Re-investigation of the conformational interconversion of the 1,2,3,6,7,8-hexahydropyrene cation radical by EPR, ENDOR and TRIPLE spectroscopy

The conformational interconversion of the 1,2,3,6,7,8-hexahydropyrene cation radical has been re-examined by EPR, ENDOR and TRIPLE spectroscopy, and the Arrhenius plot is presented for a wider temperature range than that used earlier. The EPR spectra were measured from 143 to 369 K and the ENDOR spectra from 143 to 263 K. The thermodynamic constants of the conformational interconversion of the cation radical were determined on the basis of the temperature-dependent spectra. The high-resolution spectra clearly show that there are two overlapping spectra at low temperature, and this is confirmed by simulation.

EPR and MO calculation studies on α-aminoanthraquinone anion radicals in aprotic solvents

Molecular orbital study of conformational isomers and rotational barriers of methyl substituted hydroquinone cation radicals

Abstract The torsional potential energy curve of the hydroxyl group of hydroquinone and tetramethyl-hydroquinone cation radicals were explored with various ab initio methods. The minimum and the torsional transition state geometries and energies were computed by using high accuracy density functional methods yielding the rotation barrier height and the energy difference between the cis- and trans-isomers. The obtained minimum energy geometry for the hydroquinone cation radical indicates that the CO bond has shortened when compared to the neutral species. We attribute this to the increased double-bond character of this bond. The energy minima were located for methyl-hydroquinone, 2,3-dimeth…

Effect of ischaemic preconditioning, cardiopulmonary bypass and myocardial ischaemic/reperfusion on free radical generation in CABG patients.

Abstract Objective: To investigate the free radicals (FR) generation after ischaemic preconditioning and cardiopulmonary bypass and during reperfusion in CABG patients, and the role of ischaemic preconditioning. Methods: Forty-three CABG patients were randomised into an ischaemic preconditioning and a control group. The protocol for ischaemic preconditioning was two cycles of 2-min ischaemia followed by 3-min reperfusion. Free radicals were measured using electron spin resonance spectroscopy. Global and right heart functions were collected. Results: The free radicals generation in coronary sinus blood in the ischaemic preconditioning group was 9.7 and 16.6% after the ischaemic preconditioni…

Comparison of spin density calculation methods for various alkyl-substituted 9,10-anthraquinone anion radicals in the solution phase

EPR and ENDOR spectra were recorded for 2-methyl-9,10-anthraquinone (2-methylAQ), 2-ethylAQ, 2-tertbutylAQ and 2,3-dimethylAQ anion radicals in the solution phase. The EPR spectra were simulated with the help of ENDOR data. The experimental isotropic hyperfine coupling constants (IHFCs) were compared with calculated values from semi-empirical INDO, spin-restricted AM1/CI and B3PW91 density-functional methods. The best computational methods for the IHFCs were the semi-empirical AM1/CI method and the B3PW91 density-functional method with a large basis set.

EPR, ENDOR and TRIPLE resonance of amino-substituted 9,10-anthraquinone radicals and the rotation of the amino groups in the solution phase

EPR, ENDOR and TRIPLE resonance spectra were recorded for 1-amino-9,10-anthraquinone (1-aminoAQ), 2-aminoAQ, 1,2-diaminoAQ, 1.4-diaminoAQ, 1,5-diaminoAQ and 2,6-diaminoAQ anion radicals in the solution phase. The rotation of the amino groups is discussed with reference to the experimental data. Rotation barrier calculations were carried out using B3PW91/3-21G* density functional method. The amino groups at positions 1, 4, 5, 8 were found not to be in rotational movement up to the EPR time-scale.

Electron paramagnetic resonance, ENDOR and TRIPLE resonance study of some 9,10-anthraquinone radicals in solution

EPR, ENDOR and TRIPLE resonance spectra were recorded for 1,8-dihydroxy-3-methyl-9,10-anthraquinone and 9,10-anthraquinone-2-carboxylic acid anion radicals and the 9,10-anthraquinol-2-carboxylic acid cation radical. EPR spectra were recorded for the 5,8-dideuterio-1,4-dideuterioxy-9,10-anthraquinone anion radical, the 6,7-dideuterio-1,4-dideuterioxy-9,10-anthraquinone anion radical and the 1,4-dihydroxy-9,10-anthraquinol cation radical. The coupling contants of the 1,4-dihydroxy-9,10-anthraquinone anion radical were assigned by deuteriation.

Temperature dependence of the isotropic hyperfine coupling constants in 1,4-hydroquinone and 1,4-dihydroxynaphthalene cation radicals