Detection by electron paramagnetic resonance

Shortly after, Doetschman and Hutchison reported the first example of a reactive carbene in the crystalline solid state, by preparing diphenylcarbene from diphenyldi-azomethane in mixed crystals with 1,1-diphenylethylene 84 (Scheme 7.23). When the mixed crystals were irradiated, carbene 85 was detected by electron paramagnetic resonance (EPR) and the disappearance of the signal was monitored to determine its kinetic behavior. Two reactions were shown to take place under topochemical... 

Chapman A, Cammack R, Linstead DJ, Lloyd D. 1986. Respiration of Trichomonas vaginalis components detected by electron paramagnetic resonance spectroscopy. Eur J Biochem 156 193-8. 

Pellat, C., Henry, Y., and Drapier, j. C. (1990). IFN-gamma-activated macrophages Detection by electron paramagnetic resonance of complexes between L-arginine-derived nitric oxide and nonheme iron proteins. Biochem. Biophys. Res. Commun. 166, 119-125. 

Stadler, J., Bergonia, H. A., Di Silvio, M., Sweetland, M. A., Billiar, T. R., Simmons, R. L., and Lancaster, J. R., Jr. (1993). Nonheme iron-nitrosyl complex formation in rat hepatocytes Detection by electron paramagnetic resonance spectroscopy. Arch. Biochem. Biophys. 302, 4-11. 

Kochany and Bolton (1992) studied the primary rate constants of the reactions of hydroxyl radicals, benzene, and some of its halo derivatives based on spin trapping using detection by electron paramagnetic resonance (EPR) spectroscopy. The competitive kinetic scheme and the relative initial slopes or signal amplitudes were used to deduce the kinetic model. Based on a previously published rate constant (4.3 x 109 M 1 s ) in the pH range of 6.5 to 10.0 for the reaction of hydroxyl radicals with the spin trap compound 5,5 -d i methy I pyrro I i ne N-oxide (DMPO), rate constants for the reaction of hydroxyl radicals with benzene and its halo derivatives were determined. 

The existence of free hydroxyl radicals in photo-initiated AOPs can be proven by applying a well-established method, the so-called spin trapping technique. The diamagnetic spin trap 5,5 -dimethyl-1-pyrroline N-oxide (DMPO) forms a stable paramagnetic spin-adduct with OH radicals. Its formation can be detected by electron paramagnetic resonance (EPR) spectroscopy. The underlying chemistry of... 

Kozlov AV, Bini A, Gallesi D, Giovannini F, lannone A, Masini A, Meletti E and Tomasi A, Free iron, as detected by electron paramagnetic resonance spectroscopy, increases unequally in different tissues during dietary iron overload in the rat. Biometals 9(1) 98-103, 1996. 

Voltammetric data for ester reductions are available for several aromatic esters [51-54], and in particular cyclic voltammetry shows clearly that in the absence of proton donors reversible formation of anion radical occurs [51]. In dimethylfonnamide (DMF) solution the peak potential for reduction of methyl benzoate is —2.29 V (versus SCE) for comparison dimethyl terephthalate reduces at —1.68 V and phthalic anhydride at —1.25 V [4]. Half-wave potentials for reduction of aromatic carboxylate esters in an unbuffered solution of pH 7.2 are linearly correlated with cr values [51] electron-withdrawing substituents in the ring or alkoxy group shift Ei/o toward less negative potentials. Generally, esters seem to be more easily reducible than the parent carboxylic acids. Anion radicals of methyl, ethyl, and isopropyl benzoate have been detected by electron paramagnetic resonance (epr) spectroscopy upon cathodic reduction of these esters in acetonitrile-tetrapro-pylammonium perchlorate [52]. The anion radicals of several anhydrides, including phthalic anhydride, have similarly been studied [55]. 

Cantilena, L. R., Jr., Smith, R. P., Frasur, S., Kruszyna, H., Kruszyna, R., and Wilcox, D. E. (1992). Nitric oxide hemoglobin in patients receiving nitroglycerin as detected by electron paramagnetic resonance spectroscopy [see comments]. J. Lab. Clin. Med. 120, 902-907. 

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