Lipid peroxidation initiated by superoxide-dependent hydroxyl radicals using complexed iron and hydrogen peroxide

AbstractIron salts stimulate lipid peroxidation by decomposing lipid peroxides to produce alkoxyl and peroxyl radicals which initiate further oxidation. In aqueous solution ferrous salts produce OH. radicals, a reactive species able to abstract hydrogen atoms from unsaturated fatty acids, and so can initiate lipid peroxidation. When iron salts are added to lipids, containing variable amounts of lipid peroxide, the former reaction is favoured and OH. radicals contribute little to the observed rate of peroxidation. When iron is complexed with EDTA, however, lipid peroxide decomposition is prevented, but the complex reacts with hydrogen peroxide to form OH. radicals which are seen to initiate lipid peroxidation. Superoxide radicals appear to play an important part in reducing the iron complex

Antioxidant properties of caeruloplasmin towards iron- and copper-dependent oxygen radical formation

AbstractThe antioxidant activity of caeruloplasmin can be mainly ascribed to its ferroxidase activity which effectively inhibits ferrous ion-stimulated lipid peroxidation and ferrous ion-dependent formation of hydroxyl radicals in the Fenton reaction. In addition, caeruloplasmin can prevent copper ions from stimulating lipid peroxidation

A Chemical-dynamical Model of Wave-driven Sodium Fluctuations

A comprehensive chemical-dynamical model is used to investigate the interaction of gravity waves with twenty minor species involved in the atomic sodium chemistry in the mesopause region. We find that chemistry becomes important on the underside of the sodium layer, primarily below 85 km altitude, where the relative importance of chemistry in wave-driven sodium fluctuations increases with increasing wave period and increasing horizontal wavelength. We also find that for altitudes below 80 km an adequate determination of the effects of chemistry in these fluctuations requires the inclusion of several reactions related to ozone chemistry. However, the atomic Na density is too low this region to be routinely observed by current sodium lidars. Importantly, we find that above 85 km altitude sodium can be treated as a passive tracer of gravity wave motions

Peroxynitrite releases copper from caeruloplasmin: implications for atherosclerosis

AbstractPeroxynitrite may be formed in the vasculature by the reaction of puperoxide with nitric oxide. When the blue copper-containing protein, caeruloplasmin, is incubated with peroxynitrite, copper is released, and ferroxidase activity and the blue colouration are lost. When plasma from normal subjects is incubated with peroxynitrite, the oxidant reacts with numerous plasma constituents but is still able to release copper from caeruloplasmin. As the ferroxidase activity of caeruloplasmin is lost in plasma in the presence of peroxynitrite, a second ferroxidase activity associated with peroxidised lipids, and not inhibited by azide, is formed

Allopurinol and oxypurinol are hydroxyl radical scavengers

AbstractAllopurinol is a scavenger of the highly reactive hydroxyl radical (k2 approx. 109 M−1s−1). One product of attack of hydroxyl radical upon allopurinol is oxypurinol, which is a major metabolite of allopurinol. Oxypurinol is a better hydroxyl radical scavenger than is allopurinol (k2 approx. 4 × 109 M−1s−1) and it also reacts with the myeloperoxidase-derived oxidant hypochlorous acid. Hence the protective actions of allopurinol against reperfusion damage after hypoxia need not be entirely due to xanthine oxidase inhibition

Reflections on Forty Years of Irish Membership of the European Union (special issue)

The abstract is included in the text

The Meteoric Ni Layer in the Upper Atmosphere

The first global atmospheric model of Ni (WACCM-Ni) has been developed to understand recent observations of the mesospheric Ni layer by ground-based resonance lidars. The three components of the model are: the Whole Atmospheric Community Climate Model (WACCM6); a meteoric input function derived by coupling an astronomical model of dust sources in the solar system with a chemical meteoric ablation model; and a comprehensive set of neutral, ion-molecule, and photochemical reactions pertinent to the chemistry of Ni in the upper atmosphere. In order to achieve closure on the chemistry, the reaction kinetics of three important reactions were first studied using a fast flow tube with pulsed laser ablation of a Ni target, yielding k(NiO + O) = (4.6 ± 1.4) × 10−11, k(NiO + CO) = (3.0 ± 0.5) × 10−11, and k(NiO2 + O) = (2.5 ± 1.2) × 10−11 cm3 molecule−1 s−1 at 294 K. The photodissociation rate of NiOH was computed to be J(NiOH) = 0.02 s−1. WACCM-Ni simulates satisfactorily the observed neutral Ni layer peak height and width, and Ni+ measurements from rocket-borne mass spectrometry. The Ni layer is predicted to have a similar seasonal and latitudinal variation as the Fe layer, and its unusually broad bottom-side compared with Fe is caused by the relatively fast NiO + CO reaction. The quantum yield for photon emission from the Ni + O3 reaction, observed in the nightglow, is estimated to be between 6% and 40%. ©2020. The Authors

Barkhausen Noise and Critical Scaling in the Demagnetization Curve

The demagnetization curve, or initial magnetization curve, is studied by examining the embedded Barkhausen noise using the non-equilibrium, zero temperature random-field Ising model. The demagnetization curve is found to reflect the critical point seen as the system's disorder is changed. Critical scaling is found for avalanche sizes and the size and number of spanning avalanches. The critical exponents are derived from those related to the saturation loop and subloops. Finally, the behavior in the presence of long range demagnetizing fields is discussed. Results are presented for simulations of up to one million spins.Comment: 4 pages, 4 figures, submitted to Physical Review Letter

P Cygni Profiles of Molecular Lines Toward Arp 220 Nuclei

We report ~100 pc (0farcs3) resolution observations of (sub)millimeter HCO+ and CO lines in the ultraluminous infrared galaxy Arp 220. The lines peak at two merger nuclei, with HCO+ being more spatially concentrated than CO. Asymmetric line profiles with blueshifted absorption and redshifted emission are discovered in HCO+(3-2) and (4-3) toward the two nuclei and in CO(3-2) toward one nucleus. We suggest that these P Cygni profiles are due to ~100 km s–1 outward motion of molecular gas from the nuclei. This gas is most likely outflowing from the inner regions of the two nuclear disks rotating around individual nuclei, clearing the shroud around the luminosity sources there