| Abstract: | A model system for cytochrome P-450 comprised of hemin, thiosalicylic acid, and solvent (acetone and water), oxidized cyclohemne and n-hexane at pH 2.7. Oxidation of cyclohexane yielded more cyclohexanol than cyclohexanone under mild reaction conditions, whereas the oxidation of n-hexane generated more 3- and 2-hexanones than 3- and 2-hemnols. Oxygen was a limiting factor in the reaction, and increased oxygen pressures increased the ratio of cyclohexanone to cyclohexanol formed. Lag time for product formation decreased in a linear fashion with an increase in temperature. In addition, cyclohexanone decreased relative to cyclohexanol as the temperature was increased. Antioxidants increased the lag time for product formation, but had little effect on the final quantity or ratios of the oxidative products generated. 1,3 Diphenylisobenzafiran had no effect on the lag time, whereas Tiron and catechol increased the lag time. In contrast to aliphatic thiols, aromatic thiols were capable of driving the oxidative reaction. The model hemin system was approximately 6% as active as natural cytochrome P-450. Hemin immobilized on glass beads effectively catalyzed the oxidation of cyclohexane. |
