Reduction of Chemical Reaction Networks Using Quasi-Integrals

We present a numerical method to identify possible candidates of quasi stationary manifolds in complex reaction networks governed by systems of ordinary differential equations. Inspired by singular perturbation theory we examine the ratios of certain components of the reaction rate vector. Those ratios that rapidly approach an almost constant value define a slow manifold for the original flow in terms of quasi integrals, i.e. functions that are almost constant along the trajectories. The dimensionality of the original system is thus effectively reduced without relying on a priori knowledge of the different time scales in the system. We also demonstrate the relation of our approach to singular perturbation theory which, in its simplest form, is just the wellknown quasi-steady-state approximation. In two case studies, we apply our method to oscillatory chemical systems: the 6-dimensional hemin -- hydrogen peroxide -- sulfite pH -- oscillator and a 10-dimensional mechanistic model for the peroxidase - oxidase (PO) reaction system. We conjecture that the presented method is especially suited for a straight forward reduction of higher dimensional dynamical systems where analytical methods fail to identify the different time scales associated with the slow invariant manifolds present in the system. Copyright © 2013 American Chemical Society [accessed 2013 August 21st