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Atomic-scale structures that account for the acceleration of reactivity by heterogeneous catalysts often form only under reaction conditions of high temperatures and pressures, making them impossible to observe with low-temperature, ultra-high-vacuum methods. We present velocity-resolved kinetics measurements for catalytic hydrogen oxidation on palladium over a wide range of surface concentrations and at high temperatures. The rates exhibit a complex dependence on oxygen coverage and step density, which can be quantitatively explained by a density functional and transition-state theory-based kinetic model involving a cooperatively stabilized configuration of at least three oxygen atoms at steps. Here, two oxygen atoms recruit a third oxygen atom to a nearby binding site to produce an active configuration that is far more reactive than isolated oxygen atoms. Thus, hydrogen oxidation on palladium provides a clear example of how reactivity can be enhanced on a working catalyst. [ABSTRACT FROM AUTHOR]

Air sensitivity remains a substantial barrier to the commercialization of sodium (Na)-layered oxides (NLOs). This problem has puzzled the community for decades because of the complexity of interactions between air components and their impact on both bulk and surfaces of NLOs. We show here that water vapor plays a pivotal role in initiating destructive acid and oxidative degradations of NLOs only when coupled with carbon dioxide or oxygen, respectively. Quantification analysis revealed that reducing the defined cation competition coefficient (η), which integrates the effects of ionic potential and sodium content, and increasing the particle size can enhance the resistance to acid attack, whereas using high-potential redox couples can eliminate oxidative degradation. These findings elucidate the underlying air deterioration mechanisms and rationalize the design of air-stable NLOs. [ABSTRACT FROM AUTHOR]

Consciousness is lost within seconds upon cessation of cerebral blood flow. The brain cannot store oxygen, and interruption of oxidative phosphorylation is fatal within minutes. Yet only rudimentary knowledge exists regarding cortical partial oxygen tension (PO2) dynamics under physiological conditions. Here we introduce Green enhanced Nano-lantern (GeNL), a genetically encoded bioluminescent oxygen indicator for PO2 imaging. In awake behaving mice, we uncover the existence of spontaneous, spatially defined “hypoxic pockets” and demonstrate their linkage to the abrogation of local capillary flow. Exercise reduced the burden of hypoxic pockets by 52% compared with rest. The study provides insight into cortical oxygen dynamics in awake behaving animals and concurrently establishes a tool to delineate the importance of oxygen tension in physiological processes and neurological diseases. [ABSTRACT FROM AUTHOR]

The global oceanÕs oxygen inventory is declining in response to global warming, but the future of the low-oxygen tropics is uncertain. We report new evidence for tropical oxygenation during the Paleocene-Eocene Thermal Maximum (PETM), a warming event that serves as a geologic analog to anthropogenic warming. Foraminifera-bound nitrogen isotopes indicate that the tropical North Pacific oxygen-deficient zone contracted during the PETM. A concomitant increase in foraminifera size implies that oxygen availability rose in the shallow subsurface throughout the tropical North Pacific. These changes are consistent with ocean model simulations of warming, in which a decline in biological productivity allows tropical subsurface oxygen to rise even as global ocean oxygen declines. The tropical oxygen increase may have helped avoid a mass extinction during the PETM. [ABSTRACT FROM AUTHOR]

Lipid composition determines the physical properties of biological membranes and can vary substantially between and within organisms. We describe a specific role for the viscosity of energy-transducing membranes in cellular respiration. Engineering of fatty acid biosynthesis in Escherichia coli allowed us to titrate inner membrane viscosity across a 10-fold range by controlling the abundance of unsaturated or branched lipids. These fluidizing lipids tightly controlled respiratory metabolism, an effect that can be explained with a quantitative model of the electron transport chain (ETC) that features diffusion-coupled reactions between enzymes and electron carriers (quinones). Lipid unsaturation also modulated mitochondrial respiration in engineered budding yeast strains. Thus, diffusion in the ETC may serve as an evolutionary constraint for lipid composition in respiratory membranes.

The properties of high-temperature lithospheric fluids within the early Earth are poorly known, yet many origin-of-life scenarios depend upon their characteristics. These fluids represent a key communication pathway between EarthÕs interior and hydrothermal pools. We use zircon chemistry, experiments, and modeling to infer the character of lithospheric fluids approaching 4 billion years. We constrain oxygen fugacity, chlorine content, and temperature, which allow us to model the solubility and transport of metals that are hypothesized to be crucial for the origin of life. We show that these fluids were more oxidized than the terrestrial mantle during this time and that they were interacting with near-surface aqueous systems, possibly subaerial hydrothermal pools, amplifying redox gradients in a location attractive for prebiotic molecular synthesis or sustained microbial activity. [ABSTRACT FROM AUTHOR]

Ammonia-oxidizing archaea (AOA) are one of the most abundant groups of microbes in the world’s oceans and are key players in the nitrogen cycle. Their energy metabolism—the oxidation of ammonia to nitrite—requires oxygen. Nevertheless, AOA are abundant in environments where oxygen is undetectable. By carrying out incubations for which oxygen concentrations were resolved to the nanomolar range, we show that after oxygen depletion, Nitrosopumilus maritimus produces dinitrogen and oxygen, which is used for ammonia oxidation. The pathway is not completely resolved but likely has nitric oxide and nitrous oxide as key intermediates. N. maritimus joins a handful of organisms known to produce oxygen in the dark. On the basis of this ability, we reevaluate the role of N. maritimus in oxygen-depleted marine environments. [ABSTRACT FROM AUTHOR]

Owing to the worrying increase in carbon dioxide concentrations in the atmosphere, there is a need to electrify fossil-fuel-powered chemical processes such as the Haber-Bosch ammonia synthesis. Lithium-mediated electrochemical nitrogen reduction has shown preliminary promise but still lacks sufficient faradaic efficiency and ammonia formation rate to be industrially relevant. Here, we show that oxygen, previously believed to hinder the reaction, actually greatly improves the faradaic efficiency and stability of the lithium-mediated nitrogen reduction when added to the reaction atmosphere in small amounts. With this counterintuitive discovery, we reach record high faradaic efficiencies of up to 78.0 ± 1.3% at 0.6 to 0.8 mole % oxygen in 20 bar of nitrogen. Experimental x-ray analysis and theoretical microkinetic modeling shed light on the underlying mechanism. [ABSTRACT FROM AUTHOR]

The Curiosity rover discovered fine-grained sedimentary rocks, which are inferred to represent an ancient lake and preserve evidence of an environment that would have been suited to support a martian biosphere founded on chemolithoautotrophy. This aqueous environment was characterized by neutral pH, low salinity, and variable redox states of both iron and sulfur species. Carbon, hydrogen, oxygen, sulfur, nitrogen, and phosphorus were measured directly as key biogenic elements; by inference, phosphorus is assumed to have been available. The environment probably had a minimum duration of hundreds to tens of thousands of years. These results highlight the biological viability of fluvial-lacustrine environments in the post-Noachian history of Mars.

Unconventional ferroelectricity exhibited by hafnia-based thin films—robust at nanoscale sizes—presents tremendous opportunities in nanoelectronics. However, the exact nature of polarization switching remains controversial. We investigated a La0.67Sr0.33MnO3/Hf0.5Zr0.5O2 capacitor interfaced with various top electrodes while performing in situ electrical biasing using atomic-resolution microscopy with direct oxygen imaging as well as with synchrotron nanobeam diffraction. When the top electrode is oxygen reactive, we observe reversible oxygen vacancy migration with electrodes as the source and sink of oxygen and the dielectric layer acting as a fast conduit at millisecond time scales. With nonreactive top electrodes and at longer time scales (seconds), the dielectric layer also acts as an oxygen source and sink. Our results show that ferroelectricity in hafnia-based thin films is unmistakably intertwined with oxygen voltammetry. [ABSTRACT FROM AUTHOR]

Oxygen deprivation followed by reoxygenation causes pathological responses in many disorders, including ischemic stroke, heart attacks, and reperfusion injury. Key aspects of ischemia-reperfusion can be modeled by a Caenorhabditis elegans behavior, the O2-ON response, which is suppressed by hypoxic preconditioning or inactivation of the O2-sensing HIF (hypoxia-inducible factor) hydroxylase EGL-9. From a genetic screen, we found that the cytochrome P450 oxygenase CYP-13A12 acts in response to the EGL-9-HIF-1 pathway to facilitate the O2-ON response. CYP-13A12 promotes oxidation of polyunsaturated fatty acids into eicosanoids, signaling molecules that can strongly affect inflammatory pain and ischemia-reperfusion injury responses in mammals. We propose that roles of the EGL-9-HIF-1 pathway and cytochrome P450 in controlling responses to reoxygenation after anoxia are evolutionarily conserved.

Global warming threatens marine biota with losses of unknown severity. Here, we quantify global and local extinction risks in the ocean across a range of climate futures on the basis of the ecophysiological limits of diverse animal species and calibration against the fossil record. With accelerating greenhouse gas emissions, species losses from warming and oxygen depletion alone become comparable to current direct human impacts within a century and culminate in a mass extinction rivaling those in EarthÕs past. Polar species are at highest risk of extinction, but local biological richness declines more in the tropics. Reversing greenhouse gas emissions trends would diminish extinction risks by more than 70%, preserving marine biodiversity accumulated over the past ~50 million years of evolutionary history. [ABSTRACT FROM AUTHOR]

Versatile chemical transformations of surface functional groups in two-dimensional transition-metal carbides (MXenes) open up a previously unexplored design space for this broad class of functional materials. We introduce a general strategy to install and remove surface groups by performing substitution and elimination reactions in molten inorganic salts. Successful synthesis of MXenes with oxygen, imido, sulfur, chlorine, selenium, bromine, and tellurium surface terminations, as well as bare MXenes (no surface termination), was demonstrated. These MXenes show distinctive structural and electronic properties. For example, the surface groups control interatomic distances in the MXene lattice, and Tin+1Cn (n = 1, 2) MXenes terminated with telluride (Te2−) ligands show a giant (>18%) in-plane lattice expansion compared with the unstrained titanium carbide lattice. The surface groups also control superconductivity of niobium carbide MXenes. [ABSTRACT FROM AUTHOR]

The article presents a study conducted by researcher Lars Peter Nielsen, who has found that the threads of electron-conducting cable bacteria can stretch up to 5 centimeters from deeper mud, where oxygen is scarce and hydrogen sulfide is common, to surface layers richer in oxygen. It mentions that bacteria produce compound in mud by breaking down plant debris and organic material; and in deeper sediments, hydrogen sulfide builds up as there is little oxygen to help bacteria break it down.

Oxygenation of Earth’s atmosphere and oceans occurred across three major steps during the Paleoproterozoic, Neoproterozoic, and Paleozoic eras, with each increase having profound consequences for the biosphere. Biological or tectonic revolutions have been proposed to explain each of these stepwise increases in oxygen, but the principal driver of each event remains unclear. Here we show, using a theoretical model, that the observed oxygenation steps are a simple consequence of internal feedbacks in the long-term biogeochemical cycles of carbon, oxygen, and phosphorus, and that there is no requirement for a specific stepwise external forcing to explain the course of Earth surface oxygenation. We conclude that Earth’s oxygenation events are entirely consistent with gradual oxygenation of the planetary surface after the evolution of oxygenic photosynthesis. [ABSTRACT FROM AUTHOR]

Oxygen is essential for the life of most multicellular organisms. Cells possess enzymes called molecular dioxygenases that depend on oxygen for activity. A subclass of molecular dioxygenases is the histone demethylase enzymes, which are characterized by the presence of a Jumanji-C (JmjC) domain. Hypoxia can alter chromatin, but whether this is a direct effect on JmjC-histone demethylases or due to other mechanisms is unknown. Here, we report that hypoxia induces a rapid and hypoxia-inducible factor–independent induction of histone methylation in a range of human cultured cells. Genomic locations of histone-3 lysine-4 trimethylation (H3K4me3) and H3K36me3 after a brief exposure of cultured cells to hypoxia predict the cell’s transcriptional response several hours later. We show that inactivation of one of the JmjC-containing enzymes, lysine demethylase 5A (KDM5A), mimics hypoxia-induced cellular responses. These results demonstrate that oxygen sensing by chromatin occurs via JmjC-histone demethylase inhibition. [ABSTRACT FROM AUTHOR]

How particles can move on a catalyst surface that, under the conditions of an industrial process, is highly covered by adsorbates and where most adsorption sites are occupied has remained an open question. We have studied the diffusion of O atoms on a fully CO-coveredRu(0001) surface by means of high-speed/variable-temperature scanning tunneling microscopy combined with density functional theory calculations. Atomically resolved trajectories show a surprisingly fast diffusion of the O atoms, almost as fast as on the clean surface. This finding can be explained by a“door-opening”mechanism in which local density fluctuations in the CO layer intermittently create diffusion pathways on which the O atoms can move with low activation energy. [ABSTRACT FROM AUTHOR]

The stacking of alternating charged planes in ionic crystals creates a diverging electrostatic energyÑa Òpolar catastropheÓÑthat must be compensated at the surface. We used scanning probe microscopies and density functional theory to study compensation mechanisms at the perovskite potassium tantalate (KTaO3) (001) surface as increasing degrees of freedom were enabled.The as-cleaved surface in vacuum is frozen in place but immediately responds with an insulator-to-metal transition and possibly ferroelectric lattice distortions. Annealing in vacuum allows the formation of isolated oxygen vacancies, followed by a complete rearrangement of the top layers into an ordered pattern of KO and TaO2 stripes. The optimal solution is found after exposure to water vapor through the formation of a hydroxylated overlayer with ideal geometry and charge. [ABSTRACT FROM AUTHOR]

The article presents the discussion on keeping global warming below an increase of 2°C compared with preindustrial levels. Topics include metabolic demand for oxygen to the supply of oxygen to organismal tissues as a function of temperature; and tropical oceans losing the most species as temperature and oxygen conditions exceeding the ranges tolerable for most extant species today.

The article discusses the Earth's first land ecosystem, trapped in a 3.2-billion-year-old rock formation called the MoodiesvGroup. The scientists are drilling into the terrain for the first time, retrieving fresh samples of what is expected to be Earth's first microbial producers of oxygen. The Moodies Group cores are preparing geologists for the work on the rock samples from another 3-billion-year-old terrain on the surface of Mars.

Artificial photosynthetic systems can store solar energy and chemically reduce CO2.We developed a hybrid water splitting-biosynthetic system based on a biocompatible Earth-abundant inorganic catalyst system to split water into molecular hydrogen and oxygen (H2 and O2) at low driving voltages. When grown in contact with these catalysts, Ralstonia eutropha consumed the produced H2 to synthesize biomass and fuels or chemical products from low CO2 concentration in the presence of O2. This scalable system has a CO2 reduction energy efficiency of ~50% when producing bacterial biomass and liquid fusel alcohols, scrubbing 180 grams of CO2 per kilowatt-hour of electricity. Coupling this hybrid device to existing photovoltaic systems would yield a CO2 reduction energy efficiency of ~10%, exceeding that of natural photosynthetic systems. [ABSTRACT FROM AUTHOR]

The article presents the discussion on autoantibodies neutralizing type I interferons increasing with age. Topics include SARS-CoV-2 exhibit either mild infection or severe critical COVID-19 pneumonia requiring oxygen supplementation; and mutations in interferon regulatory factor 7 (IRF7) already known to underlie severe viral infections such as fulminant influenza pneumonia.

The article presents the discussion on single-cell organism self-producing oxygen for ammonia oxidation. Topics include microbial plankton in the oceans playing a key role in the marine nitrogen and carbon cycle; and anoxic conditions producing oxygen for ammonia oxidation by itself while simultaneously reducing nitrite to nitrous oxide (N2O).

Mitochondria generate adenosine 5'-triphosphate (ATP) and are a source of potentially toxic reactive oxygen species (ROS). It has been suggested that the gradual mitochondrial dysfunction that is observed to accompany aging could in fact be causal to the aging process. Here we review findings that suggest that age-dependent mitochondrial dysfunction is not sufficient to limit life span. Furthermore, mitochondrial ROS are not always deleterious and can even stimulate pro-longevity pathways. Thus, mitochondrial dysfunction plays a complex role in regulating longevity. [ABSTRACT FROM AUTHOR]

The article presents the discussion on lower atmospheric processes being vital for assessing water loss from Mars. Topics include leading to the current cold and dry state which being important for understanding habitability; diminishing the atmospheric water reservoir through loss of atomic oxygen and hydrogen into space; and connecting dust storms, atmospheric waves, and atmospheric water.

The abundances of molecules containing more than one rare isotope have been applied broadly to determine formation temperatures of natural materials. These applications of "clumped" isotopes rely on the assumption that isotope-exchange equilibrium is reached, or at least approached, during the formation of those materials. In a closed-system terrarium experiment, we demonstrate that biological oxygen (O2) cycling drives the clumped-isotope composition of O2 away from isotopic equilibrium. Our model of the system suggests that unique biological signatures are present in clumped isotopes of O2--and not formation temperatures. Photosynthetic O2 is depleted in 18O18O and 17O18O relative to a stochastic distribution of isotopes, unlike at equilibrium, where heavy-isotope pairs are enriched. Similar signatures may be widespread in nature, offering new tracers of biological and geochemical cycling. [ABSTRACT FROM AUTHOR]

Structural alloys are often strengthened through the addition of solute atoms. However, given that solute atoms interact weakly with the elastic fields of screw dislocations, it has long been accepted that solution hardening is only marginally effective in materials with mobile screw dislocations. By using transmission electron microscopy and nanomechanical characterization, we report that the intense hardening effect of dilute oxygen solutes in pure α-Ti is due to the interaction between oxygen and the core of screw dislocations that mainly glide on prismatic planes. First-principles calculations reveal that distortion of the interstitial sites at the screw dislocation core creates a very strong but short-range repulsion for oxygen that is consistent with experimental observations.These results establish a highly effective mechanism for strengthening by interstitial solutes. [ABSTRACT FROM AUTHOR]

The article discusses the proposal by researchers, published in "Nature Geoscience" that longer days could have coaxed more photosynthesis from similar mats, allowing oxygen to build up in ancient seas and diffuse up into the atmosphere. Topics include the most substantial environmental change in the history of Earth according to geobiologist Woodward Fischer and realization by biogeochemist Judith Klatt about slowdowns in Earth's rate of spin.

In November and December 2012, the Hubble Space Telescope (HST) imaged Europa's ultraviolet emissions in the search for vapor plume activity. We report statistically significant coincident surpluses of hydrogen Lyman-a and oxygen 01 130.4-nanometer emissions above the southern hemisphere in December 2012. These emissions were persistently found in the same area over the 7 hours of the observation, suggesting atmospheric inhomogeneity; they are consistent with two 200-km-high plumes of water vapor with line-of-sight column densities of about 1020 per square meter. Nondetection in November 2012 and in previous HST images from 1999 suggests varying plume activity that might depend on changing surface stresses based on Europa's orbital phases. The plume was present when Europa was near apocenter and was not detected close to its pericenter, in agreement with tidal modeling predictions. [ABSTRACT FROM AUTHOR]

Cytochrome P450 enzymes activate oxygen at heme iron centers to oxidize relatively inert substrate carbon-hydrogen bonds. Cysteine thiolate coordination to iron is posited to increase the pKa (where Ka is the acid dissociation constant) of compound II, an iron(IV)hydroxide complex, correspondingly lowering the one-electron reduction potential of compound I, the active catalytic intermediate, and decreasing the driving force for deleterious auto-oxidation of tyrosine and tryptophan residues in the enzyme's framework. Here, we report on the preparation of an iron(IV)hydroxide complex in a P450 enzyme (CYP158) in ≤ 90% yield. Using rapid mixing technologies in conjunction with Mössbauer, ultraviolet/visible, and x-ray absorption spectroscopies, we determine a pKa value for this compound of 11.9. Marcus theory analysis indicates that this elevated pKa results in a >10,000-fold reduction in the rate constant for oxidations of the protein framework, making these processes noncompetitive with substrate oxidation. [ABSTRACT FROM AUTHOR]

The growth of high-quality single crystals of graphene by chemical vapor deposition on copper (Cu) has not always achieved control over domain size and morphology, and the results vary from lab to lab under presumably similar growth conditions. We discovered that oxygen (O) on the Cu surface substantially decreased the graphene nucleation density by passivating Cu surface active sites. Control of surface O enabled repeatable growth of centimeter-scale single-crystal graphene domains. Oxygen also accelerated graphene domain growth and shifted the growth kinetics from edge-attachment-limited to diffusion-limited. Correspondingly, the compact graphene domain shapes became dendritic. The electrical quality of the graphene films was equivalent to that of mechanically exfoliated graphene, in spite of being grown in the presence of O. [ABSTRACT FROM AUTHOR]

Oxygen (O2) adsorbed on metal oxides is important in catalytic oxidation reactions, chemical sensing, and photocatalysis. Strong adsorption requires transfer of negative charge from oxygen vacancies (VO5) or dopants, for example. With scanning tunneling microscopy, we observed, transformed, and, in conjunction with theory, identified the nature of O2 molecules on the (101) surface of anatase (titanium oxide, TiO2) doped with niobium. VO5 reside exclusively in the bulk, but we pull them to the surface with a strongly negatively charged scanning tunneling microscope tip. O2 adsorbed as superoxo (O2-) at fivefold-coordinated Ti sites was transformed to peroxo (O22-) and, via reaction with a VO, placed into an anion surface lattice site as an (O2)O species. This so-called bridging dimer also formed when O2 directly reacted with V0s at or below the surface. [ABSTRACT FROM AUTHOR]