Superoxide metal induction

The earlier references, which state that this powerful oxidant is stable when pure, but explosive when formed as a layer on metallic potassium [1,2], are not wholly correct [3], because the superoxide is manufactured uneventfully by spraying the molten metal into air to effect oxidation [4], Previous incidents appear to have involved the explosive oxidation of unsuspected traces of mineral oil or solvents [3]. However, mixtures of the superoxide with liquid or solid potassium-sodimn alloys will ignite spontaneously after an induction period of 18 min, but combustion while violent is not explosive [3], The additional presence of water (which reduces the induction period) or hydrocarbon contaminant did produce explosion hazards under various circumstances [5], Contact of liquid potassium with the superoxide gives no obvious reaction below 117°C and a controlled reaction between 117 and 177°C, but an explosive reaction occurs above 177°C. Heating at 100°C/min from IT caused explosion at 208°C [6],... 

Many free-radical scavengers (including dithiols and dithiocarbamates) have potential therapeutic usefulness as radioprotective agents. Copper complexes are known to be scavenging agents for the superoxide radical, which is believed to play a role in the induction of radiation damage. The toxic effects of superoxide are believed to lie in its ability to reduce metal ions, for example Cu(II) to Cu(I),... 

However, these indirect effects of nitric oxide derived products are far more prevalent under pathological conditions such as inflammation, where the production of both NO and by the professional phagocytic cell NADPH oxidase enzyme, and induction of iNOS yields the potent cytotoxic species peroxynitrite. Whilst nitric oxide will react with metal centres (as discussed above) at a rate of 5x 10 M" s and the superoxide anion can be dismutated by SOD at a rate of 2.3x10 M s the combined reaction below (Eq. 9), proceeds at a rate faster than either of these individual reactions ... 

Especially transition metal icMis play an important role in the induction of oxidative DNA damage. While neither superoxide anions nor hydrogen peroxide are able to react with DNA directly, in the presence of transition metals like iron, copper, cobalt, or nickel they are converted into highly reactive hydroxyl radicals by Fenton-type reactions. In contrast, cadmium ions are not able to participate in redox reactions under physiological conditions, yet, oxidative stress and the interference with cellular redox regulation may be of high relevance in cadmium-induced carcinogenicity. Increased levels of ROS due to cadmium exposure have been observed both in vitro and in vivo [31]. Different cadmium compounds have been shown to induce DNA strand breaks and oxidative DNA base modifications in... 

The induction of DNA strand breaks and chromosomal aberrations by cadmium in mammalian cells was suppressed by antioxidants and antioxidant enzymes, indicating the involvement of ROS [34—36], Since the extent of ROS and damage to cellular macromolecules depends on the equilibrium between their generation and detoxification or repair, respectively, the occurrence of oxidative DNA damage is assumed to be due to an inhibition of the antioxidant defense by cadmium, such as the antioxidant enzymes catalase, superoxide dismutase, glutathione reductase, and glutathione peroxidase. One other mechanism proposed consists in the displacements of redox active metal ions, e.g., Fe ", for example in metallothionein, giving rise to Fenton reactions [35-37]. 

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