Reactive oxygen species reactions

The trypanocidal action of nifurtimox derives from its ability to undergo activation by partial reduction to nitro radical anions. Transfer of electrons from the activated drug then forms superoxide radical anions and other reactive oxygen species. Reaction of free radicals results in lipid peroxidation and membrane injury, enzyme inactivation, and DNA damage. Benznidazole also requires a one-electron transfer that generates nitro anion radicals, leading to cellular damage that kills the parasites. 

Lipid peroxidation (see Fig. 17.2) is a chain reaction that can be attacked in many ways. The chain reaction can be inhibited by use of radical scavengers (chain termination). Initiation of the chain reaction can be blocked by either inhibiting synthesis. of reactive oxygen species (ROS) or by use of antioxidant enzymes like superoxide dismutase (SOD), complexes of SOD and catalase. Finally, agents that chelate iron can remove free iron and thus reduce Flaber-Weiss-mediated iron/oxygen injury. 

Spin trapping methods were also used to show that when carotenoid-P-cyclodextrin 1 1 inclusion complex is formed (Polyakov et al. 2004), cyclodextrin does not prevent the reaction of carotenoids with Fe3+ ions but does reduce their scavenging rate toward OOH radicals. This implies that different sites of the carotenoid interact with free radicals and the Fe3+ ions. Presumably, the OOH radical attacks only the cyclohexene ring of the carotenoid. This indicates that the torus-shaped cyclodextrins, Scheme 9.6, protects the incorporated carotenoids from reactive oxygen species. Since cyclodextrins are widely used as carriers and stabilizers of dietary carotenoids, this demonstrates a mechanism for their safe delivery to the cell membrane before reaction with oxygen species occurs. 

Antioxidant and Photoprotection Functions and Reactions Involving Singlet Oxygen and Reactive Oxygen Species... 

Different mechanisms to explain the disinfection ability of photocatalysts have been proposed [136]. One of the first studies of Escherichia coli inactivation by photocatalytic Ti02 action suggested the lipid peroxidation reaction as the mechanism of bacterial death [137]. A recent study indicated that both degradation of formaldehyde and inactivation of E. coli depended on the amount of reactive oxygen species formed under irradiation [138]. The action with which viruses and bacteria are inactivated by Ti02 photocatalysts seems to involve various species, namely free hydroxyl radicals in the bulk solution for the former and free and surface-bound hydroxyl radicals and other oxygen reactive species for the latter [139]. Different factors were taken into account in a study of E. coli inactivation in addition to the presence of the photocatalyst treatment with H202, which enhanced the inactivation... 

Oxidation reactions are the most studied processes owing to the well-known ability of illuminated Ti02 in water to produce reactive oxygen species. In this context, heterogeneous photocatalysis could contribute to the replacement of hazardous compounds such as KMn04 and K2Cr20 [13]. 

That the oxidative burst is directly involved in the chemical defense of these algae is clear. This reaction can be inhibited by diphenyleneiodonium, a suicide inhibitor of NADPH-oxidase which suppresses both the production of reactive oxygen species and the natural resistance to epiphytic bacteria. In addition a role in the defense against endophytes was indicated, since pre-treatment with oligomeric guluronates resulted in decreased infection of L. digitata with the pathogen Laminariocolax tomentosoides [141]. 

Figure 28.19 The cleavage reaction of FeBABE involves a catalytic process using peroxide and ascorbate to form reactive oxygen species. Any protein structure in the immediate vicinity of the FeBABE label on the bait protein will undergo peptide bond cleavage.

The formation of hydroxyl or hydroxyl-like radicals in the reaction of ferrous ions with hydrogen peroxide (the Fenton reaction) is usually considered as a main mechanism of free radical damage. However, Qian and Buettner [172] have recently proposed that at high [02]/ [H202] ratios the formation of reactive oxygen species such as perferryl ion at the oxidation of ferrous ions by dioxygen (Reaction 46) may compete with the Fenton reaction (2) ... 

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