Decay chemically-induced

Time-resolved laser flash ESR spectroscopy generates radicals with nonequilibrium spin populations and causes spectra with unusual signal directions and intensities. The signals may show absorption, emission, or both and be enhanced as much as 100-fold. Deviations from Boltzmann intensities, first noted in 1963, are known as chemically induced dynamic electron polarization (CIDEP). Because the splitting pattern of the intermediate remains unaffected, the CIDEP enhancement facilitates the detection of short-lived radicals. A related technique, fluorescence detected magnetic resonance (FDMR) offers improved time resolution and its sensitivity exceeds that of ESR. The FDMR experiment probes short-lived radical ion pairs, which form reaction products in electronically excited states that decay radiatively. ... 

Table 1 Composite of our own SW data [14] on the chemically induced variations of the EC decay constant X of Cr" with the corresponding SR-SW results [13] (in parentheses, the Bahcall correction factors have been introduced by us, for the sake of comparability).

Leather can be considered as a relatively chemically-stable material. In general objects made from leather reach the end of their useful lives as a result of fair wear and tear rather than chemically-induced decay. If a pair of shoes lasts for 10 years or a wallet or briefcase for 20 years, the owner is usually satisfied. Books are different. Many leather-bound books spend the majority of their lives sitting unused on shelves. Libraries in historic houses, for instance, contain thousands of books which are rarely read but whose bindings remain sound after a century or more. It is not surprising, therefore, that when in the middle of the nineteenth century it was discovered that many new bindings were deteriorating rapidly, an explanation was sought. 

Oxidation The radiation-chemically induced ionization of chlorinated hydrocarbons, i.e., dichloroethane (DCE) leads to the initial generation of the corresponding solvent radical cation, [DCE] ". The electron affinity of the latter is sufficient to oxidize the fullerene moiety ([60]fullerene E1/2 = +1.26 versus Fc / Fc ). Pulse radiolytic experiments with [60]fullerene in nitrogen-saturated or aerated DCM solutions yielded a doublet with maxima at 960 and 980 nm (Figure 1) (12-18). This fingerprint is identical to that detected in photolytic oxidation experiments and that computed in CNDO/S calculations. Rate constants for the [60]fullerene oxidation are typically very fast with estimated values IC7 > 2 x 10 ° M s. The 7t-radical cation is short-lived and decays via a concentration-dependent bimolecular dimerization reaction with a ground state molecule (kg = 6 x lO M s ) (13). 

Hartmann et al. were the first to apply the X -SW calculation to estimate the chemically induced decay constant variation of Tc. The method meets the conditions to calculate the X-ray intensity ratio variation due to chemical environments as described above. Following their success in applying the X -SW method to inner shell problems in transition elements, a considerable volume of work has been published to explain such phenomena by MO calculations. 

Very important features of solitons, such as their rate of creation and decay, their density on the chain, the effects of external perturbations (for instance, changes of the soliton density and decay rate induced by variations of the physical and chemical structure of the chain) are yet a matter of investigation. 

In order to study the viscosity effect on the quenching of triplet excited state of (53) by TEMPO, chemically induced dynamic electron polarization and transient absorption spectra have been measured in ethylene glycol, 1,2-propanol and their mixtures. The results indicate that the quenching rate constant is viscosity-dependent and decreases linearly with the increase in solvent viscosity. The spectroscopy and dynamics of near-threshold excited states of the isolated chloranil radical anion have been studied using photoelectron imaging taken at 480 nm, which clearly indicates resonance-enhanced photodetachment via a bound electronic excited state. Time-resolved photoelectron imaging reveals that the excited state rapidly decays on a timescale of 130 fs via internal conversion. ... 

Spin dynamic studies, including saturation and inversion recovery, Hahn echo and stimulated echo decay, as well as Carr-Purcell-Meiboom-Gill sequences, can be performed, yielding relaxation times. When rapid reaction kinetics are being measured, information is also gained on transient phenomena such as chemically induced electron polarization (CIDEP). 

The existence of the biradicals and the multipHcity of the surfaces on which these are formed have not been demonstrated directly however, experimental results (stereochemistry of the reaction, CIDNP [chemically induced dynamic nuclear polarization], radical trapping experiments, and quantum yield measurements) support their existence. Recently, the mechanism of 1,3-migration and oxa-di-Jt-methane reactions in terms of potential energy surface and decay funnels has been described this also supports the aforementioned mechanistic impHcations. The detailed mechanism, however, depends, in a very subtle way, on the structure of the chromophoric system and the presence of the functional groups. 

Well before the advent of modern analytical instruments, it was demonstrated by chemical techniques that shear-induced polymer degradation occurred by homoly-tic bond scission. The presence of free radicals was detected photometrically after chemical reaction with a strong UV-absorbing radical scavenger like DPPH, or by analysis of the stable products formed from subsequent reactions of the generated radicals. The apparition of time-resolved ESR spectroscopy in the 1950s permitted identification of the structure of the macroradicals and elucidation of the kinetics and mechanisms of its formation and decay [15]. 

A thorough consideration of mechanisms of formation of the organometallic products led to the conclusion " that the j5-decay itself must be the cause of the molecule formation. Neither purely mechanical collisiona substitution, nor thermal chemical reactions, nor radical reactions, nor radiation-induced reactions seem to be responsible for the synthesis reactions. 

Agarwal et al. 1978), the quantification of these specific enzymes may indicate that exposure to endosulfan has occurred. Blood tests, such as decay curves for aminopyrine in plasma, which are semiquantitative indices of liver enzyme induction, have been used successfully in the past to demonstrate enzyme induction in pesticide-exposed workers. Because numerous chemicals found at hazardous waste sites also induce these hepatic enzymes, these measurements are not specific for endosulfan exposure. However, measurements of enzyme activity, together with the detection of the parent compound or its metabolites in tissue or excreta, can be useful indicators of exposure. All of these potential biomarkers require further verification in epidemiological studies. Further studies with focus on the development of methods to separate and measure the estrogenicity of endosulfan in in vitro assays would be valuable since these assays are more sensitive and discriminative than other conventional biomarkers. Preliminary results have been presented by Sonnenschein et al. (1995). 

When a nucleus is placed in a flux of neutrons, it may capture another neutron. It thus is often unstable toward further decay by j3 -emission. The induced radioactivity is critical to the study of chemical consequences of neutron capture, since so few of these new nuclei are produced that generally they cannot be observed by any other means. This radioactivity is not, however, a part of the phenomenon which we wish to observe and, moreover, is occasionally a distraction. 

Analyte stability is another source of concern the chemical identity should be preserved all through the analytical process. This is not always guaranteed. Analytes may be oxidised or hydrolysed during extraction. Compound integrity can also suffer in the chromatographic column, through heat-induced decay. Extraction... 

Such highly ionized species have been detected for Cl-37 produced by the EC decay of Ar-37 in gaseous phase ((>). In solids, however, such anomalous states are not realized or their life time is much shorter than the half-life of the Mossbauer level (Fe-57 98 ns and Sn-119 17-8 ns) because of fast electron transfer, and usually species in ordinary valence states (2+, 3+ for Fe-57 and 2+, 4+ for Sn-119) are observed in emission Mossbauer spectra (7,8). The distribution of Fe-57 and Sn-119 between the two valence states depends on the physical and chemical environments of the decaying atom in a very complicated way, and detection of the counterparts of the redox reaction is generally very difficult. The recoil energy associated with the EC decays of Co-57 and Sb-119 is estimated to be insufficient to induce displacement of the atom in solids. 

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