Biomedical subjects

J C Corchado

Publications and source records attributed to J C Corchado.

4 recordsLinked to original sources

PubMed2006

Product angular distribution for the H + CD4 --> HD + CD3 reaction.

Using an analytical potential energy surface previously developed by our group, namely PES-2002, we analyzed the gas-phase reaction between a hydrogen atom and perdeuterated methane. We studied the effect of quasiclassical trajectory (QCT) and reduced dimensionality quantum-scattering (QM) calculations, with their respective limitations, on CD3 product angular distributions in the collision energy range 16.1-46.1 kcal x mol(-1). It was found that at low collision energy, 16.1 kcal x mol(-1), both the QCT and QM calculations yielded forward scattered CD3 products, i.e., a rebound mechanism. However, at high energies only the QM calculations on the PES-2002 surface reproduced the angular scattering found experimentally.

Journal Article↗

PubMed2006

Quasi-classical trajectory calculations analyzing the role of bending mode excitations of methane in the Cl + CH4 reaction.

The effects of the methane torsional (nu(2)), umbrella (nu(4)), and the combination nu(2)+nu(4) bending mode excitations on the reactivity and dynamics of the gas-phase Cl + CH(4) --> HCl + CH(3) reaction were analyzed. Quasi-classical trajectory (QCT) calculations, including corrections to avoid zero-point energy leakage along the trajectories, were used on an analytical potential energy surface previously developed by our group. With respect to the reactivity, we found that excitation of either bending mode independently gave similar increases in the reactivity, while the increase observed upon excitation of both modes was larger than the sum of the effect of exciting them independently. Both results agree with recent experimental measures. With respect to the dynamics (rotovibrational and angular distributions of the products), the two bending modes and their combination gave very similar pictures, reproducing the experimental behavior. The satisfactory agreement obtained with a great variety of experimental data (always qualitatively acceptable and sometimes even quantitatively) of the present QCT study lends confidence to the potential energy surface constructed by our group.

Journal Article↗

PubMed2006

Quasiclassical trajectory calculations comparing the reactivity and dynamics of symmetric and asymmetric stretch and the role of the bending mode excitations of methane in the Cl + CH4 reaction.

To analyze the effects of the symmetric (nu(1)) and asymmetric (nu(3)) stretch mode excitations and the role played by the "umbrella" bending (nu(4)) mode excitation in the reactivity and the dynamics of the gas-phase Cl+CH(4) reaction, an exhaustive dynamics study was performed. Quasiclassical trajectory (QCT) calculations, including corrections to avoid zero-point energy leakage along the trajectories, were used in this work on an analytical potential energy surface previously developed by Espinosa-Garcia et al. [J. Chem. Phys. (to be published)]. First, with respect to the reactivity, we found that the nu(1) mode excitation is more reactive than the nu(3) mode by a factor of 1.20, in agreement with the experimental tendency between these modes. The inclusion of the nu(4) bending mode practically does not affect this relative reactivity, (nu(1+)nu(4))(nu(3+)nu(4)) = 1.16. Second, with respect to the dynamics (rotovibrational and angular distributions of the products), the two stretch modes, nu(1) and nu(3), give very similar pictures, reproducing the experimental behavior, and the nu(4) "umbrella" mode does not affect the dynamics. The satisfactory reproduction (always qualitatively acceptable and sometimes even quantitatively) of a great variety of experimental data by the QCT study presented here lends confidence to the potential energy surface constructed by Espinosa-Garcia et al. [J. Chem. Phys. (to be published)].

Journal Article↗

PubMed2005

Trapping of the OH radical by alpha-tocopherol: a theoretical study.

The antioxidant activity of alpha-tocopherol against the damaging hydroxyl radical was analyzed theoretically by hybrid density functional theory, following the direct dynamics method, where the thermal rate constants were calculated using variational transition-state theory with multidimensional tunneling. We found that the OH radical is only slightly or not at all selective, attacking by different mechanisms at several positions of the alpha-tocopherol molecule, giving competitive reactions. The most favorable pathways are the hydrogen abstraction reaction from the phenolic hydrogen and the electrophilic addition onto the aromatic ring. We propose a final rate constant, the sum of the competitive hydrogen abstraction and addition reactions, > or =2.7 x 10(8) M(-1) s(-1) at 298 K, where the hydrogen abstraction reaction represents only 20% of the total OH radical reaction. This result indicates that, molecule by molecule, in an apolar environment, alpha-tocopherol is less effective than coenzyme Q (which presents a rate constant of 6.2 x 10(10) M(-1) s(-1) at 298 K) as a scavenger of OH radicals. It was also found that both mechanisms are not direct but pass through intermediates in the entry channel, with little or no influence on the dynamics of the reactions. The hydrogen abstraction reaction also presents another intermediate in the exit channel, which may have a significant role in preventing the pro-oxidant effects of alpha-tocopherol, although less important than with free radicals other than OH.

Antioxidants↗