The relationship between ionization potential and horseradish peroxidase/hydrogen peroxide-catalyzed binding of aromatic hydrocarbons to DNA.

The ionization potentials (IP) of 91 alternant polycyclic aromatic hydrocarbons (PAH) were determined from the absorption maximum of the charge-transfer complex of each hydrocarbon and chloranil in chloroform. The extent of horseradish peroxidase (HRP)-catalyzed binding to DNA of 14 hydrocarbons of varying IP was measured. Only hydrocarbons with IP less than approx. 7.35 eV were significantly bound to DNA. These results provide further evidence that HRP-mediated binding of PAH to DNA occurs by one-electron oxidation and indicate that hydrocarbons must have IP less than approx. 7.35 eV to be activated by one-electron oxidation. Thus, determination of IP and HRP-catalyzed binding to DNA can offer some guidelines for selecting aromatic hydrocarbons which might undergo carcinogenic activation by this mechanism.