The Radicals in Cigarette Tar: Their Nature and Suggested Physiological Implications

The paramagnetism of cigarette tar is found to be associated with at least four different types of species. One of the types is responsible for over 80 percent of the total paramagnetism and has a signal intensity that is independent of temperature from 60 to 250 K. This non-Curie-Weiss temperature dependence indicates that the principal paramagnetic species in tar is not an organic monoradical (doublet) species but instead is a donor-acceptor excimer with a paramagnetic excited state and a diamagnetic ground state. Modeling experiments suggest that the excimer consists of quinone (Q) and hydroquinone (QH$_{2}$) molecules held in a tar matrix. Since such Q-QH$_{2}$ species are catalysts for the oxidation of hydrocarbons and are very active redox systems, this paramagnetic species may be implicated in the cocarcinogenic properties of tar. Alternatively, since semiquinone radicals are known to bind to DNA, the tar paramagnetic species may be directly involved in the carcinogenic properties of tar.