Sources of Oxidants

Thermally induced homolytic decomposition of peroxides and hydroperoxides to free radicals (eqs. 2—4) increases the rate of oxidation. Decomposition to nonradical species removes hydroperoxides as potential sources of oxidation initiators. Most peroxide decomposers are derived from divalent sulfur and trivalent phosphoms. 

So the ultimate source of oxidant is O2, although the actual species involved in the oxidation is not O2. 

As mentioned previously, in the AMD retina iron metabolism is compromised (He et al., 2007 Wong et al., 2007). Thus, it is of interest to determine the effects of potential antioxidants in the presence of iron. In an in vitro study of ARPE-19 cells, addition of a lipophilic iron complex led to about a ninefold increase in the photosensitized yield of 7a,(3-cholesterol hydroperoxides (Wrona et al., 2004). In the presence of the iron, ascorbate exerted pro-oxidant effects, while the effects of a-tocopherol, zeaxanthin, or their combination were still protective (Wrona et al., 2004). Thus, it appears that the effects of potential antioxidants are strongly dependent on the sources of oxidative damage. The same antioxidant may be protective under certain conditions and exert deleterious effects when the conditions are changed. Therefore a detailed understanding of the sources of the oxidative damage is required in order to design an adequate antioxidant mixture. 

It is proposed that 32 reacts from its nn excited state by the nitro-to-nitrite (33) inversion followed by nitrite homolysis, when the naphthoxy radical must diffuse away from the cages to obtain the dimerization intermediate 35. However, the source of oxidizing agents is not identified. In comparison, o-nitro-ferf-butylbenzenes 37 are excited to undergo intramolecular H-atom transfer and cyclization to give indol-IV-oxides 40 (equation 34)38. The discrepancy may arise from the nature of the excited state, e.g. that of 37 may react from its njr state. 

Air-blown gasifiers benefit from a low-cost (free) source of oxidant, but produce a gasifier product gas that has a very low heating value (approximately 5MJ/m3 for air-blown gasification of coal, compared to 38MJ/m3 for a typical natural gas) and which is too dilute to use for liquid fuel synthesis. 

Recently, we also documented that PS oxidation during oxidant-induced apoptosis occurred within the plasma membrane, the largest source of oxidized PS compared to other cellular organells (Kawai et al, 2000). 

Insects. See Macroarthropods Internal-combustion engine, as source of oxidants, 14... 

Excipients play a key role in oxidation, either as a primary source of oxidants, trace amounts of metals, or other contaminants. Auto-oxidation of diethylstilbes-terol to the peroxide and conjugated quinone degradation products was attributable to the presence of colloidal silicon dioxide, used as a glidant in solid oral dosage forms [48]. This was ascribed to the fact that silicon dioxide can act as a Lewis acid (an election acceptor or oxidising agent), under anhydrous conditions. 

The inabihty of the neurons to eliminate the oxidative load may result in a self-perpetuating cycle of oxidative damage that ultimately leads to neuronal death. One source of oxidative stress may be dopamine metabolism (Fig. 31.2). The excessive excitatory activity in the substantia nigra created by the loss of dopamine actions within the striatum could lead to excitotoxicity that is mediated by glutamate. 

There are also significant natural sources of oxides of nitrogen, in particular nitric oxide, which is produced by biomass burning as well as by soils where nitrification, denitrification, and the decomposition of nitrite (N02) contribute to NO production. Figure 2.4b, for example, shows the relative emission rates for biogenically produced NO in the United States in 1990 (EPA, 1995). 

It is now known that the quantum yield of (9b) is less than 1% (Greenblatt and Ravishankara, 1990). However, NzO is still the major source of oxides of nitrogen in the stratosphere (McElroy and McConnell, 1971) via its minor (compared to loss by photolysis) reaction with electronically excited oxygen atoms,... 

Given that the source of oxidants for S02 in both the gas and liquid phases is the VOC-NO chemistiy discussed earlier and that a major contributor to acid deposition is nitric acid, it is clear that one cannot treat acid deposition and photochemical oxidant formation as separate phenomena. Rather, they are very closely intertwined and should be considered as a whole in developing cost-effective control strategies for both. For a representative description of this interaction, see the modeling study of Gao et al. (1996). 

Cigarette smoking is a major risk factor for coronary disease. It is associated with reduced levels of HDL, impairment of cholesterol retrieval, cytotoxic effects on the endothelium, increased oxidation of lipoproteins, and stimulation of thrombogenesis. Diabetes, also a major risk factor, is another source of oxidative stress. 

In practice, the required ratio can be different from theoretical, as quite often additional bleach is required to provide HOC1 as an oxidant for algal slimes and other forms of chlorine demand. Also, it is necessary to have a permanent source of oxidant available to effect the promotion of HOBr. However, not all the available bromine generated is lost by biocidal reaction or by (limited) volatility. There is, in fact, some degree of recycling of the bromide ion (Br ) back into HOBr, so monitoring of bromine plus the combined free and total chlorine is necessary to strike the correct halogen balance. 

Y H2FuelSupply=0.70 Ymole fraction of hydrogen in raw source of fuel Y O2CathodeSupply=0.21 tmole fraction of oxygen in raw source of oxidant Pop=101000.0 %Pa—operating pressure... 

Oxidation. The side chains of cysteine (Cys), histidine (His), methionine (Met), tryptophan (Trp), and tyrosine (Tyr) residues are susceptible to oxidation. Oxidation can result in loss of protein activity. Met is the most reactive residue, oxidizing even with atmospheric oxygen to form Met-sulfoxide, which is frequently observed in proteins (Fig. 135). Additional sources of oxidation include oxidizing agents (peroxides in excipients), metal-catalyzed oxidation and photo-oxidation. Oxidation can be detected... 

The definition of an antioxidant suggests a functional assay of antioxidants by measuring inhibition of appropriate (easy to study) oxidation reactions. Such assays can be called inhibition assays for antioxidants (Fig. 2). Various oxidants are used in TAC assays. In many cases, thermal decomposition of 2,2 -azobis (2-amidopropane) (ABAP) is the source of oxidizing radicals. ABAP undergoes temperature-dependent homolysis. The primary radicals produced by thermal decomposition of the initiator react with oxygen to produce peroxyl and alkoxyl radicals, which are oxidizing species in the system (Fig. 3). The amount of free radicals formed in an aqueous medium by decomposition of ABAP at pH 7.4 and at 37°C equals 1.36 x 10-6 [ABAP] x t, where t is time in seconds and [ABAP] is in mol L-1 (N8). 

Therefore, this incomplete reduction may lead to redox cycling, and the presence of nitrated proteins in the cell may be a source of oxidative stress (K25). 

F19. Fu, S., Fu, M. X., Baynes, J. W., Thorpe, S. R., and Dean, R. T., Presence of dopa and amino acid hydroperoxides in proteins modified with advanced glycation end products (AGEs) Amino acid oxidation products as a possible source of oxidative stress induced by AGE proteins. Biochem. J. 330, 233-239 (1998). 

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