Exotic Kinetic Phenomena

A number of autoxidation reactions exhibit exotic kinetic phenomena under specific experimental conditions. One of the most widely studied systems is the peroxidase-oxidase (PO) oscillator which is the only enzyme reaction showing oscillation in vitro in homogeneous stirred solution. The net reaction is the oxidation of nicotinamide adenine dinucleotide (NADH), a biologically vital coenzyme, by dioxygen in a horseradish peroxidase enzyme (HRP) catalyzed process  

Since the first report of oscillation in 1965 (159), a variety of other nonlinear kinetic phenomena have been observed in this reaction, such as bi-stability, bi-rhythmicity, complex oscillations, quasi-periodicity, stochastic resonance, period-adding and period-doubling to chaos. Recently, the details and sub-systems of the PO reaction were surveyed and a critical assessment of earlier experiments was given by Scheeline and co-workers (160). This reaction is beyond the scope of this chapter and therefore, the mechanistic details will not be discussed here. Nevertheless, it is worthwhile to mention that many studies were designed to explore non-linear autoxidation phenomena in less complicated systems with an ultimate goal of understanding the PO reaction better. 

The main features of the copper catalyzed autoxidation of ascorbic acid were summarized in detail in Section III. Recently, Strizhak and coworkers demonstrated that in a continuously stirred tank reactor (CSTR) as well as in a batch reactor, the reaction shows various non-linear phenomena, such as bi-stability, oscillations and stochastic resonance (161). The results from the batch experiments can be suitably illustrated with a two-dimensional parameter diagram shown in Pig. 5. 

At high [Cu(II)] and low [H2A] initial concentrations, the Pt electrode potential, used to follow the chemical process, increased monotonously. When both species were present at high initial concentrations, a monotonous decrease was observed. Various non-monotonic transient regimes were found at approximate initial concentrations of [Cu(II)] 10-4 M and [H2A] 10-4 M. Thus, the batch experiments properly illustrate that the system is sensitive to variations of the initial concentrations of ascorbic acid and copper(II) ion, and the observations can be indicative of a transient bi-stability. 

The experiments were performed at a constant inflow concentration of ascorbic acid ([H2A]) in the CSTR. Oscillations were found by changing the flow rate and the inflow concentration of the copper(II) ion systematically. At constant Cu(II) inflow concentration, the electrode potential measured on the Pt electrode showed hysteresis between two stable steady-states when first the flow-rate was increased, and then decreased to its original starting value. The results of the CSTR experiments were summarized in a phase diagram (Fig. 6). 

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