Interactive self-modelling of chemical reaction systems using multivariate data analysis

Sans, D.; Nomen, R.; Sempere, J.

doi:10.1016/s0098-1354(97)87573-4

Cited by 2 publications

(2 citation statements)

References 12 publications

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“…The absorbance is proportional to the concentration of species according to the Lambert−Beer law. Interpretation of these principal components requires independently derived chemical, spectral, and kinetic data, only some of which are available. ,, …”

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confidence: 99%

Principal Component Analysis of Dynamical Features in the Peroxidase−Oxidase Reaction

Kirkor

Scheeline

Hauser³

2000

Anal. Chem.

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Inherent variance due to oscillations in the peroxidase-oxidase (PO) reaction was studied using principal component analysis (PCA). The substrates were oxygen and reduced nicotinamide adenine dinucleotide (NADH). Horseradish peroxidase (HRP) catalyzed the reaction. The concentration of a cofactor, methylene blue (MB), was varied, and 2,4-dichlorophenol was kept constant. Increase in the NADH influx was used to change the reaction dynamics from periodic to chaotic. The reaction space was abstracted to the most significant, mutually independent, pairs of absorption and kinetic basis vectors (principal components). Typically, two significant principal components were extracted from the periodic time series and three from the chaotic data. The PCA models accounted for 70-97% of experimental variance. The greatest fraction of the total variance was accounted for in experiments exhibiting periodic dynamics and less than 25 nM MB. More MB induced an increased contribution of NADH to the PO oscillator variance, as did increased NADH influx. A simulated absorption time series, computed from a mass-action model of the chemistry, was analyzed by PCA as well. The comparison of simulation with experiment indicates that the chemical model renders the time series for HRP oxidation forms with fidelity, but incompletely represents NADH chemistry and other salient processes underlying the observed dynamics.

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confidence: 99%

Principal Component Analysis of Dynamical Features in the Peroxidase−Oxidase Reaction

Kirkor

Scheeline

Hauser³

2000

Anal. Chem.

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“…The collection of the spectra of these samples is usually difficult and time-consuming. Calibration free monitoring − is appealing, but these methods are not easy to apply since they often give no unique solution and several constraints are required.…”

Section: Theorymentioning

confidence: 99%

Tackling Calibration Problems of Spectroscopic Analysis in High-Throughput Experimentation

et al. 2005

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High-throughput experimentation and screening methods are changing work flows and creating new possibilities in biochemistry, organometallic chemistry, and catalysis. However, many high-throughput systems rely on off-line chromatography methods that shift the bottleneck to the analysis stage. On-line or at-line spectroscopic analysis is an attractive alternative. It is fast, noninvasive, and nondestructive and requires no sample handling. The disadvantage is that spectroscopic calibration is time-consuming and complex. Ideally, the calibration model should give reliable predictions while keeping the number of calibration samples to a minimum. In this paper, we employ the net analyte signal approach to build a calibration model for Fourier transform near-infrared measurements, using a minimum number of calibration samples based on blank samples. This approach fits very well to high-throughput setups. With this approach, we can reduce the number of calibration samples to the number of chemical components in the system. Thus, the question is no longer how many but which type of calibration samples should one include in the model to obtain reliable predictions. Various calibration models are tested using Monte Carlo simulations, and the results are compared with experimental data for palladium-catalyzed Heck cross-coupling.

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Interactive self-modelling of chemical reaction systems using multivariate data analysis

Cited by 2 publications

References 12 publications

Principal Component Analysis of Dynamical Features in the Peroxidase−Oxidase Reaction

Principal Component Analysis of Dynamical Features in the Peroxidase−Oxidase Reaction

Tackling Calibration Problems of Spectroscopic Analysis in High-Throughput Experimentation

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