Investigation of metabolic changes in irradiated rat brain tissue by means of 1H NMR in vitro relaxation study

The effect of irradiation on concentrations and relaxation behaviour of brain metabolites was studied by means of high-resolution 1H NMR in vitro. The studies were performed on rat brains irradiated with the doses of 20 Gy applied in fractions of 2 Gy. Standard procedures were used to obtain HClO4 extracts of rat brains. The 1H NMR studies of the extracts solutions in D2O were performed using a Varian Inova-300 NMR spectrometer. The integral intensities of the metabolite signals were found to change during the irradiation cycle and after it. These changes are accompanied by the variations in the T1 relaxation times. N-acetylaspartate, glycerophosphocholine, phosphocholine, choline, creatine and phosphocreatine, myoinositol and taurine were analysed as potential markers of irradiation injury.     

Mechanism of an alcohol-trapping reaction in the direct and benzophenone-sensitized photodenitrogenation of a spiroepoxy-substituted azoalkane: solvent effects and stereochemical deuterium labeling

The spin-state-dependent reactivity, singlet versus triplet, of the 2-spiroepoxy-1,3-cyclopentane-1,3-diyl DR2 has been assessed through alcohol-trapping reactions for which the effect of solvent acidity on the product distribution of the alcohol trapping products 2 versus 3 + 4 and stereochemical deuterium-labeling studies have been performed. The proposed mechanism for the solvent effect on the product ratio (2/3 + 4) reveals the importance of the hydrogen-bonded intermediates I1 and I2 in the trapping reactions; the stereochemical deuterium-labeling results clarify the dipole structure trapped by the alcohol. The dipoles DP1 and DP2, in which the configuration between the epoxide oxygen and the deuterium atoms is retained, are inferred for the direct photodenitrogenation reactions (singlet state), whereas for the benzophenone-sensitized photoreactions (triplet state), after ISC, the ring-opened dipole DP3 is implied as the intermediate that is trapped by the alcohol.     

Intramolecular and intermolecular kinetic isotope effects (KIE) in the nitrosoarene ene reaction: experimental evidence for reversible intermediate formation

The intramolecular and intermolecular kinetic isotope effects (KIE) have been determined for the nitrosoarene ene reaction with deuterium-stereolabeled 2,3-dimethyl-2-butenes (TME). trans-TME-d(6) (k(H)/k(D) = 3.0) and gem-TME-d(6) (k(H)/k(D) = 4.0) show large intramolecular primary isotope effects. In contrast, the intramolecular competition in cis-TME-d(6) (k(H)/k(D) = 1.5) and the intermolecular competition for the TME-d(0)/TME-d(12) pair (k(H)/k(D) = 1.98) show considerably smaller, but mechanistically significant kinetic isotope effects. The latter fact is rationalized in terms of reversible formation of a three-membered-ring intermediate, namely the aziridine N-oxide, or a similar unsymmetrical, polarized diradical in the first step of the reaction. Such reversibility has also been implied earlier for triazolinedione (TAD) and singlet oxygen ((1)O(2)) with deuterium-stereolabeled 2-butenes, but of the three enophiles, ArNO is the most sensitive toward reversibility, which is due to its moderate reactivity and its high steric demand.     

Multipliers and singular integrals on exponential growth groups

We propose a simple abstract version of Calderón–Zygmund theory, which is applicable to spaces with exponential volume growth, and then show that important specific operators can be treated within this framework. Both authors are part of the European TMR network entitled ``Harmonic Analysis'. The first author was partially supported by KBN grant 5 P03A 050 20 and by the TMR network. The second author was partially supported by his university and by the Italian M.U.R.S.T     

Unbound exciton–phonon states in oligothiophene crystals – A model approach for spectroscopic purposes

A simple model of exciton–phonon interaction in a crystal with one molecule in the unit cell is used to simulate some peculiar features of the oligothiophene absorption spectra. The model is treated in the limit of weak vibronic coupling, and the configuration interaction between the intense zero-phonon Frenkel state and the one-phonon continuum is described in terms of the Fano formalism. The good agreement between the calculated curve and a part of the experimental absorption profile allows one to discriminate some features that are physically relevant but are not accounted for in the model.     

Das Lucassche Ehepaarproblem

Ohne Zusammenfassung     

Zur Analyse von Ferrozirkon

Ohne Zusammenfassung