935-6304
    Keywords: Capillary GC ; Electron capture detection ; Time constant, purge flow ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 5 (1982), S. 222-222 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 5 (1982), S. 218-220 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 5 (1982), S. 236-244 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary columns ; Rotary valve ; Cold trap ; Reinjection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper describes a cold trap/reinjection system for capillary columns which utilizes a flow switching rotary valve. Sample enrichment is performed in a liquid nitrogen-cooled glass trap attached to the valve. Evaporation of enriched compounds is carried out with the aid of an electric heating coil. Parameters such as cryogenic trapping efficiency, reinjection rates, transference of sample, and adsorption, as well as overall performance, are examined. In addition, a comparison is made between the cold trap/reinjection technique and injection with a gas-tight syringe.
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    Journal of High Resolution Chromatography 5 (1982), S. 265-266 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary column ; Helium ionization detector ; Aroma ; Coffee ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 5 (1982), S. 13-18 
    ISSN: 0935-6304
    Keywords: Gas chromatography, capillary ; Column preparation ; Immobilization of stationary phases ; Procedure for polar phases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Whereas the immobilization of apolar silicone phases is essentially understood and mastered, the corresponding treatment of even moderately polar phases remains problematical. Upon attack by peroxide radicals, these phases respond by forming active transformation products rather than by bonding to the support surface or to neighboring molecules. OV-1701 is at present the most polar stationary phase which can reasonably be immobilized. An essential feature of the practical procedure is the prevention of film breakage after coating the inert support surface and before immobilization. Two ways of overcoming this problem are presented.
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    Journal of High Resolution Chromatography 5 (1982), S. 45-47 
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    Keywords: Gas chromatography ; Capillary, glass ; Fast screening of drugs and adulterants ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 5 (1982), S. 55-56 
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    Keywords: Gas chromatography ; Non-uniformity of distribution of stationary phase confirmed ; Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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    Journal of High Resolution Chromatography 5 (1982), S. 60-60 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 5 (1982) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of High Resolution Chromatography 5 (1982), S. 19-26 
    ISSN: 0935-6304
    Keywords: Gas chromatography, glass capillary ; Selective detection ; Nitrated polycyclic aromatic hydrocarbons ; Carbon black ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glass capillary gas chromatography has been investigated as a method for the analysis of nitrated polycyclic aromatic hydrocarbons (nitro-PAH) using both splitless and on-column injection techniques. The nitro-PAH showed good chromatographic performance and thermal stability under the GC conditions used. Retention times and response factors of several nitro-PAH were compared to those of conventional PAH.Simultaneous flame ionization and thermionic nitrogen selective detection was used to facilitate identification of nitro-PAH in complex samples. The feasibility of the method is demonstrated on two samples of commercial carbon black. Besides 1-nitropyrene several isomeric dinitropyrenes have been identified.
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    Journal of High Resolution Chromatography 5 (1982), S. 27-30 
    ISSN: 0935-6304
    Keywords: Gas chromatography/mass spectrometry ; Capillary columns, fused silica ; Response factors, interlaboratory ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A quality control procedure for Fused Silica Capillary Column Gas Chromatography/Mass Spectroscopy (FSCC GC/MS) was tested and shown to produce similar response factors at five Spectroscopy (FSCC GC/MS) was tested and shown to produce similar response factors at five laboratories. The average relative standard deviation (RSD) of interlaboratory response factors for fifty three compounds of environmental interest determined at each laboratory at nominal injected weights of 20, 100, and 200 ng was found to be 18.9% for four of the five laboratories which participated in this work. These data demonstrate that similar response factors can be attained in routine GC/MS measurements when adequate quality control is maintained.
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  • 77
    ISSN: 0935-6304
    Keywords: Chromatography theory, GC and LC ; Statistical independence of various band broadening processes ; Variance addition rule for statistically independent processes ; Random walk description of longitudinal diffusion ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The total length-based second moment contribution from longitudinal sample diffusion in both phases on a column, σc,2D, is derived by adding individual partial differential contributions to a partial differential equation accounting for the longitudinal diffusion processes only. Although each diffusion-dispersed sample part is equilibrated between two phases, the resulting σc,2,D (= 2Dmtm + 2Dsts) can be interpreted as the sum of two independent contributions in accordance with the variance addition rule. (Dm and Ds are the mean diffusion coefficients and tmand ts the mean residence times of the sample in the mobile and stationary phases, respectively.) The same σc,2D expression is derived from the random walk model of Giddings by treating the diffusional process in each phase as statistically independent of the other processes. Under these conditions the broadening contribution from longitudinal diffusion in the mobile phase is shown to be independent of the velocity profile.
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    Journal of High Resolution Chromatography 5 (1982), S. 53-55 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, fused silica ; Thermal aging regeneration of fused silica capillaries ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 79
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary ; SD-E enrichment ; Pesticide residues ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple method is described for the quantitative determination of organochlorine pesticides and polychlorinated biphenyls (PCB's) in water at the sub-ppb level. A micro gas-phase extractor advantageously replaces other preconcentration and purification techniques. The extract is analyzed by capillary gas chromatography without further enrichment. The recovery at the ppb level was nearly 100% for organochlorine pesticides and more than 80% for PCB's. The complete procedure including sample preparation, steam distillation-extraction, and capillary gas chromatographic analysis is carried out in less than four hours.
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  • 80
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    Journal of High Resolution Chromatography 5 (1982), S. 360-363 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Microbore columns ; Reverse-phase mode ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure for packing reverse-phase microbore columns using moderate pressure is described. Columns packed from different manufacturer's tubing are compared with commercially available columns. A method for coupling the column to the injection valve is suggested. The effect of detector cell volume on overall efficiency of the system is also examined.
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  • 81
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    Journal of High Resolution Chromatography 5 (1982), S. 377-378 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Glass capillary columns ; Headspace analysis ; Alcohols in blood ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 82
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    Journal of High Resolution Chromatography 5 (1982), S. 381-381 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 83
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    Journal of High Resolution Chromatography 5 (1982), S. 692-693 
    ISSN: 0935-6304
    Keywords: Liquid-liquid partition chromatography, HPLC ; Liquid-liquid distribution ; Toluoylglycines, methylhippuric acids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    Journal of High Resolution Chromatography 5 (1982), S. 158-160 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Reversed-phase mode ; Good separation of preservatives from matrix and from each other at optimum pH and mobile phase ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
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    Journal of High Resolution Chromatography 5 (1982), S. 165-166 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Pulse flow reaction chromatography ; Two-detector system ; Reactions in a two-detector system ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 86
    ISSN: 0935-6304
    Keywords: Gas chromatogarphy ; Capillary columns ; Headspace analysis ; Both headspace and essential oil chromatograms required for evaluation of herbs ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: GC headspace analyses of various aromatizing herbs have been compared with those relating to the essential oils, obtained by steam distillation, of the same plants. In this way it was possible to establish the most significant differences between the composition of a herb flavor and that of its essential oil. In particular, we observed some very volatile compounds in the headspace samples which were absent from the essential oil; these components may make an important contribution to the herb flavor. The identification of these substances is still in progress.
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  • 87
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    Journal of High Resolution Chromatography 5 (1982), S. 285-290 
    ISSN: 0935-6304
    Keywords: Gas chromatography, capillary ; Column preparation ; Neutral and amino sugars, alditol acetates ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The development of improved high resolulation glass capillary columns for separating the alditol acetates of neutral and amino sugars is described. Different capillary column treatments were evaluated for their activity toward amino sugar derivatives and for their effect on the efficiency of the completed column. The simple two-step procedure of leaching with aqueous hydrochloric acid and dynamic coating with SP-2330 was found to produce efficient and inert columns.
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  • 88
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    Journal of High Resolution Chromatography 5 (1982), S. 321-321 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, fused silica ; Pyrolysis studies ; Cryofocusing device ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 89
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    Journal of High Resolution Chromatography 5 (1982), S. 349-354 
    ISSN: 0935-6304
    Keywords: Gas chromatography, capillary ; Persilylated, apolar columns ; Immobilized coatings ; Determination of column bleeding ; Re-silylation of fresh and used columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bleeding of apolar high temperature columns may well be the critical factor limiting their applicability for GC/MS-coupling, and for high temperature analyses. Therefore, a bleeding determination procedure has been designed as a basis for a systematic approach to the production of low-bleed columns. Re-silylation is a traditional method of reducing column bleeding. Increased efficiency of re-silylation becomes feasible with immoblized coatings. Experience gained so far shows that resilylation of immoblized coatings may indeed result in the expected strongly reduced bleed rates and in improved overall column quality. Re-silylation may also contribute to column washing by enhancing the solubility of adsorbed contaminants.
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  • 90
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    Journal of High Resolution Chromatography 5 (1982), S. 80-84 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass ; Triglycerides in cocoa butter, hazelnut oil ; Separation according to the number of unsaturated fatty acids (N.U.F.A.) ; Ozonolysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structure determination of triglycerides according to their number of unsaturated fatty acids (N.U.F.A.) is more easily achieved after ozonolysis of their mixtures (fats and oils) than by capillary gas chromatographic analysis of the mixture as such. Analyses performed before and after ozonolysis of cocoa buttel, hazelnut oil, and a mixture of both fats illustrate the potential of this approach to the structure elucidation of triglycerides by chromatographic techniques.
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  • 91
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    Journal of High Resolution Chromatography 5 (1982), S. 100-101 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; High performance thin-layer chromatography ; Lipid analysis ; Quantitative interpretation ; High-temperature transesterification by tetramethylammonium hydroxide ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 92
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    Journal of High Resolution Chromatography 5 (1982), S. 102-103 
    ISSN: 0935-6304
    Keywords: Micro HPLC ; Isotope separation ; Packed micro glass capillary ; Reversed phase mode ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
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    Journal of High Resolution Chromatography 5 (1982), S. 109-112 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 94
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    Journal of High Resolution Chromatography 5 (1982), S. 150-150 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 95
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    Journal of High Resolution Chromatography 5 (1982), S. 156-157 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary column ; Cold trapping ; Use of ABT concept in evaluating effect of trapping on peak ; shape ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 96
    ISSN: 0935-6304
    Keywords: Chromatography theory, GC and LC ; Revised “stage” model of Said ; Revised relaxation-time model of Giddings ; Statistically independent partial differential contributions ; Relation between HETP and true theoretical plate height ΔL ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass balance changes of Said's so-called “stage” model, based on the movement of the mobile phase with mean velocity ū (=L/tm), are synchronized by introduction of the relaxation time of Giddings, tr=1/(km+ks) where km and ks are the general overall mass rate constants for sample transfer to and from the stationary phase, respectively. This makes the “stage” length equal to the true theoretical plate height, ΔL, related to the classical HETP contribution due to non-equilibrium, H(α), according to the “discontinuous-ΔL” relation \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm H}_{{\rm (\alpha)}} {\rm =}\frac{{{\rm L\sigma}^{\rm 2} _{{\rm (\alpha)}}}}{{\overline {\rm t} _{{\rm ms}}^{\rm 2}}}{\rm = \Delta L}\frac{{\overline {\rm k}}}{{{\rm 1 + k}}} $$\end{document} Here k= (tms - tm)/tm is the central moment-based capacity ratio, L the column length, and σ2(α) the second moment contribution from the non-equilibrium only. Correct application of the relaxation-time model to chromatography requires that the real sample concentration in the stationary phase at a given position and time, Cs,l,t, is in a continuous equilibrium with the real sample concentration in the mobile phase, Cm,l+ΔL/2,t at that time displaced down the column by a distance \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{{\rm \Delta L}}}{{\rm 2}}{\rm = t}_{\rm r} \overline {\rm u} {\rm =}\frac{{\rm L}}{{k_{\rm m} \overline {\rm t} _{\rm m}}}\frac{{\overline {\rm k}}}{{{\rm 1 +}\overline {\rm k}}} $$\end{document} This leads to the classical HETP contribution \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm H}_{{\rm (\alpha)}} {\rm =}\frac{{{\rm 2L}}}{{k_{\rm m} \overline {\rm t} _{\rm m}}}\frac{{\overline {\rm k}}}{{{\rm (1 +}\overline {\rm k})^2}} $$\end{document} obtained from various other continuous models, which implies that ΔL is a good estimation of the true theoretical plate height.
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  • 97
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    Journal of High Resolution Chromatography 5 (1982), S. 163-164 
    ISSN: 0935-6304
    Keywords: High performance thin-layer chromatography, HPTLC ; HPTLC bonded phases ; 3-Aminopropyltriethoxysilane-treated plate ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 98
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    Journal of High Resolution Chromatography 5 (1982), S. 175-181 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary columns ; Discrimination factor non-vaporizing on-column/vaporizing splitless injection for underivatized steroids ; Quantitation feasible for most underivatized steroid hormones except corticosteroids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Recent developments in the preparation of capillary columns by persilanization of the glass surfaces have resulted in highly inactive, heat-stable columns. With this type of column certain steroid hormone classes can be analyzed without derivatization; these include the 17-keto steroids, 11-oxo compounds, estrogens, and progesterone metabolites. It has been found that good quantitative analysis calls for non-vaporizing, on-column injection, as normal vaporizing injection results in breakdown of thermolabile compounds such as estriol and 17-OH progesterone metabolites. The gas chromatographic method described was used to obtain urinary steroid profiles.
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  • 99
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    Journal of High Resolution Chromatography 5 (1982), S. 208-209 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Liquid chromatography ; Capillary glass ; Capillary columns with inside splitting of eluent ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 100
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    Journal of High Resolution Chromatography 5 (1982), S. 211-212 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary, glass ; On-column injection ; Elimination of discrimination ; Sliding sample inlet ; Cooling column system ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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