The solid state physical theory of cytochrome oxidase kinetics. Inhibition of second order rate constant,and second to first order kinetic shift with increasing oxygen,predicted from electron injection and trapping

Conduction of electrons through the solid protein cytochrome oxidase particle in accord with Ohm's law, driven by the difference in electrode potentials of two substrates which exchange electrons with the two sides of the enzyme particle, was previously shown to explain the inhibitory effect of cytochromec on the first order rate constant, and to predict the low semiconduction activation energy of dried cytochrome oxidase. If the solid conduction path in the cytochrome oxidase particle shows electron injection from sites of electron exchange with substrate, and shows trapping of conduction electrons by reversible O₂ complexes, then one may also predict that the first order kinetics observed as high O₂ concentrations will change to second order kinetics at lower O₂ concentrations, as observed by Gibson and Wharton. One may also predict quantitatively the inhibitory effect of increasing O₂ concentrations on the second order rate constant as observed by Gibson and Wharton. The same concept of electron trapping by O₂ complexes provides a possible reason for the unusually low semiconduction activation energy of cytochrome oxidase.