Determination of Rate Constants for Complex Kinetics Models

A direct-indirect procedure for estimation of kinetic parameters

“…It may be readily verified that the above algorithm is the natural generalization of the conventional discrete-time least squares method [4]. In reaction kinetics this approach was first used by Himmelblau et al [2] for cases in which rate eqns (1) are linear in the parameters. Since spline interpolation follows by analytic integration is much faster than the numerical integration of the differential equations, the superiority of the direct method over the indirect one is obvious in terms of numerical efficiency.…”

“…Since spline interpolation follows by analytic integration is much faster than the numerical integration of the differential equations, the superiority of the direct method over the indirect one is obvious in terms of numerical efficiency. As will be shown, the direct approach is less sensitive to the first guess k. In particular for linear systems, no initial estimates are required [2].…”

Diverse metabolic model parameters generate similar methionine cycle dynamics

“…Global optimization methods such as simulated annealing (Eftaxias et al, 2002;Kirkpatrick et al, 1983), scatter search (RodriguezFernandez et al, 2006b), evolutionary computation (Fogel, 2000;Goldberg, 1989;Moles et al, 2003;Tsuchiya and Ross, 2001), and variants (Rodriguez-Fernandez et al, 2006a), are generally more reliable in these situations. The application of global methods has been reported in a few studies modeling metabolic networks (Himmelblau et al, 1967;Moles et al, 2003;Polisetty et al, 2006).…”

Parameterization of complex reaction systems: Model fitting vs. fundamental kinetics

“…Computer simulation has found increasing application in both the chemical plant and the laboratory for the description of complex reaction and transport systems (Himmelblau et al, 1967(Himmelblau et al, , 1968. In the former case it is generally recognized that the rate equations and parameters used to describe the kinetics of the reactions represent a gross oversimplification of the chemistry and merely provide a convenient way of reproducing numerically the observed behavior of the process.…”