Stepwise kinetics definition

It is essential that the functionals are positively defined in all of the considered examples to imply stability of the stationary state in the relevant stepwise processes. Strongly nonlinear kinetic schemes need special procedures for analyzing the stability. While doing so, it is easy to demonstrate that the positive definition of functional is indeed the sufficient condition of stability of the chemical process (in the case, naturally, when these functionals exist). 

As demonstrated in the definition of Mi, M2 and M3, kinetic parameters preset as constants for kinetic analysis of GST reaction curve should have strong covariance. Except Kiq as an unknown kinetic parameter for optimization, other kinetic parameters are those reported (Kunze, 1997 Pabst, et al, 1974). To optimize Kiq, two criteria are used. The first is the consistency of predicted Am at a series of GSH concentrations using data of 6.0-min reaction with that by the equilibrium method after 40 min reaction (GST activity is optimized to complete the reaction within 40 min). The second is the resistance of Vm to reasonable changes in data ranges for analyses. After stepwise optimization, Kiq is fixed at 4.0 pmol/L Am predicted for GSH from 5.0 pmol/L to 50 pmol/L is consistent with that by the equilibrium method (Zhao, L.N., et al. 2006) the estimation of Vm is resistant to changes of data ranges (Fig. 5). Therefore, Kiq is optimized and fixed as a constant at 4.0 pmol/L. 

In this review, the phrase PCET is used to comprise kinetically gated and coupled stepwise mechanisms as well as concerted PCET reactions. The reasons for this broad definition are rooted in the experimental challenge of... 

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