Free-Radical Chemistry of Cigarette Smoke and Its Toxicological Implications

Abstract

Cigarette smoke contains two very different populations of free radicals, one in the tar and one in the gas phase. The tar phase contains several relatively stable free radicals; we have identified the principal radical as a quinone/hydroquinone (Q/QH2) complex held in the tarry matrix. We suggest that this Q/QH2 polymer is an active redox system that is capable of reducing molecular oxygen to produce superoxide, eventually leading to hydrogen peroxide and hydroxyl radicals. In addition, we have shown that the principal radical in tar reacts with DNA in vitro, possibly by covalent binding.The gas phase of cigarette smoke contains small oxygen-and carbon-centered radicals that are much more reactive than are the tar-phase radicals. These gas-phase radicals do not arise in the flame, but rather are produced in a steady state by the oxidation of NO to NO2, which then reacts with reactive species in smoke such as isoprene. We suggest that these radicals and the metastable products derived from these radical reactions may be responsible for the inactivation of a,-proteinase inhibitor by fresh smoke.Cigarette smoke oxidizes thiols to disulfides; we suggest the active oxidants are NO and NO2. The effects of smoke on lipid peroxidation are complex, and this is discussed. We also discuss the toxicological implications for the radicals in smoke in terms of a number of radical-mediated disease processes, including emphysema and cancer.

Correlation of EPHX1, GSTP1, GSTM1, and GSTT1 genetic polymorphisms with antioxidative stress markers in chronic obstructive pulmonary disease

“…In COPD patients, alterations in several antioxidants have been found in blood [28] and our observations are in accordance with previous reports [17,18,[29][30][31][32].…”

Cigarette smokers develop structurally modified hemoglobin: a possible way of increasing oxidative stress

“…(Ambrose & Barua, 2004), which are capable of causing an increase in generation of various reactive species, specially reactive oxygen species (ROS). Therefore, by each puff one smoker is exposed to a free radical load by such oxidizing agents (Padmavathi et al, 2010) with an estimation of 10 15 free radicals per puff (Church & Pryor, 1985). Due to extreme reactivity, the ROS may react with many compounds in the neighborhood.…”

Increased Oxidative Stress Related To Using Smokeless Tobacco Maras Powder

“…Yine sigara da nitrik oksit, hidrokarbonlar, aldehidler, fenollar, kinon ve semikinon radikalleri gibi pek çok kimyasal maddeyi bünyesinde barındırmakta ve bu kimyasal maddeler direkt ya da indirekt olarak oksijen kaynaklı serbest radikal oluşumuna yol açmaktadır [11]. Serbest oksijen radikal (SOR) düzeyi de normalde vücudun antioksidan savunma sistemleri tarafından nötralize edilerek dengede tutulmaktadır.…”