Free radical reactions in atherosclerosis; An EPR spectrometry study

The copper catalysed oxidation of homocysteine has been studied by electron paramagnetic resonance (EPR) spectroscopy and spin trapping techniques to determine the nature of free radical species formed under varying experimental conditions. Three radicals; thiyl, alkyl and hydroxyl were detected with hydroxyl being predominant. A reaction mechanism is proposed involving Fenton chemistry. Inclusion of catalase to test for intermediate generation of hydrogen peroxide showed a marked reduction in amount of hydroxyl radical generated. In contrast, the addition of superoxide dismutase showed no significant effect on the level of hydroxyl radical formed. Enhanced radical formation was observed at higher levels of oxygen, an effect which has consequences for differential oxygen levels in arterial and venous systems. Implications are drawn for a higher incidence of atherosclerotic plaque formation in arteries versus veins. © 2006 - IOS Press and the authors. All rights reserved.

A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X -band electron paramagnetic resonance spectroscopy. © 2010 American Institute of Physics.

Radical intermediates in chloroform reactions over triphenylphosphine-protected Au nanoparticles

Reactions of chloroform over triphenylphosphine-protected Au nanoparticles have been studied using electron paramagnetic resonance (EPR) spectroscopy and a spin trapping technique. Two competing reactions, abstraction of hydrogen and halogen atoms, were identified. The hydrogen abstraction reaction showed an inverse kinetic isotope effect. Treatment of nanoparticles with oxidizing or reducing reagents made it possible to tune the selectivity of radical formation from halogen to hydrogen (deuterium) abstraction. Treatment with PbO2 promoted the deuterium abstraction reaction followed by the loss of nanoparticle activity, whereas treatment with NaBH4 regenerated the nanoparticle activity towards Cl atom abstraction. X-ray photoelectron spectroscopy showed an increased Au:P ratio upon treatment with oxidizing reagents. This is likely due to the oxidation of some phosphine ligands to phosphine oxides which then desorb from the nanoparticle surface. © 2009 The Royal Societ of Chemistry.

Designing intrinsically photostable low band gap polymers:a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.