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Reactions spin trapping

Nitroso compounds, nitrones, and other diamagnetic molecules are used as spin traps. Capturing radicals prodnced in the reaction, spin traps form the so-called spin adducts—stable nitroxyl radicals easily detectable by ESR spectroscopy. In other words, the progress of the reaction can easily be followed by an increasing intensity of the spin-adduct signal. By and large, the method of traps reveals radicals by the disappearance (or appearance) of the ESR signal. [Pg.227]

ESR studies on the initial free radicals were carried out by using MNP(2-methyl-2-nitrosopropane) or DMPO (5,5-dimethylpyrroline N-oxide) as the spin-trapping agent. The reactions are shown as ... [Pg.232]

Various oligomers formed by Diels-Alder/ene reactions are observed.333 334 For S-MA11 polymerization Sato et ci//31 used spin trapping to identify the initialing species. On the other hand, in the case of S-AN copolymerization, Ihe... [Pg.110]

In spin trapping, radicals are trapped by reaction with a diamagnetic molecule to give a radical product.476 This feature (i.e. that the free spin is retained in the trapped product) distinguishes it from the other trapping methods. The technique involves EPR detection of the relatively stable radicals which result front the trapping of the more transient radicals. No product isolation or separation is required. The use of the technique in studies of polymerization is covered in reviews by Kamachi477 and Yamada ft a/.478... [Pg.134]

The application of RPR in the detection and quantification of species formed by spin-trapping the products of radical-monomer reactions is described in Section 3.5.2.1, The application of time-resolved F.PR spectroscopy to study intermolecular radical-alkene reactions in solution is mentioned in Section 3.5.1. [Pg.143]

Many nitrones and nitroso-compounds have been exploited as spin traps in elucidating radical reaction mechanisms by EPR spectroscopy (Section 3.5.2.1). The initial adducts are nitroxides which can trap further radicals (Scheme 5.17). [Pg.272]

In related work, the reactions of hydrogen peroxide with iron(II) complexes, including Feu(edta), were examined.3 Some experiments were carried out with added 5.5"-dimethyl-1-pyrroline-N-oxide (DMPO) as a trapping reagent fa so-called spin trap) for HO. These experiments were done to learn whether HO was truly as free as it is when generated photochemically. The hydroxyl radical adduct was indeed detected. but for some (not all) iron complexes evidence was obtained for an additional oxidizing intermediate, presumably an oxo-iron complex. [Pg.102]

The reaction of OH radicals with dimethyl sulfoxide in aqueous solution was studied already in 1964 by Norman and coworkers37 38. They used the system T1m-H202 to produce OH radicals and using ESR/rapid mixing techniques they were able to demonstrate elimination of a methyl radical during the OH induced oxidation. Further studies showed the formation of sulfmic radicals in this reaction either directly or by spin trapping experiments39-44. [Pg.899]

It is unfortunate that typical concentrations of free-radical species present in biological systems are only at the limit of e.s.r. detection sensitivity and, of course, there are major technical difficulties in studying whole animals in this manner. Therefore, the most successful e.s.r. experiments have adopted the approach of spin trapping in which very reactive and thus transient radical species are converted to long-lived adducts via reaction with a trap such as a nitrone, e.g. Equation 1.1 ... [Pg.2]

Oxidation of the fatty acids in an LDL particle shares many of the characteristics associated with lipid peroxidation in other biological or chemical systems. Once initiated peroxyl radicals are formed and this results in the oxidation of a-tocopherol to give the a-tocopheroyl radical (Kalyanaraman etal., 1990). This can be demonstrated by e.s.r. techniques that allow the direct observation of stable radicals such as the a-tocopheroyl radical. After the a-tocopheryl radical is consumed, lipid-derived peroxyl radicals can be detected after reaction with spin traps (Kalyanaraman etal., 1990, 1991). [Pg.30]

Despite their short half-lives, it is possible to detect free radicals in biological tissues by the addition of nonradicals such as nitrones or nitroso compounds, which act as spin traps by forming relatively stable free radicals on reaction with the endogenous radical species. Utilizing the technique of electron spin resonance (e.s.r.) spectroscopy, we have demonstrated ROM generation by human rheumatoid synovium when subjected to cycles of hypoxia/normoxia in vitro. Using 3,5-dibromo-4-nitroso-benzenesulphonate (DBNBS) as a spin trap, a... [Pg.100]

Historically, spin traps have been used as an analytical tool to determine the nature of free radicals being generated in reactions (Janzen, 1971). By design, they react with free radicals to form a stable radical product. They... [Pg.270]

The presence of /3-hydrogen in the nitroxide radical may lead to disproportionation reactions. In spin-trapping experiments, N-t-butyl-a-phenyl nitrone yields rather unstable spin adducts. This type of radical can be stabilized by coordination to Nin. The Ni11 complex with N-oxy-A-r-butyl-(2-pyridyl)phenylmethanamine (923) reveals a distorted octahedral geometry with antiferromagnetic interactions between the unpaired electrons of the metal ion and the radical spins.00... [Pg.480]

Spin trapping EPR technique and UV-Vis spectroscopy have been used (Polyakov et al. 2001b) to determine the relative rates of reaction of carotenoids with OOH radicals formed by the Fenton reaction in organic solvents. The Fe3+ species generated via the Fenton reaction... [Pg.165]

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. [Pg.167]

Spin traps which scavenge a reactive radical to give a more persistent radical may be used to detect the intermediacy of such transient radicals in sorting out a reaction mechanism.39... [Pg.18]

Electron transfer, in thermal and photochemical activation of electron donor-acceptor complexes in organic and organometallic reactions, 29,185 Electron-transfer, single, and nucleophilic substitution, 26,1 Electron-transfer, spin trapping and, 31,91 Electron-transfer paradigm for organic reactivity, 35, 193... [Pg.337]

Thus, superoxide itself is obviously too inert to be a direct initiator of lipid peroxidation. However, it may be converted into some reactive species in superoxide-dependent oxidative processes. It has been suggested that superoxide can initiate lipid peroxidation by reducing ferric into ferrous iron, which is able to catalyze the formation of free hydroxyl radicals via the Fenton reaction. The possibility of hydroxyl-initiated lipid peroxidation was considered in earlier studies. For example, Lai and Piette [8] identified hydroxyl radicals in NADPH-dependent microsomal lipid peroxidation by EPR spectroscopy using the spin-trapping agents DMPO and phenyl-tcrt-butylnitrone. They proposed that hydroxyl radicals are generated by the Fenton reaction between ferrous ions and hydrogen peroxide formed by the dismutation of superoxide. Later on, the formation of hydroxyl radicals was shown in the oxidation of NADPH catalyzed by microsomal NADPH-cytochrome P-450 reductase [9,10]. [Pg.774]

Recently, Batthyany et al. [133] pointed out that the reduction of cupric ions bound to apolipoprotein B-100 by endogenous LDL components might be an initiation step in copper-mediated LDL oxidation. They suggested that this reaction proceeds to form cuprous ion and the protein-tryptophanyl free radical the latter was identified on the basis of EPR spectrum with spin-trap 2-methyl-2-nitrosopropane. [Pg.793]

Neither Suzuki et al. [206] nor Scott et al. [207] found any effect of LA on superoxide production by xanthine oxidase. Scott et al. also concluded that DHLA is incapable of reacting with superoxide. The last conclusion seems highly improbable. The ability of superoxide to react with thiols with the rate constants equal to 105 to 106lmol 1s 1 has been shown in chemical studies [208]. Dikalov et al. [209] estimated the rate constant for the reaction of DHLA with superoxide as (4.8 + 2)x 105 lmol-1 s-1 using the competition experiments with spin trap DMPO, which is very close to the previous value of (7.3+ 0.24) x 105 1 mol 1 s 1 reported for this reaction [210]. Negative results obtained by Scott et al. [207] are probably explained by the use of unreliable NBT assay for superoxide detection [211]. [Pg.874]

Early methods of superoxide detection are well known and described in many books and reviews. They include cytochrome c reduction, nitroblue tetrazolium reduction, spin trapping, etc. (see, for example, Ref. [1]). The most efficient assays are based on the ability of superoxide to reduce some compounds by one-electron transfer mechanism because such processes (Reaction (1)) proceed with high rates [2] ... [Pg.961]

Another approach to this problem is a search for the other more effective spin traps. Frejaville et al. [23] demonstrated that the half-life of spin-adduct of superoxide with 5-(diethoxyphosphoryl)-5-mcthyl-l -pyrrolinc-/V-oxide (DEMPO) is about tenfold longer than that of DMPO OOH. Despite a much more efficiency of this spin trap, its hydrophilic properties limit its use for superoxide detection in lipid membranes. Stolze et al. [24] studied the efficiency of some lipophilic derivatives of DEMPO in the reaction with superoxide. These authors demonstrated a higher stability of superoxide spin-adducts with 5-(di- -propoxypho-sphoryl)-5-methyl-1 -pyrrolinc-A -oxidc (DPPMPO) and 5-(di- -butoxyphosphoryl)-5-methyl-... [Pg.964]

Unfortunately, due to the above shortcomings of hydroxylamine derivatives as spin traps, the uncertainties of the mechanism of their reactions with superoxide are added. Although it is supposed that nitroxide radicals are formed by oxidation with superoxide (Reaction (6)), this reaction cannot be an elemental stage because superoxide cannot abstract a hydrogen atom. [Pg.964]

There is also a big uncertainty in published rate constants for Reaction (6). In Refs. [25 27] these rate constants are found to be of 103 1041 mol 1 s 1. However, these values are apparently overestimated because Bielski et al. [28] earlier showed that the rate constant for the reaction of superoxide with hydroxylamine does not exceed 301 mol 1 s 1. Thus, the use of hydroxylamines as spin traps for superoxide detection has several disadvantages. [Pg.965]


See other pages where Reactions spin trapping is mentioned: [Pg.1548]    [Pg.262]    [Pg.14]    [Pg.670]    [Pg.132]    [Pg.122]    [Pg.182]    [Pg.74]    [Pg.74]    [Pg.190]    [Pg.271]    [Pg.341]    [Pg.218]    [Pg.101]    [Pg.51]    [Pg.170]    [Pg.172]    [Pg.782]    [Pg.805]    [Pg.806]    [Pg.908]    [Pg.919]    [Pg.963]    [Pg.966]   
See also in sourсe #XX -- [ Pg.128 ]




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