Systematic comparison of data-processing options for kinetic-based single-component determinations of non-catalysts

Love, Michael D.; Pardue, Harry L.

doi:10.1016/0003-2670(94)00362-9

Cited by 16 publications

(1 citation statement)

References 57 publications

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“…Curve-fitting methods for multicomponent kinetic analysis are based on the preliminary postulation of a chemical model (hard-modeling methods), for instance, through the order and the stoichiometry of the reaction. The experimental data (a data vector or a data matrix) are then fitted to the proposed model, and the best set of parameters is obtained by using a least-squares optimization. − The Kalman filter procedure has been also widely used in the analysis of kinetic data, allowing the estimation of a set of optimized parameters that describe the system under the assumption of a certain kinetic model. − Depending on the model to be fitted, either linear or nonlinear (extended) Kalman filters can be used. The Kalman filter approach has been successfully applied to the simultaneous determination of several analytes .…”

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confidence: 99%

Multivariate Curve Resolution and Trilinear Decomposition Methods in the Analysis of Stopped-Flow Kinetic Data for Binary Amino Acid Mixtures

1997

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A stopped-flow method is proposed to carry out the kinetic development of the reaction between amino acids and 1,2-naphthoquinone-4-sulfonate by mixing analytes and reagent in a three-channel continuous-flow system. The process is monitored using a diode array spectrophotometer. Thus, every sample produces a data matrix built up from the spectra registered at regular steps of time. As the reaction is faster for secondary amino acids than for primary ones, it is possible to distinguish between the kinetic formation of their corresponding derivatives. The method is applied to the simultaneous determination of phenylalanine and proline by using second-order multivariate curve resolution. The derivatives of these two amino acids present some differences in both orders of measure, i.e., their spectra and kinetic profiles, which can be exploited advantageously to quantify one of the analytes in the presence of the other as interference, without including any information about this interference in the modeling of the system.

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Multivariate Curve Resolution and Trilinear Decomposition Methods in the Analysis of Stopped-Flow Kinetic Data for Binary Amino Acid Mixtures

1997

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Differential Rate Determinations

Pérez‐Bendito

2000

Encyclopedia of Analytical Chemistry

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Uncatalyzed Kinetic Determinations

Koupparis

2000

Encyclopedia of Analytical Chemistry

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Analytical procedures in which the measurement step (chemical, physical or physicochemical) is influenced by a transient (kinetic) process, can strictly be classified as kinetic method. Thus, the majority of modern analytical methods (continuous‐flow, time‐resolved fluorimetric and chromatographic methods, among others) are kinetic in nature. Nevertheless, the term “kinetic method”, for historical reasons, is incorrectly limited to methods based on direct or indirect measurements of the rate of a chemical reaction, which should be classified as “reaction‐rate methods”. Analytical methods based on signal measurements made under dynamic conditions compete in efficiency with static and equilibrium measurements. The growing development of kinetic methods is due to the need for quantification of microamounts of substances, increasing knowledge of reaction mechanisms, and breakthroughs in instrumentation and data handling and interpretation. The most popular classification of kinetic methods of analysis is based on the chemistry of reactions employed and distinguishes between catalytic (nonenzymatic, enzymatic and electrochemical), and noncatalytic methods. The latter are further categorized into those used to determine a single species or several components in mixtures (differential reaction‐rate methods). This article deals with kinetic methods for the determination of single noncatalytic species. Although the majority of kinetic‐based determinations depend on catalytic systems, some analytical applications using the rate of uncatalyzed reactions are of analytical interest, mainly those involving organic chemical species. Advances in instrumentation: (1) improved signal detection, (2) resolving of problems arising from time measurements especially in fast processes, and (3) availability of automated mixing devices and data processing (error‐compensated methods, curve‐fitting and predictive approaches) establish noncatalytic methods as powerful alternatives to equilibrium methods. The main field of application of noncatalytic reactions is organic analysis, unlike catalytic reactions where a metal ion usually acts as the catalyst.

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Systematic comparison of data-processing options for kinetic-based single-component determinations of non-catalysts

Cited by 16 publications

References 57 publications

Multivariate Curve Resolution and Trilinear Decomposition Methods in the Analysis of Stopped-Flow Kinetic Data for Binary Amino Acid Mixtures

Multivariate Curve Resolution and Trilinear Decomposition Methods in the Analysis of Stopped-Flow Kinetic Data for Binary Amino Acid Mixtures

Differential Rate Determinations

Uncatalyzed Kinetic Determinations

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