Showing papers on "Oxygen published in 1995"

Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen

Abstract: The maintenance of life on earth, our food, oxygen, and fossil fuels depend upon the conversion of solar energy into chemical energy by biological photosynthesis carried out by green plants and photosynthetic bacteria. In this process sunlight and available abundant raw materials (water, carbon dioxide) are converted to oxygen and the reduced organic species that serve as food and fuel. A long-standing challenge has been the development of a practical artificial photosynthetic system that can roughly mimic the biological one, not by duplicating the self-organization and reproduction of the biological system nor the aesthetic beauty of trees and plants, but rather by being able to use sunlight to drive a thermodynamically uphill reaction of an abundant materials to produce a fuel. In this Account we focus on “water splitting”, the photodriven conversion of liquid water to gaseous hydrogen and oxygen:

Activated Carbon Surface Modifications by Nitric Acid, Hydrogen Peroxide, and Ammonium Peroxydisulfate Treatments

Abstract: A series of activated carbons with different degrees of activation was treated with HNO 3 , H 2 O 2 , and (NH 4 ) 2 S 2 O 8 in order to introduce oxygen surface complexes. The effects of the oxidizing treatments on the surface area, the pore texture, and the surface chemical nature were analyzed by means of N 2 and CO 2 adsorption, mercury porosimetry, FTIR, TPD, electrophoretic, and mass titration measurements. Results obtained show that the HNO 3 treatment affects the surface area and the porosity of the samples to a greater extent than the other treatments. Carboxyl groups were essentially fixed after the three treatments, although ketone and ether groups, as detected by FTIR, were also fixed after the treatments with peroxides. The most important conclusion was that the stronger acid groups were fixed after the (NH4) 2 S 2 O 5 treatment rather than after the HNO 3 treatment, in spite of the fact that this latter treatment fixed the largest number of oxygen complexes that evolved as CO 2 .

Fiber‐optic oxygen microsensors, a new tool in aquatic biology

Abstract: A new fiber-optic oxygen microsensor (microoptrode) based on dynamic fluorescence quenching has been developed to measure oxygen gradients in marine sediments and microbial mats. The microoptrodes are fabricated by immobilizing an oxygen-quenchable fluorophore at the tapered tip of an optical fiber. A special optoelectronic system has been designed to measure oxygen with these microoptrodes. It is based on small and cheap optical components and can easily be miniaturized for field applications. In contrast to oxygen microelectrodes, the new oxygen microoptrodes are easy to make, do not consume oxygen, and show no stirring dependence of the signal. In addition, they show excellent long-term stability and storage stability. Hydrogen sulfide, carbon dioxide, and other relevant chemical parameters do not interfere with the measurement. Oxygen profiles in marine sediments obtained from measurements with microoptrodes show good correlation to profiles measured with oxygen microelectrodes.

Detection of an oxygen atmosphere on Jupiter's moon Europa

Abstract: EUROPA, the second large satellite out from Jupiter, is roughly the size of Earth's Moon, but unlike the Moon, it has water ice on its surface1. There have been suggestions that an oxygen atmosphere should accumulate around such a body, through reactions which break up the water molecules and form molecular hydrogen and oxygen2,3. The lighter H2 molecules would escape from Europa relatively easily, leaving behind an atmosphere rich in oxygen. Here we report the detection of atomic oxygen emission from Europa, which we interpret as being produced by the simultaneous dissociation and excitation of atmospheric O2 by electrons from Jupiter's magnetosphere. Europa's molecular oxygen atmosphere is very tenuous, with a surface pressure about 10−11 that of the Earth's atmosphere at sea level.

Singlet Oxygen as a Reactive Intermediate in the Photodegradation of an Electroluminescent Polymer

Abstract: Singlet molecular oxygen (a{sup 1}{Delta}{sub g}) is shown to be a reactive intermediate in the photoinduced oxidative decomposition of the electroluminescent material poly(2,5-bis(5,6-dihydrocholestanoxy)-1,4-phenylenevinylene) [BCHA-PPV] in both liquid solutions and solid films. Upon irradiation of this polymer in CS{sub 2}, singlet oxygen is produced by energy transfer from the BCHA-PPV triplet state to ground state oxygen with a quantum yield of nearly 0.025. Singlet oxygen reacts with BCHA-PPV, resulting in extensive chain scission of the macromolecule. The reaction with singlet oxygen is unique to the polymer; the monomeric analog of this system, stilbene, does not appreciably react with singlet oxygen. Polymer degradation is proposed to proceed via addition of singlet oxygen in a{sub {pi}} 2+{sub {pi}}2 cycloaddition reaction to the double bond that connects phenylene groups in the macromolecule. 60 refs., 6 figs.

Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions

Abstract: Solid membranes comprising an intimate, gas-impervious, multi-phase mixture of an electronically-conductive material and an oxygen ion-conductive material and/or a mixed metal oxide of a perovskite structure are described. Electrochemical reactor components, such as reactor cells, and electrochemical reactors are also described for transporting oxygen from any oxygen-containing gas to any gas or mixture of gases that consume oxygen. The reactor cells generally comprise first and second zones separated by an element having a first surface capable of reducing oxygen to oxygen ions, a second surface capable of reacting oxygen ions with an oxygen-consuming gas, an electron-conductive path between the first and second surfaces and an oxygen ion-conductive path between the first and second surfaces. The element may further comprise (1) a porous substrate, (2) an electron-conductive metal, metal oxide or mixture thereof and/or (3) a catalyst. The reactor cell may further comprise a catalyst in the zone which comprises a passageway from an entrance end to an exit end of the element. Processes described which may be conducted with the disclosed reactor cells and reactors include, for example, the partial oxidation of methane to produce unsaturated compounds or synthesis gas, the partial oxidation of ethane, substitution of aromatic compounds, extraction of oxygen from oxygen-containing gases, including oxidized gases, ammoxidation of methane, etc. The extraction of oxygen from oxidized gases may be used for flue or exhaust gas cleanup.

Antioxidants in Nutrition, Health, and Disease

Abstract: i) Oxygen, the breath of life or oxygen, the first toxic oxidizing air pollutant ii) Metals and oxygen: Respiration, oxidation, and oxygen toxicity iii) Antioxidants: elixirs of life or media hype v) Oxidative stress vi) Free radicals and antioxidants in ageing and disease: Fact or fantasy? vii) Free radicals and cardiovascular disease

Phosphorescent Complexes of Porphyrin Ketones: Optical Properties and Application to Oxygen Sensing

Abstract: A new class of dyes, platinum(II) and palladium(II) complexes of the porphyrin ketones (or oxochlorins), exhibiting strong phosphorescence at room temperature is described. Several representative compounds were prepared and studied by spectral luminescence methods in solution. Compared to the related porphyrin and chlorin complexes, the new dyes display high photochemical stability, long wave spectral characteristics, and good compatibility with semiconductor optoelectronics (e.g., excitation by light-emitting diodes). These properties make the new dyes promising for a number of relevant applications, such as quenched phosphorescence sensing and phosphorescence probing (e.g., in binding assays). Analytical application of the porphyrin ketone complexes to phosphorescence lifetime-based sensing of molecular oxygen is described. Platinum(II) octaethylporphine ketone was dissolved in a polystyrene layer to give an oxygen-sensitive film. Oxygen measurements were performed with a prototype fiber-optic instrument based on solid-state components, such as light-emitting diodes and photodiodes. The instrument measured phosphorescence lifetime via changes in phase shift. The phosphorescence lifetime was determined to change from about 61.4 μs at zero oxygen to 16.3 μs in air (210 hPa of oxygen) at 22 °C. The analytically useful range of the sensor was 0-210 hPa of oxygen partial pressure, with a detection limit of 1.5 hPa. The precision of the device was 1.0 hPa at 210 hPa of oxygen and 0.5 hPa at zero oxygen.

Control of mitochondrial and cellular respiration by oxygen.

Abstract: Control and regulation of mitochondrial and cellular respiration by oxygen is discussed with three aims: (1) A review of intracellular oxygen levels and gradients, particularly in heart, emphasizes the dominance of extracellular oxygen gradients. Intracellular oxygen pressure,\(p_{O_2 } \), is low, typically one to two orders of magnitude below incubation conditions used routinely for the study of respiratory control in isolated mitochondria. The\(p_{O_2 } \) range of respiratory control by oxygen overlaps with cellular oxygen profiles, indicating the significance of\(p_{O_2 } \) in actual metabolic regulation. (2) A methodologically detailed discussion of high-resolution respirometry is necessary for the controversial topic of respiratory control by oxygen, since the risk of methodological artefact is closely connected with far-reaching theoretical implications. Instrumental and analytical errors may mask effects of energetic state and partially explain the divergent views on the regulatory role of intracellular\(p_{O_2 } \). Oxygen pressure for half-maximum respiration,p50, in isolated mitochondria at state 4 was 0.025 kPa (0.2 Torr; 0.3 ΜM O2), whereasp50 in endothelial cells was 0.06–0.08 kPa (0.5 Torr). (3) A model derived from the thermodynamics of irreversible processes was developed which quantitatively accounts for near-hyperbolic flux/\(p_{O_2 } \) relations in isolated mitochondria. The apparentp50 is a function of redox potential and protonmotive force. The protonmotive force collapses after uncoupling and consequently causes a decrease inp50. Whereas it is becoming accepted that flux control is shared by several enzymes, insufficient attention is paid to the notion of complementary kinetic and thermodynamic flux control mechanisms.

UV-B-Induced PR-1 Accumulation Is Mediated by Active Oxygen Species.

Abstract: Depletion of the stratospheric ozone layer may result in an increase in the levels of potentially harmful UV-B radiation reaching the surface of the earth. We have found that UV-B is a potent inducer of the plant pathogenesis-related protein PR-1 in tobacco leaves. UV-B fluences required for PR-1 accumulation are similar to those of other UV-B-induced responses. The UV-B-induced PR-1 accumulation was confined precisely to the irradiated area of the leaf but displayed no leaf tissue specificity. A study of some of the possible components of the signal transduction pathway between UV-B and PR-1 induction showed that photosynthetic processes are not essential, and photoreversible DNA damage is not involved. Antioxidants and cycloheximide were able to block the induction of PR-1 by UV-B, and treatment of leaves with a generator of reactive oxygen resulted in the accumulation of PR-1 protein. These results demonstrate an absolute requirement for active oxygen species and protein synthesis in this UV-B signal transduction pathway. In contrast, we also show that other elicitors, notably salicylic acid, are able to elicit PR-1 via nonreactive oxygen species-requiring pathways.

Analysis of the Effects of Oxygen Supply and Demand on Hypoxic Fraction in Tumors

Abstract: The extent of hypoxic regions in a tumor tissue depends on the arrangement, blood flow rate and blood oxygen content of microvessels, and on the tissue's oxygen consumption rate. Here, the effects of blood flow rate, blood oxygen content and oxygen consumption on hypoxic fraction are simulated theoretically, for a region whose microvascular geometry was derived from observations of a transplanted mammary andenocarcinoma (R3230AC) in a rat dorsal skin flap preparation. In the control state, arterial PO2 is 100 mmHg, consumption rate is 2.4 cm3 O2/100 g/min, and hypoxic fraction (tissue with PO2 < 3 mmHg) is 30%. Hypoxia is abolished by a reduction in consumption rate of at least 30%, relative to control, or an increase in flow rate by a factor of 4 or more, or an increase in arterial PO2 by a factor of 11 or more. These results suggest that reducing oxygen consumption rate may be more effective than elevating blood flow or oxygen content as a method to reduce tumor hypoxia.

Oxidative coupling of methane in a mixed-conducting perovskite membrane reactor

Abstract: Ionic-electronic mixed-conducting perovskite-type oxide La0.6Sr0.4Co0.8Fe0.2O3 was applied as a dense membrane for oxygen supply in a reactor for methane coupling. The oxygen permeation properties were studied in the pO2-range of 10?3?1 bar at 1073?1273 K, using helium as a sweeping gas at the permeate side of the membrane. The oxygen semi-permeability has a value close to 1 mmol m?2 s?1 at 1173 K with a corresponding activation energy of 130?140 kJ/mol. The oxygen flux is limited by a surface process at the permeate side of the membrane. It was found that the oxygen flux is only slightly enhanced if methane is admixed with helium. Methane is converted to ethane and ethene with selectivities up to 70%, albeit that conversions are low, typically 1?3% at 1073?1173 K. When oxygen was admixed with methane rather than supplied through the membrane, selectivities obtained were found to be in the range 30?35%. Segregation of strontium was found at both sides of the membrane, being seriously affected by the presence of an oxygen pressure gradient across it. The importance of a surface limited oxygen flux for application of perovskite membranes for methane coupling is emphasized.

Biological sulphide oxidation in a fed‐batch reactor

Abstract: This study shows that, in a sulphide-oxidizing bioreactor with a mixed culture of Thiobacilli, the formation of sulphur and sulphate as end-products from the oxidation of sulphide can be controiledinstantaneously and reversibiy by the amount of oxygen supplied. It was found that at sulphide loading rates of up to 2.33 mmol7/L . h, both products can be formed already at oxygen concentrations below 0.1 mg/L. Because the microorganisms tend to form sulphate rather than forming sulphur, the oxygen concentration is not appropriate to optimize the sulphur production. Within less than 2 h, the system can be switched reversibly from sulphur to sulphate formation by adjusting the oxygen flow. This is below the minimum doubling time (2.85 h) of, e.g., Thiobacillus neapolitanus and Thiobacillus 0,(18) which indicates that one metabolic type of organism can probably perform both reactions. Under highly oxygen-limited circumstances, that is, at an oxygen/sulphide consumption ratio below 0.7 mol . h(-1) mol . h(-1) thiosulphate is abundantly formed. Because the chemical sulphide oxidation results mainly in the formation of thiosulphate, it is concluded that, under these circumstances, the biological oxidation capacity of the system is lower than the chemical oxidation capacity. The oxidation rate of the chemical sulphide oxidation can be described by a first-order process (k =-0.87 h(-1)).(c) 1995 John Wiley & Sons, Inc.

The adsorption and photodesorption of oxygen on the tio2(110) surface

Abstract: We have investigated the adsorption and thermal conversion of molecular oxygen (O2) states on the TiO2(110) surface by making use of the distinct photodesorption behavior of each adsorption state. Oxygen chemisorbs at the oxygen vacancy defect sites on the annealed TiO2(110) surface at 105 K to a saturation coverage of less than 0.12 monolayers (ML), producing mostly the α‐O2 species which is observed to undergo slow photodesorption. Upon heating this surface to above 250 K, the α‐O2 is converted to the β‐O2 state which can photodesorb at a significantly higher rate. The β‐O2 species dissociates above 400 K to produce atomic oxygen, eliminating the oxygen anionic vacancies. Both the α‐ and β‐photodesorption processes have a threshold energy at the TiO2 band gap (3.1 eV), indicating a substrate excitation mediated process. The photodesorption time‐profile is fitted with an exponential decay function with a cross section of ∼8×10−17 cm2 for the α‐O2 and ∼1.5×10−15 cm2 for the β‐O2 species at a photon energy...

Glucose hydrolysis and oxidation in supercritical water

Abstract: Glucose hydrolysis and oxidation occurred rapidly in supercritical water at 246 bar and at 425 to 600°C. A diverse set of products, present in the liquid-phase reactor effluent and also subject to hydrolysis, was formed. At 600°C and a 6-s reactor residence time, glucose is completely gasified, even in the absence of oxygen. In the presence of oxygen, destruction of liquid-phase products is enhanced, with none found above 550°C at a 6-s reactor residence time. Major products formed wee acetic acid, acetonylacetone, propenoic acid, and acetaldehyde in the liquid phase, and carbon monoxide, carbon dioxide, methane, ethane, ethylene, and hydrogen in the gas phase. Methane and hydrogen were present among the products at temperatures up to 600°C for reactor residence times of 6 s.

The range of PaO2 variation determines the severity of oxygen-induced retinopathy in newborn rats

Abstract: Purpose. This study was conducted to determine the potential influence of PaO 2 fluctuation on the retinal neovascular response known to occur in newborn rats exposed to hyperoxic conditions. As an inherent corollary, the authors also defined the relationship between the fraction of inspired oxygen (Fio 2 ) and the arterial blood oxygen tension (Pao 2 ) in newborn rats. Methods. Experiment 1 was composed of several oxygen-exposure protocols in which atmospheres of 10% oxygen concentration were alternated with different higher levels of ambient oxygen (50%, 40%, 30%, and room air). In experiment 2, two alternating oxygen concentrations were made to converge toward room air (20.9% oxygen) with each successive group of four treatment groups. These included another group exposed to alternating 50% and 10% oxygen, a group exposed to alternating 45% and 12.5% oxygen concentrations, one exposed to alternating concentrations of 40% and 15% oxygen, and a final group exposed to 35% and room air oxygen concentrations. In each case, oxygen was alternated between the two exposure concentrations every 24 hours. The term ΔFio 2 is used to designate the difference in the two oxygen concentrations to which a treatment group was subjected, applying the units of fraction of inspired oxygen (i.e., ΔFio 2 = 0.4 for the exposure to alternating 50% and 10% oxygen). At birth, litters of albino rats were placed in each of these environments for 13 or 14 days, after which Pao 2 and retinal vascular development were assessed in some rats. The remainder were removed to room air for 4 days before the incidence and severity of abnormal neovascularization were measured. Results. Pao 2 and Fio 2 were directly and linearly correlated (r 2 0.998). In experiment 1, the extent of retinal vascular development on removal from oxygen was a linear function of ΔFiO 2 . Retinal neovascularization subsequently occurred in all rats exposed to alternating 50% and 10% or 40% and 10% oxygen concentrations, but only a third of the 30% and 10% exposure group, indicating a minimum threshold for proliferative disease at ΔFio 2 = 0.2. In experiment 2, retinal avascularity also increased linearly with increasing ΔFio 2 . There was a threshold for neovascularization between the exposure to alternating 45% and 12.5% oxygen and the 40% and 15% oxygen exposure (100% versus 4.8% incidence of neovascularization), indicating a requirement of ≤12.5% oxygen episodes to stimulate a consistent proliferative response. Conclusions. These results suggest that Pao 2 fluctuation and degree of hypoxia may have more influence on proliferative retinal disease in newborn rats than the extended hyperoxia that has historically received greater attention. Experimental designs that address the inherent differences in pulmonary iunction between intrinsically healthy animals and compromised premature infants are of substantial value to our understanding of the pathogenesis of retinopathy of prematurity. Invest Ophthalmol Vis Sci. 1995 ;36 :2063-2070.

Method and apparatus for forming silicon oxide film by chemical vapor deposition

Abstract: The subject is a plasma-enhanced CVD process for depositing a silicon oxide film on a substrate by using an organosilicon compound such as tetraethoxysilane and oxygen or ozone as the essential reactants. The disclosed CVD method uses a plasma containing oxygen ions, and the density of oxygen ions impinging on the substrate surface is cyclically decreased and increased with a short period such as, e.g., 1 sec. In extreme cases which are rather preferable, the effect of the oxygen plasma is cyclically nullified and returned to a maximum to thereby alternate plasma CVD and plain thermal CVD. The obtained film is comparable in film properties to silicon oxide films deposited by known plasma CVD methods and, when the substrate has steps such as aluminum wiring lines, is better in step coverage and gap filling capability. The film exhibits a still better profile when hydrogen peroxide gas or an alternative hydrogen containing gas is added to the reactant gas mixture.

Development of a Submicrometer Optical Fiber Oxygen Sensor

Abstract: A submicrometer optical fiber oxygen sensor has been fabricated, based on the fluorescence quenching of tris-(1,10-phenanthroline)ruthenium(II) chloride in the presence of oxygen or dissolved oxygen. The Ru compound has been incorporated into acrylamide polymer that is attached covalently to a silanized optical fiber tip surface by photoinitiated polymerization. Leaching of the sensing reagent from the polymer host matrix has been minimized by the optimization of the ratio between the acrylamide monomer and the cross-linker, N,N-methylenebisacrylamide. The sensor is fully reversible and highly reproducible. A standard deviation of approximately 2% for 10 consecutive fluorescence measurements has been observed for several oxygen concentrations. The sample volume required for measurements is 100 fL. An absolute detection limit of 1 x 10(-17) mol is achieved. This is an improvement by a factor of 10(6) as compared to other existing optical fiber oxygen sensors.