Direct electron spin resonance, radical

Although Otsu et al. [12] have studied the BPO-DMA system by electron spin resonance (ESR) technique and trapped the aminomethyl radical, there is still a lack of direct proof of the above second step, particularly concerning the behavior of the aminium radical salt. We [13] have proposed the aminium radical salt with purple color through this reaction of DMT with CCI4 in the presence of O2 following the displacement reaction as ... 

Electron paramagnetic resonance spectroscopy (HER), also called electron spin resonance spectroscopy (ESR), may be used for direct detection and conformational and structural characterization of paramagnetic species. Good introductions to F.PR have been provided by Fischer8 and I.effler9 and most books on radical chemistry have a section on EPR. EPR detection limits arc dependent on radical structure and the signal complexity. However, with modern instrumentation, radical concentrations > 1 O 9 M can be detected and concentrations > I0"7 M can be reliably quantified. 

It is likely that the answers to these questions will come only from more selective and sophisticated experiments than have been done hitherto, although some useful directions have been established. The use of high-sensitivity electron spin resonance for the study in situ of anticipated radical species will likely be possible, if the background signals from other radiation-produced species are not too intense. Studies of the chemistry of implanted atoms and ions in solid organometallic substrates will make it possible to start with totally unbound atoms which suffer no Auger ionization and thus to simulate the extreme of the total recoil. Careful studies of the thermal annealing effects, especially in the presence of reactive atmospheres, will... 

Although Ce(IV) oxidation of carboxylic acids is slow and incomplete under similar reaction conditions , the rate is greatly enhanced on addition of perchloric acid. No kinetics were obtained but product analysis of the oxidations of -butyric, isobutyric, pivalic and acetic acids indicates an identical oxidative decarboxylation to take place. Photochemical decomposition of Ce(IV) carbo-xylates is highly efficient unity) and Cu(ll) diverts the course of reaction in the same way as in the thermal oxidation by Co(IIl). Direct spectroscopic evidence for the intermediate formation of alkyl radicals was obtained by Greatorex and Kemp ° who photoirradiated several Ce(IV) carboxylates in a degassed perchloric acid glass at 77 °K in the cavity of an electron spin resonance spectro-... 

The direct measurement of CH,- radicals, using a matrix isolation electron spin resonance system (MIESR), has previously demonstrated that surface-generated CH,-radicals are produced during the oxidative coupling of CH4 and emanate into the gas phase... 

A number of the techniques that have been employed have the ability to directly monitor free-radical species either in vitro or in vivo [predominantly those involving electron spin resonance (e.s.r.) spectroscopy]. However, since many physiologically relevant free radicals have extremely short half-lives (e.g. 10 s for OH), the majority of the methods utilized detect products arising from their reactions with chemical components present (i.e. indirect methods). These indirect methods for... 

Garlick, P.B., Davies, M.J., Hearse, D.J. and Slater, T.F. (1987). Direct detection of free radicals in the reperfused rat heart using electron spin resonance spectroscopy. Circ. Res. 61, 757-760. 

Radiation techniques, application to the study of organic radicals, 12, 223 Radical addition reactions, gas-phase, directive effects in, 16, 51 Radicals, cation in solution, formation, properties and reactions of, 13, 155 Radicals, organic application of radiation techniques, 12,223 Radicals, organic cation, in solution kinetics and mechanisms of reaction of, 20, 55 Radicals, organic free, identification by electron spin resonance, 1,284 Radicals, short-lived organic, electron spin resonance studies of, 5, 53 Rates and mechanisms of solvolytic reactions, medium effects on, 14, 1 Reaction kinetics, polarography and, 5, 1... 

NMR observes the chemistry of only the proton nucleus (though it can observe many other nuclei independently). This means that hetero and metallic chemistry cannot be observed directly. Thus, sulfur, nitrogen, oxygen, and metals cannot be directly analyzed by NMR, though secondary correlations can be obtained from the proton chemistry of the sample. In combination with electron spin resonance (ESR) analyzers that can operate in the fringe fields of the NMR magnet the presence of paramagnetic metals and free radicals can be quantified. 

The reactive intermediates mentioned above are initially ions and excited molecules and subsequently may be free radicals. Many ions are probably formed on irradiating PET, as judged by the large concentration of spins detected at —196°C. by electron spin resonance (ESR), but nothing is known directly about their chemical structure or reactivity. Any chemical role of excited molecules is equally a matter of conjecture. In these circumstances, the influence of dose rate will be discussed by reference to free radicals. Eventually, when more quantitative experimental data are obtained, the adequacy of free radical reactions may be better assessed, and the role of ions and excited molecules brought into perspective. 

The problem of bringing a large magnet into the field for ambient measurements has been overcome in electron paramagnetic resonance (EPR, also called electron spin resonance, ESR) by Mihelcic, Helten, and coworkers (93-99). They combined EPR with a matrix isolation technique to allow the sampling and radical quantification to occur in separate steps. The matrix isolation is also required in this case because EPR is not sensitive enough to measure peroxy radicals directly in the atmosphere. EPR spectroscopy has also been used in laboratory studies of peroxy radical reactions (100, 101). 

The idea that free radicals occur in many chemical reactions is as old as the study of the mechanisms of these reactions. However, direct physical evidence for the existence of free radicals and for their presence in certain reactions is comparatively recent. Such evidence has been obtained in recent years by the methods of mass spectrometry, optical spectroscopy, and electron spin resonance spectrometry. The optical method of detecting free radicals has the advantage that it simultaneously supplies information about the structure of the radical. Indeed, in many instances the nature of the free radical has been identified by the structure of the spectrum without any assumptions about the mechanism of the reaction in which it appears.1... 

For chainwise polymerizations, the analysis of model systems implies consideration of the homopolymerization or copolymerization of bifunctional monomers. Kinetic results cannot be directly extrapolated to the case of networks, because very important features such as intramolecular cycliza-tion reactions are not present in the case of linear polymers. However, the nature of initiation and termination reactions may be assessed. For example, using electron spin resonance (ESR), Brown and Sandreczki (1990) identified different types of radicals produced during the homopolymerization of a monomaleimide (a model compound of bismaleimides). 

The electron spin resonance (E.S.R.) spectra of a paramagnetic organic molecule, e.g. free radical, radical cation or radical anion, is directly related to its unpaired electron distribution (spin density). In the region of a magnetic nucleus the hyperfine interaction between the magnetic moments of the nucleus and the electron is a function of the spin density. It has been shown that, for an atom N, a direct correlation exists between its observed hyperfine coupling constant, and [pa—pP), the unpaired electron population of its atomic orbitals 1). 

Experimental evidence for the presence of radical intermediates is provided by the identification of expected products from radical rearrangements, by the use of appropriate radical probes and by direct detection by electron spin resonance (ESR). Other mechanistic evidence includes inhibition by radical traps, such as di-t-butylnitroxide (DTBN), TEMPO (2,2,6,6-tetramethyl-l-piperidinyloxy), galvinoxyl and oxygen, and by radical anion scavengers such as p-dinitrobenzene (p-DNB). 

Direct observation of transition-state selectivity has been observed from the low-temperature cyclization of dienes inside H-mordenite and H-ZSM-5 (9). By using electron spin resonance (ESR) spectroscopy, it has been possible to explore radical formation upon the sorption of dienes on H-mordenite and H-ZSM-5. From the analysis obtained, it was found that the dienes are not very reactive for oligomerization inside H-mordenite channels. Heating H-mordenite with presorbed 1,4-pentadiene or 1,5-hexadiene yields selective cyclization of molecules via cycloalkenie radicals inside the H-mordenite channel. However, in the smaller pores of H-ZSM-5 (although die nature of both acid and redox sites in both zeolites are the same) no eyclo-olefinie radicals are formed as shown by the ESR spectrum. These experiments illustrate the reality of transition-state selectivity inside the pores of zeolites. 

---