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When either the reactant (O) or product (R) is adsorbed (but not both), one expects to observe a postpeak or prepeak, respectively (at potentials more negative or positive than the diffusion-controlled peak). 5 Potential (V) FIGURE 2-9 Repetitive cyclic voltammograms illustrating the continuous growth of polyaniline on a platinum surface. of the reactant and product (11-14). The rates of fast adsorption processes can be characterized by high-speed cyclic voltammetry at ultramicroelectrodes (15).
These repetitive scanning in-vivo experiments generate large quantities of data that are best represented as three-dimensional (potential, current, time) color contour images (17). For example, the temporal release of dopamine following electrical stimulation is evidenced from the rapid increase in color around its peak potential. The ultrafast scanning also eliminates interferences from adsorption processes and chemical reactions that are coupled to the primary oxidation reaction of catecholamine neurotransmitters (18): O He + 2H + 2e (2-15) For more detailed information on the theory of cyclic voltammetry, and the interpretation of cyclic voltammograms, see references (1,7,19,20).
The extraction of such information commonly requires background subtraction to correct for the large charging current contribution associated with ultrafast scan rates. A special case of the EC mechanism is the catalytic regeneration of O during the chemical step: O + ne~ ^ R (2-8) R+A ^ O (2-9) An example of such a catalytic EC process is the oxidation of dopamine in the presence of ascorbic acid (4). The dopamine quinone formed in the redox step is reduced back to dopamine by the ascorbate ion.