EXPLORATORY STUDY OF POTASSIUM AND SODIUM SUPEROXIDE FOR OXYGEN CONTROL IN MANNED SPACE VEHICLES.
Exploratory study of potassium and sodium superoxide for oxygen control in manned spacecraft
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Exploratory study of potassium and sodium superoxide for oxygen control in manned spacecraft
High density metallic superoxide microcontactor for air revitalization oxygen source in sealed cabin atmosphere
Alkali metal peroxide and superoxide blown ceramic foam bodies for thermal insulation
Sodium superoxide isothermal decomposition, detailing metallic oxide effects with differential thermal analysis, thermogravimetry and differential thermogravimetry
Production of alkali metal superoxides by interaction of molecular oxygen with alkali metals or their salts is discussed. Diagram of reactor to show components and operating principles is provided. Analysis of chemical reactions involved is developed.
The effects of disproportionations at lower temperatures and also of a range of reaction chamber pressures on the preparation of calcium superoxide, Ca(O2)2, from calcium peroxide diperoxyhydrate were studied. About 60% purity of product was obtained by a disproportionation procedure. The significance of features of this procedure for a prospective scale-up of the mass prepared in a single experiment is considered. The optimum pressure for product purity was determined, and the use of a molecular sieve desiccant is described.
High-frequency discharge in oxygen can be used to prepare superoxides of alkali and alkaline-earth metals. Since no direct-current discharge at the electrodes is present, no sputtering can contaminate the product, hence a high conversion efficiency.
The bond dissociation energies for the alkali-metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional level. Our computed D0 values are 61.4, 37.2, 40.6, and 38.4 kcal/mol for LiO2, NaO2, KO2, and RbO2, respectively. These values, which are expected to be lower bounds and accurate to 2 kcal/mol, agree well with some of the older flame data, but rule out several recent experimental measurements.
The computed 2A2-2B2 separations of the alkali superoxides are in good agreement with those deduced from electron-spin resonance spectra. The calculations definitively show that the ground state of CsO2 is 2A2. The larger than expected separation for CsO2, based on the trend from LiO2 to RbO2, is attributed primarily to the differential effects of core relaxation. The CsO2 dissociation energy is computed to be 42.7 kcal/mol, with an uncertainty conservatively estimated as +/- 4 kcal/mol.
The purpose of this study was to examine the biochemical response of the green thermophilic photosynthetic bacterium Chloroflexus aurantiacus to oxidative stress. Lab experiments focused primarily on characterizing the antioxidant enzyme superoxide dismutase and the response of this organism to oxidative stress. Experiments in the field at the hotsprings in Yellowstone National Park focused on the changes in the level of these enzymes during the day in response to oxidants and to the different types of ultraviolet radiation.
Oscillatory shear stress occurs at sites of the circulation that are vulnerable to atherosclerosis. Because oxidative stress contributes to atherosclerosis, we sought to determine whether oscillatory shear stress increases endothelial production of reactive oxygen species and to define the enzymes responsible for this phenomenon. Bovine aortic endothelial cells were exposed to static, laminar (15 dyn/cm2), and oscillatory shear stress (+/-15 dyn/cm2). Oscillatory shear increased superoxide (O2.-) production by more than threefold over static and laminar conditions as detected using electron spin resonance (ESR). This increase in O2*- was inhibited by oxypurinol and culture of endothelial cells with tungsten but not by inhibitors of other enzymatic sources. Oxypurinol also prevented H2O2 production in response to oscillatory shear stress as measured by dichlorofluorescin diacetate and Amplex Red fluorescence. Xanthine-dependent O2*- production was increased in homogenates of endothelial cells exposed to oscillatory shear stress. This was associated with decreased xanthine dehydrogenase (XDH) protein levels and enzymatic activity resulting in an elevated ratio of xanthine oxidase (XO) to XDH. We also studied endothelial cells lacking the p47phox subunit of the NAD(P)H oxidase. These cells exhibited dramatically depressed O2*- production and had minimal XO protein and activity. Transfection of these cells with p47phox restored XO protein levels. Finally, in bovine aortic endothelial cells, prolonged inhibition of the NAD(P)H oxidase with apocynin decreased XO protein levels and prevented endothelial cell stimulation of O2*- production in response to oscillatory shear stress. These data suggest that the NAD(P)H oxidase maintains endothelial cell XO levels and that XO is responsible for increased reactive oxygen species production in response to oscillatory shear stress.
The evolution of N2, Ar, O2, and CO2 from Martian soil as a function of humidity in the Gas Exchange Experiment are correlated with the mean level of water vapor in the Martian atmosphere. All but O2 are associated with desorption. The evolution of oxygen is consistent with the presence of alkaline earth and alkali metal superoxides; and their peroxides and the gamma-Fe2O3 in the soil can account for the generation of radioactive gas in the Labeled Release Experiment. The slower evolution of CO2 from both the Gas Exchange Experiment and the Labeled Release Experiment are associated with the direct oxidation of organics by gamma-Fe2O3. The Pyrolytic Release Experiment's second peak may be carbon suboxide as demonstrated by laboratory experiments. A necessary condition is that the polymer exists in the Martian soil. We ascribe the activity of the surface samples to the reaction of Martian particulates with an anhydrous CO2 atmosphere activated by uv and ionizing radiations. The surface particles are ultimately altered by exposure to small but significant amounts of water at the sites. From the working model, we have predicted the peculiar nature of the chemical entities and demonstrated that the model is justified by laboratory data. The final confirmation of this model will entail a return to Mars, but the nature and implications of this chemistry for the Martian surface is predicted to reveal even more about Mars with further simulations in the laboratory.
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Pressure and temperature are controlled precisely and water is rapidly removed to inhibit back reaction in process.
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Chloroflexus aurantiacus is a thermotolerant anoxygenic green phototrophic bacterium that is prominent in alkaline hot springs at temperatures between 52 and 60 C. This species often grows in the hyperoxic environment beneath cyanobacterial mats at higher temperatures up to 70 - 72 C. Cf. aurantiacus is an evolutionarily important organism since it is in the earliest branch of the eubacteria that are capable of photosynthesis and many of its characteristics can be found in other diverse groups of phototrophic bacteria. Additional information is contained in the original extended abstract.
The Viking Landers were unable to detect evidence of Life on Mars but, instead, found a chemically reactive soil capable of decomposing organic molecules.
Skeletal muscle disuse with space-flight and ground-based models (e.g., hindlimb unloading) results in dramatic skeletal muscle atrophy and weakness. Pathological conditions that cause muscle wasting (i.e., heart failure, muscular dystrophy, sepsis, COPD, cancer) are characterized by elevated "oxidative stress," where antioxidant defenses are overwhelmed by oxidant production. However, the existence, cellular mechanisms, and ramifications of oxidative stress in skeletal muscle subjected to hindlimb unloading are poorly understood. Thus we examined the effects of hindlimb unloading on hindlimb muscle antioxidant enzymes (e.g., superoxide dismutase, catalase, glutathione peroxidase), nonenzymatic antioxidant scavenging capacity (ASC), total hydroperoxides, and dichlorohydrofluorescein diacetate (DCFH-DA) oxidation, a direct indicator of oxidative stress. Twelve 6 month old Sprague Dawley rats were divided into two groups: 28 d of hindlimb unloading (n = 6) and controls (n = 6). Hindlimb unloading resulted in a small decrease in Mn-superoxide dismutase activity (10.1%) in the soleus muscle, while Cu,Zn-superoxide dismutase increased 71.2%. In contrast, catalase and glutathione peroxidase, antioxidant enzymes that remove hydroperoxides, were significantly reduced in the soleus with hindlimb unloading by 54.5 and 16.1%, respectively. Hindlimb unloading also significantly reduced ASC. Hindlimb unloading increased soleus lipid hydroperoxide levels by 21.6% and hindlimb muscle DCFH-DA oxidation by 162.1%. These results indicate that hindlimb unloading results in a disruption of antioxidant status, elevation of hydroperoxides, and an increase in oxidative stress.