Electron spin resonance compounds

Unpaired electrons and magnetism - One of the consequences of the open (incompletely filled) d" configuration of transition-metal ions may be the presence of one or more unpaired electrons. Such compounds could be described as radicals, and they are detected by techniques such as electron spin resonance spectroscopy. 

Despite the fact that natural elemental sulfur contains 0.75% of the isotope [4] with a nuclear spin of 7 = /2 no NMR spectra of elemental sulfur have ever been reported. Such spectra are however well-known for compounds containing just one or two sulfur atoms [5]. Electron spin resonance spectra of irradiated elemental sulfur samples and of quenched sulfur vapor have been reviewed elsewhere [6-8]. 

The basic methods of the identification and study of matrix-isolated intermediates are infrared (IR), ultraviolet-visible (UV-vis), Raman and electron spin resonance (esr) spectroscopy. The most widely used is IR spectroscopy, which has some significant advantages. One of them is its high information content, and the other lies in the absence of overlapping bands in matrix IR spectra because the peaks are very narrow (about 1 cm ), due to the low temperature and the absence of rotation and interaction between molecules in the matrix. This fact allows the identification of practically all the compounds present, even in multicomponent reaetion mixtures, and the determination of vibrational frequencies of molecules with high accuracy (up to 0.01 cm when Fourier transform infrared spectrometers are used). 

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... 

Inoue, K., Murayama, S., Seshimo, F., Takeba, K., Yoshimura, Y., and Nakazawa, H. (2005). Identification of phenolic compound in manuka honey as specific superoxide anion radical scavenger using electron spin resonance (ESR) and liquid chromatography with coulometric array detection. /. Sci. Food Agric. 85, 872-878. 

Matsuo, M. Matsumoto, S. Electron spin resonance spectra of the chromanoxyl radicals derived from tocopherols (vitaminE) and theirrelated compounds. Lipids 1983,18, 81-86. 

As with the nitroxalkylcobalamins (119) and cobinamides, the co-binamides in which nitroxide is coordinated show electron spin resonance spectra very similar to the spectrum of free nitroxide. The high field line is not broadened as much as in the spectrum of a nitroxalkyl-cobinamide. No hyperfine splitting from methyl protons in the 2 or 6 positions can be observed for the bound nitroxide. However, treatment of the coordinate spin labeled compounds with cyanide releases the nitroxide. When this happens, the proton hyperfine can be observed (Fig. 25). Thus treatment with cyanide simply displaces the nitroxide and a spectrum for free nitroxide is observed. 

The electron spin resonance (ESR) spectra of free radicals obtained by electrolytic or microsomal reduction of several potential antiprotozoal 1,2,5-oxadiazoles were characterized and analyzed. Ab initio MO calculations were performed to obtain the optimized geometries, and the theoretical hyperfine constant was carried out using Zerner s intermediate neglect of differential overlap (ZINDO) semi-empirical methodology. DFT was used to rationalize the reduction potentials of these compounds <2003SAA69>. 

Selected electron spin resonance data for spin adducts of C-nitroso-compounds (see also Table l)0 ... 

Investigations on the electron spin resonance of the radical anions 29 31> of [2.2]-and higher [n.n]paracyclophanes have shown that delocalization of the unpaired electrons over both aromatic nuclei is scarcely possible until the number of bridge members n >3 31>. In open-chain compounds of the type Ar-[CH2] -Ar the corresponding condition is n> 1. This would suggest that the mechanism responsible for the transfer of elec-... 

Thus cooling-warming cycles, suitably induced, allowed temporal resolution of the reaction, step by step. The absorption, optical rotary dispersion, and electron spin resonance (ESR) spectra of pure compounds I and II were then recorded and found to be similar to those obtained under fast-reaction conditions (Douzou et al., 1970 Douzou and Leter-rier, 1970). Additional interesting observations were made possible by the low-temperature technique for instance, instead of making the time scale of reactions feasible exp>erimentally by increasing the substrate concentrations as in fast techniques, reactions at low temperatures could be performed with stoichiometric concentrations of enzyme. Such con-... 

Chaillot B, Labrude P, Vigneron C, et al. Freeze-drying of hemoglobin solutions without adjuvant and in presence of glucose, tris, and beta-alanine a study by electron spin resonance of the oxidized compounds produced. Am J Hematol 1981 10 319. 

The effects of ultrasound upon the permeability of the cell walls of the gram-negative bacteria Pseudomonas aeruginosa toward hydrophobic compounds particularly antibiotics have been examined [8]. The penetration and distribution of 16-dosylstearic acid (16-DS) in the cell membranes of the bacteria was quantified by a spin-labeling electron spin resonance (ESR) method. The results indicated that the intracellular concentration of 16- D S was higher in insonated cells and increased linearly with the sonication power. 

Electron-spin resonance (e.s.r.) spectra with characteristic hyperfine structure have been recorded during the initial stages of the Maillard reaction between various sugar and amino compounds. The products responsible for the spectra appear to be IV, Af -disubstituted pyrazine radical cations. The pyrazine derivatives are assumed to be formed by the bimolecular condensation of two- and three-carbon enaminol compo-... 

Explaining just how this happens is far from simple. Electron spin resonance is a phenomenon of molecular structure in which high frequency energy is put into the molecular system and electron spin resonance signals emerge from the system. But not all compounds have an electron spin resonation to exhibit ESR activity a... 

In the anion-radicals of nitro compounds, an unpaired electron is localized on the nitro group and this localization depends on the nature of the core molecule bearing this nitro substituent. The value of the hyperfine coupling (HFC) constant in the electron-spin resonance (ESR) spectrum reflects the extent of localization of the unpaired electron values of several nitro compounds are given in Table 1.1. 

The electron spin resonance spectra were run in nitrogen-saturated solutions of aromatic compound ca. 10" m) and nucleophile (0-05-0-1 M) in the solvent(s) indicated. Irradiation in the cavity was effected with a high pressure mercury arc. Electrolysis was performed with the platinum cathode in the cavity, tetraethyl-ammonium perchlorate as electrolyte and electric currents of 10-250 /lA. 

Unequivocal confirmation of its structure was furnished by X-ray crystallography. Compound B forms a blue solution in a variety of solvents. Its solution in benzene shows electron spin resonance (ESR) signal. 

Electron spin resonance, see also specific compounds... 

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