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We describe the impact of post-annealing on ferroelectric-domain structures in arrays of BiFeO3 (BFO) epitaxial nanoislands, which exhibit a domain evolution from an initial 71° stripe/vortex domains to center-convergent topological domains. These results suggest that the increase and redistribution of charged defects, e.g., oxygen vacancies, in BFO nanoislands play a crucial role in driving the formation of center-type domain structures. The observation of defect-driven domain evolution in BFO nanoislands provides a path for further exploring their formation mechanism, topological properties, novel functionalities, and potential applications. [ABSTRACT FROM AUTHOR]

We present a detailed study on the effects of oxygen on the photoluminescence properties of CdSe/CdS quantum dots (QDs). We investigated the role of oxygen by performing confocal measurements on thin films as well as on single particles while rapidly exchanging the gaseous environment between oxygen and an inert gas atmosphere. We found that the deionization of negatively charged particles by oxygen depends on both the excitation power and the shell thickness of the QDs. For QDs with thin shells, which exhibit strong photoluminescence blinking, we observed that the presence of oxygen affects both band-edge carrier blinking and hot-carrier blinking. [ABSTRACT FROM AUTHOR]

To tackle the challenge of ground-level ozone pollution, this study proposed a potential catalytic design approach for ozone decomposition using Cu–Mn bimetallic oxide. This approach is grounded in an understanding of the intrinsic reactivity for catalyst and incorporates a novel potassium-driven low-temperature oxidation process for catalyst synthesis. The research highlights the creation of a highly reactive Cu–Mn oxide phase with extensive defect coverage, leading to significantly increased reaction rates. It also identifies the MnO2(100) facet as a crucial active phase, where oxygen vacancies simultaneously enhance O3 adsorption and decomposition, albeit with a concurrent risk of O2 poisoning due to the stabilization of adsorbed O2. Crucially, the incorporation of Cu offsets the effects of oxygen vacancies, influencing conversion rates and lessening O2 poisoning. The synergistic interplay between Cu and oxygen vacancies elevates the performance of the defect-rich Cu–Mn oxide catalyst. By combining computational and experimental methods, this study not only advances the understanding of the Cu–Mn oxide system for ozone decomposition but also contributes valuable insights into developing more efficient catalysts to mitigate ozone pollution. [ABSTRACT FROM AUTHOR]

The molybdenum- and tungsten-containing formate dehydrogenases from a variety of microorganisms catalyze the reversible interconversion of formate and CO2; several, in fact, function as CO2 reductases in the reverse direction under physiological conditions. CO2 reduction catalyzed by these enzymes occurs under mild temperature and pressure rather than the elevated conditions required for current industrial processes. Given the contemporary importance of remediation of atmospheric CO2 to address global warming, there has been considerable interest in the application of these enzymes in bioreactors. Equally important, understanding the detailed means by which these biological catalysts convert CO2 to formate, a useful and easily transported feedstock chemical, might also inspire the development of a new generation of highly efficient, biomimetic synthetic catalysts. Here we have examined the ability of the FdsDABG formate dehydrogenase from Cupriavidus necator to catalyze the exchange of solvent oxygen into product CO2 during the course of formate oxidation under single-turnover conditions. Negligible incorporation of 18O is observed when the experiment is performed in H218O, indicating that bicarbonate cannot be the immediate product of the enzyme-catalyzed reaction, as previously concluded. These results, in conjunction with the observation that the reductive half-reaction exhibits mildly acid-catalyzed rather than base-catalyzed chemistry, are consistent with a reaction mechanism involving direct hydride transfer from formate to the enzymes molybdenum center, directly yielding CO2. Our results are inconsistent with any mechanism in which the initial product formed on oxidation of formate is bicarbonate.

BACKGROUND: Osteosarcoma (OS) survival rates and outcome have not improved in 50 years since the advent of modern chemotherapeutics. Thus, there is a critical need for an improved understanding of the tumor microenvironment to identify better therapies. Extracellular matrix (ECM) deposition and hypoxia are known to abrogate the efficacy of various chemical and cell-based therapeutics. Here, we aim to mechanistically investigate the combinatorial effects of hypoxia and matrix deposition with the use of OS spheroids. METHODS: We use two murine OS cell lines with differential metastatic potential to form spheroids. We form spheroids of two sizes, use ascorbate-2-phosphate supplementation to enhance ECM deposition, and study cell response under standard (21% O2) and physiologic (5% O2) oxygen tensions. Finally, we examine chemotherapeutic responses to doxorubicin treatment. RESULTS: ECM production and oxygen tension are key determinants of spheroid size through cell organization based on nutrient and oxygen distribution. Interestingly, highly metastatic OS is more susceptible to chemotherapeutics compared to less metastatic OS when matrix production increases. Together, these data suggest that dynamic interactions between ECM production and oxygen diffusion may result in distinct chemotherapeutic responses despite inherent tumor aggressiveness. CONCLUSION: This work establishes OS spheroids as a valuable tool for early OS tumor formation investigation and holds potential for novel therapeutic target and prognostic indicator discovery.

Oxygen defects are introduced into PbZr0.5Ti0.5O3 films and their impact on ferroelectric behavior, linear dielectric response (LDR), and nonlinear dielectric response (NDR) is studied. Apart from a notable decrease in both polarization and LDR permittivity, the frequency spectra of LDR exhibit a distinctive loss peak. The peak position varies with temperature and oxygen defect concentration. NDR parameters, including the Rayleigh coefficient (α1), the slope (α2) correlating the imaginary part of permittivity with the ac electric field, and the slope (k) between the real and the imaginary parts of permittivity, demonstrate diverse behaviors in response to temperature and oxygen defect concentration. The similarity in the frequency spectra of tanδ and 1/k reveals the correlation between LDR and NDR induced by the presence of oxygen defects. These observations are attributed to the behavior of the single and composite defects associated with oxygen vacancies. [ABSTRACT FROM AUTHOR]

A fundamental equation of state in terms of the Helmholtz energy is presented for mixtures of nitrogen, oxygen, and argon at any composition. It is expressed in terms of the residual Helmholtz energy and can be used to calculate all thermodynamic equilibrium properties including vapor–liquid equilibria. The parameters of the equations for the pure-fluid and mixture contributions are fitted exclusively to molecular simulation data so that the model has a predictive character. The description of the mixture-specific reducing parameters is realized via generalized correlations of the critical parameters of the pure fluids so that an extension of the model to additional components can be implemented straightforwardly. Extensive comparisons to experimental data and the GERG-2008 reference equation of state show that the prediction of thermodynamic properties is satisfactory. [ABSTRACT FROM AUTHOR]

We present a method by which the direct detection effect in superconducting hot-electron bolometer mixers can be analytically accounted for with sufficient practical accuracy. This is achieved by means of the advanced uniform, non-linear two-temperature model that considers the effective temperatures of electrons and phonons alongside established material parameters. We demonstrate the efficacy of this approach for the ex situ correction of the radiance of the emission line of atomic oxygen under conditions when the direct detection causes a 30% error in the line magnitude. The correction was applied to data collected by a balloon-borne heterodyne receiver operating in the upper atmosphere of Earth. The corrected line shape and magnitude are in reasonable agreement with the predictions of atmospheric radiation transfer models. [ABSTRACT FROM AUTHOR]

Scandium nitride (ScN) is an attractive material for electronic applications due to its high n -type conductivity. Native defects and unintentional impurities may limit its electron concentration and reduce its mobility; therefore, it is important to control their formation and incorporation. Hydrogen and oxygen are unintentional impurities that are commonly present during growth and processing. They act as shallow donors in ScN and hence may be regarded as harmless or even favorable to achieving n -type conductivity. Here we show, using state-of-the-art first-principles calculations, that these impurities can be detrimental because they readily form complexes with scandium vacancies (V Sc ). Isolated V Sc have relatively high formation energies and thus have low concentrations and little impact on electronic properties. However, complexes between V Sc and either hydrogen or oxygen form more readily than the pristine vacancy and will act as both compensating and scattering centers. Our results point to the importance of controlling the incorporation of hydrogen and oxygen in ScN (and AlScN alloys) to avoid degradation of the electronic properties. [ABSTRACT FROM AUTHOR]

In this work, bottom-Schottky-structure InGaZnOx (IGZO) Schottky barrier diodes (SBDs) with sputtered PtOx anodes were fabricated and annealed in oxygen at different temperatures. Critical parameters and negative bias stress (NBS) stability of SBDs with different annealing temperatures are investigated. With the annealing temperature increases, the barrier height and rectification ratio of the SBDs exhibited a rising-then-declining trend, while the ideality factor slightly increased until 200 °C. The SBDs show up overall reliability except for a leakage current rising trend under light, which can be attributed to free electron generation from the ionized oxygen vacancy. Among all the SBDs, the 175 °C annealed ones exhibited the best overall performance, including a high barrier height of 0.89 eV, an ideality factor of 1.14, and a large rectification ratio of over 108. Compared to the initial SBDs, the annealed ones showed up great improvement in NBS stability except for the 200 °C annealed ones, which was permanently degraded and not able to recover to original states. According to experimental result analysis and IGZO material characteristics, a stability model based on the subgap trap transition from V O 2 + to VO and new V O 2 + creation was proposed, which applies to both the short-term and long-term NBS tests. The results above demonstrate that oxygen annealing at appropriate temperature is an effective method to improve both device performance and NBS stability for PtOx–IGZO SBDs. [ABSTRACT FROM AUTHOR]

This study analyzes the regulatory mechanism of oxygen vacancy concentration on tail-to-tail charged domain walls (T–T CDWs), along with the writing time, conduction current magnitude, and retention performance of through-type T–T CDWs. The research results show that the highest density and length of T–T CDWs are achieved when the oxygen vacancy concentration is 1 × 1020 cm−3. Moreover, the successful writing of through-type T–T CDWs is limited to a certain electric field range, which is controlled by oxygen vacancy concentration. An increase in the oxygen vacancy concentration leads to a decrease in the maximum and minimum threshold electric fields required for writing through-type charged domain walls. The writing time and conductivity of through-type T–T CDWs determine the information writing speed and signal strength of domain wall memories, and the oxygen vacancy concentration also plays a regulatory role in both aspects. When the oxygen vacancy concentration is 1 × 1020 cm−3, the through-type T–T CDW exhibits the fastest writing speed, requiring only 8 ns. The magnitude of the conduction current of through-type T–T CDWs is directly proportional to the oxygen vacancy concentration. The through-type T–T CDWs formed by the aggregation of oxygen vacancies exhibit excellent retention performance, making them highly promising for applications in ferroelectric domain wall memories. Our research demonstrates that oxygen vacancies have a significant regulatory effect on the morphology and current response of charged domain walls, opening up new avenues for the study of domain wall memories. [ABSTRACT FROM AUTHOR]

In view of the inherent pseudocapacitance, rich redox pairs (Nb5+/Nb4+ and Nb4+/Nb3+), and high lithiation potential (1.0–3.0 V vs Li/Li+), Nb2O5 is considered a promising anode material. However, the inherent low electronic conductivity of Nb2O5 limits its lithium storage performance, and the rate performance after carbon modification is still unsatisfactory because the intrinsic conductivity of Nb2O5 has not been substantially improved. In this experiment, taking the improvement of the intrinsic electrical conductivity of Nb2O5 as the guiding ideology, we prepared F-doped Nb2O5@fluorocarbon composites (F–Nb2O5@FC) with a large number of oxygen vacancies by one-step annealing. As the anode electrode of lithium-ion batteries, the reversible specific capacity of F–Nb2O5@FC reaches 150 mA g−1 at 5 A g−1 after 1100 cycles, and the rate performance is particularly outstanding, with a capacity up to 130 mA g−1 at 16 A g−1, which is far superior to other Nb2O5@carbon-based anode electrodes. Compared with other single conductivity sources of Nb2O5@carbon-based composites, the electrical conductivity of F–Nb2O5@FC composites is greatly improved in many aspects, including the introduction of free electrons by F− doping, the generation of oxygen vacancies, and the provision of a three-dimensional conductive network by FC. Through analytical chemistry (work function, UV–Vis diffuse reflectance spectroscopy, and EIS) and theoretical calculations, it is proved that F–Nb2O5@FC has high electrical conductivity and realizes rapid electron transfer. [ABSTRACT FROM AUTHOR]

There is a strong relationship between metazoan body size and extinction risk. However, the size selectivity and underlying mechanisms in foraminifera, a common marine protozoa, remain controversial. Here, we found that foraminifera exhibit size-dependent extinction selectivity, favoring larger groups (>7.4 log10 cubic micrometer) over smaller ones. Foraminifera showed significant size selectivity in the Guadalupian-Lopingian, Permian-Triassic, and Cretaceous-Paleogene extinctions where the proportion of large genera exceeded 50%. Conversely, in extinctions where the proportion of large genera was

With ascent to high altitude (HA), compensatory increases in cerebral blood flow and oxygen delivery must occur to preserve cerebral metabolism and consciousness. We hypothesized that this compensation in cerebral blood flow and oxygen delivery preserves tolerance to simulated hemorrhage (via lower body negative pressure, LBNP), such that tolerance is similar during sustained exposure to HA vs. low altitude (LA). Healthy humans (4F/4 M) participated in LBNP protocols to presyncope at LA (1130 m) and 5-7 days following ascent to HA (3800 m). Internal carotid artery (ICA) blood flow, cerebral delivery of oxygen (CDO2) through the ICA, and cerebral tissue oxygen saturation (ScO2) were determined. LBNP tolerance was similar between conditions (LA: 1276 ± 304 s vs. HA: 1208 ± 306 s; P = 0.58). Overall, ICA blood flow and CDO2 were elevated at HA vs. LA (P ≤ 0.01) and decreased with LBNP under both conditions (P

Climate changes significantly impact greenhouse gas emissions from wetland soil. Specifically, wetland soil may be exposed to oxygen (O2) during droughts, or to sulfate (SO42-) as a result of sea level rise. How these stressors - separately and together - impact microbial food webs driving carbon cycling in the wetlands is still not understood. To investigate this, we integrated geochemical analysis, proteogenomics, and stoichiometric modeling to characterize the impact of elevated SO42- and O2 levels on microbial methane (CH4) and carbon dioxide (CO2) emissions. The results uncovered the adaptive responses of this community to changes in SO42- and O2 availability and identified altered microbial guilds and metabolic processes driving CH4 and CO2 emissions. Elevated SO42- reduced CH4 emissions, with hydrogenotrophic methanogenesis more suppressed than acetoclastic. Elevated O2 shifted the greenhouse gas emissions from CH4 to CO2. The metabolic effects of combined SO42- and O2 exposures on CH4 and CO2 emissions were similar to those of O2 exposure alone. The reduction in CH4 emission by increased SO42- and O2 was much greater than the concomitant increase in CO2 emission. Thus, greater SO42- and O2 exposure in wetlands is expected to reduce the aggregate warming effect of CH4 and CO2. Metaproteomics and stoichiometric modeling revealed a unique subnetwork involving carbon metabolism that converts lactate and SO42- to produce acetate, H2S, and CO2 when SO42- is elevated under oxic conditions. This study provides greater quantitative resolution of key metabolic processes necessary for the prediction of CH4 and CO2 emissions from wetlands under future climate scenarios.

The oxygenation of Earths atmosphere represents the quintessential transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution; molecular clock models indicate the diversification and ecological expansion of respiratory metabolisms in the several hundred million years following atmospheric oxygenation. Across this same interval, the geological record preserves 13C enrichment in some carbonate rocks, called the Lomagundi-Jatuli excursion (LJE). By combining data from geologic and genomic records, a self-consistent metabolic evolution model emerges for the LJE. First, fermentation and methanogenesis were major processes remineralizing organic carbon before atmospheric oxygenation. Once an ozone layer formed, shallow water and exposed environments were shielded from UVB/C radiation, allowing the expansion of cyanobacterial primary productivity. High primary productivity and methanogenesis led to preferential removal of 12C into organic carbon and CH4. Extreme and variable 13C enrichments in carbonates were caused by 13C-depleted CH4 loss to the atmosphere. Through time, aerobic respiration diversified and became ecologically widespread, as did other new metabolisms. Respiration displaced fermentation and methanogenesis as the dominant organic matter remineralization processes. As CH4 loss slowed, dissolved inorganic carbon in shallow environments was no longer highly 13C enriched. Thus, the loss of extreme 13C enrichments in carbonates marks the establishment of a new microbial mat ecosystem structure, one dominated by respiratory processes distributed along steep redox gradients. These gradients allowed the exchange of metabolic by-products among metabolically diverse organisms, providing novel metabolic opportunities. Thus, the microbially induced oxygenation of Earths atmosphere led to the transformation of microbial ecosystems, an archetypal example of planetary microbiology.IMPORTANCEThe oxygenation of Earths atmosphere represents the most extensive known chemical transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution by providing oxidants independent of the sites of photosynthesis. Thus, the evolutionary changes during this interval and their effects on planetary-scale biogeochemical cycles are fundamental to our understanding of the interdependencies among genomes, organisms, ecosystems, elemental cycles, and Earths surface chemistry through time.

Amorphous ice phases are key constituents of water's complex structural landscape. This study investigates the polyamorphic nature of water, focusing on the complexities within low-density amorphous ice (LDA), high-density amorphous ice, and the recently discovered medium-density amorphous ice (MDA). We use rotationally invariant, high-dimensional order parameters to capture a wide spectrum of local symmetries for the characterization of local oxygen environments. We train a neural network to classify these local environments and investigate the distinctiveness of MDA within the structural landscape of amorphous ice. Our results highlight the difficulty in accurately differentiating MDA from LDA due to structural similarities. Beyond water, our methodology can be applied to investigate the structural properties and phases of disordered materials. [ABSTRACT FROM AUTHOR]

Reliable nanoswitch operation requires low contact voltages and stable electrical contact resistance (E C R). Surface cleanliness is crucial to prevent nanomechanical switch failure, which can occur due to the presence of insulating adventitious hydrocarbon films. In situ O2 plasma cleaning is effective but oxidizes metal surfaces. Here, the noble metal Pt, which forms PtOx, is employed to form electrodes. Previous studies report on PtOx electrical resistivity, but the effects of PtOx evolution at contacting interfaces due to electrical and mechanical stimuli have not been explored. This study investigates the impact of PtOx on E C R at low contact voltages under hot switching, cold switching, and mechanical cycling conditions. An increase in E C R upon plasma cleaning indicates the presence of a resistive PtOx layer. After hot and cold switch cycling at applied voltages of 300 mV or less, a low stable E C R is achieved. A higher contact voltage accelerates E C R stabilization. The results are consistent with PtOx film volatilization, which is primarily due to Joule heating rather than mechanical rupture. This investigation advances the understanding of interface evolution in plasma-cleaned nanoswitches. [ABSTRACT FROM AUTHOR]

Subtropical oceans contribute significantly to global primary production, but the fate of the picophytoplankton that dominate in these low-nutrient regions is poorly understood. Working in the subtropical Mediterranean, we demonstrate that subduction of water at ocean fronts generates 3D intrusions with uncharacteristically high carbon, chlorophyll, and oxygen that extend below the sunlit photic zone into the dark ocean. These contain fresh picophytoplankton assemblages that resemble the photic-zone regions where the water originated. Intrusions propagate depth-dependent seasonal variations in microbial assemblages into the ocean interior. Strikingly, the intrusions included dominant biomass contributions from nonphotosynthetic bacteria and enrichment of enigmatic heterotrophic bacterial lineages. Thus, the intrusions not only deliver material that differs in composition and nutritional character from sinking detrital particles, but also drive shifts in bacterial community composition, organic matter processing, and interactions between surface and deep communities. Modeling efforts paired with global observations demonstrate that subduction can flux similar magnitudes of particulate organic carbon as sinking export, but is not accounted for in current export estimates and carbon cycle models. Intrusions formed by subduction are a particularly important mechanism for enhancing connectivity between surface and upper mesopelagic ecosystems in stratified subtropical ocean environments that are expanding due to the warming climate.

Scientific theories on the functioning and dysfunction of the human brain require an understanding of its development-before and after birth and through maturation to adulthood-and its evolution. Here we bring together several accounts of human brain evolution by focusing on the central role of oxygen and brain metabolism. We argue that evolutionary expansion of human transmodal association cortices exceeded the capacity of oxygen delivery by the vascular system, which led these brain tissues to rely on nonoxidative glycolysis for additional energy supply. We draw a link between the resulting lower oxygen tension and its effect on cytoarchitecture, which we posit as a key driver of genetic developmental programs for the human brain-favoring lower intracortical myelination and the presence of biosynthetic materials for synapse turnover. Across biological and temporal scales, this protracted capacity for neural plasticity sets the conditions for cognitive flexibility and ongoing learning, supporting complex group dynamics and intergenerational learning that in turn enabled improved nutrition to fuel the metabolic costs of further cortical expansion. Our proposed model delineates explicit mechanistic links among metabolism, molecular and cellular brain heterogeneity, and behavior, which may lead toward a clearer understanding of brain development and its disorders.

Photodynamic therapy (PDT) is a promising cancer treatment but has limitations due to its dependence on oxygen and high-power-density photoexcitation. Here, we report polymer-based organic photosensitizers (PSs) through rational PS skeleton design and precise side-chain engineering to generate •O2- and •OH under oxygen-free conditions using ultralow-power 808 nm photoexcitation for tumor-specific photodynamic ablation. The designed organic PS skeletons can generate electron-hole pairs to sensitize H2O into •O2- and •OH under oxygen-free conditions with 808 nm photoexcitation, achieving NIR-photoexcited and oxygen-independent •O2- and •OH production. Further, compared with commonly used alkyl side chains, glycol oligomer as the PS side chain mitigates electron-hole recombination and offers more H2O molecules around the electron-hole pairs generated from the hydrophobic PS skeletons, which can yield 4-fold stronger •O2- and •OH production, thus allowing an ultralow-power photoexcitation to yield high PDT effect. Finally, the feasibility of developing activatable PSs for tumor-specific photodynamic therapy in female mice is further demonstrated under 808 nm irradiation with an ultralow-power of 15 mW cm-2. The study not only provides further insights into the PDT mechanism but also offers a general design guideline to develop an oxygen-independent organic PS using ultralow-power NIR photoexcitation for tumor-specific PDT.

PurposeDiabetes mellitus causes diabetic keratopathy (DK). This and other ocular surface disorders are underdiagnosed and problematic for affected patients as well as recipients of diabetic donor corneas. Thus, it is important to find noninvasive means to facilitate determination of the potentially vision-threatening DK. It has been reported that diabetic corneas uptake significantly less oxygen (O2) than healthy controls. However, an integral assessment of the ocular surface is missing.MethodsUsing an optic-fiber O2 micro-sensor (optrode) we demonstrated recently that the healthy ocular surface displays a unique spatiotemporal map of O2 consumption. We hypothesize that diabetes impairs the spatiotemporal profile of O2 uptake at the ocular surface.ResultsUsing streptozotocin (STZ)-induced diabetic mice, we found diminished O2 uptake and loss of the unique pattern across the ocular surface. A diabetic cornea consumes significantly less O2 at the bulbar conjunctiva and limbus, but not the central and peripheral cornea, compared to controls. Further, we show that, contrary to the healthy cornea, the diabetic cornea does not increase the O2 consumption at the limbus in the evening as the normal control.ConclusionsAltogether, our measurements reveal a previously unknown impairment in O2 uptake at the diabetic cornea, making it a potential tool to diagnose ocular surface abnormalities and suggesting a new etiology mechanism.

A key control on the magnitude of coastal eutrophication is the degree to which currents quickly transport nitrogen derived from human sources away from the coast to the open ocean before eutrophication develops. In the Southern California Bight (SCB), an upwelling-dominated eastern boundary current ecosystem, anthropogenic nitrogen inputs increase algal productivity and cause subsurface acidification and oxygen (O 2 ) loss along the coast. However, the extent of anthropogenic influence on eutrophication beyond the coastal band, and the physical transport mechanisms and biogeochemical processes responsible for these effects are still poorly understood. Here, we use a submesoscale-resolving numerical model to document the detailed biogeochemical mass balance of nitrogen, carbon and oxygen, their physical transport, and effects on offshore habitats. Despite management of terrestrial nutrients that has occurred in the region over the last 20 years, coastal eutrophication continues to persist. The input of anthropogenic nutrients promote an increase in productivity, remineralization and respiration offshore, with recurrent O 2 loss and pH decline in a region located 30-90 km from the mainland. During 2013 to 2017, the spatially averaged 5-year loss rate across the Bight was 1.3 mmol m -3 O 2 , with some locations losing on average up to 14.2 mmol m -3 O 2 . The magnitude of loss is greater than model uncertainty assessed from data-model comparisons and from quantification of intrinsic variability. This phenomenon persists for 4 to 6 months of the year over an area of 278,40 km 2 ( ∼ 30% of SCB area). These recurrent features of acidification and oxygen loss are associated with cross-shore transport of nutrients by eddies and plankton biomass and their accumulation and retention within persistent eddies offshore within the SCB.

Accurate Force Fields (FFs) are essential for Molecular Dynamics (MD) simulations of the dynamics of realistic materials in terms of atomic-level interactions. The FF parameters of short-range valence interactions can be derived through Quantum Mechanical (QM) calculations on model systems practical for QM (<300 atoms). Similarly, the dynamic electrostatic interactions can be described with methods such as QEq or PQEq that allow charges and polarization to adjust dynamically. However, accurately extracting long-range van der Waals (vdW) interactions from QM calculations poses challenges due to the absence of a definitive method to distinguish between the different energetic components of electrostatics, polarization, vdW, hydrogen bonding, and valence interactions. To do this we use the Perdew–Burke–Ernzerhof flavor of Density Functional Theory, including empirical D3 vdW corrections, to predict the Equation of State for each element (keeping any covalent bonds fixed), from which we obtain the two-body vdW nonbond potential. Here, we extend these calculations to include non-bonded parameters for the N and O columns of the periodic table so that we now describe columns 15 (N), 16 (O), 17 (F), and 18 (Ne) of the periodic table. For these 20 elements, we find that the two-body vdW potentials can all be mapped to a single universal two-body curve, with just three scaling parameters: Re, De, and L. We refer to this as the Universal NonBond (UNB) potential. We expect this to be useful for new MD simulations and a helpful starting point to obtain UNB parameters for the remainder of the periodic table. [ABSTRACT FROM AUTHOR]

We present theory and a simulation framework to model three-body collisions and gas phase recombination in dilute atom/diatom mixtures of pure oxygen (O/O2) and nitrogen (N/N2) using the Quasi-Classical Trajectory method. We formulate a three-body collision rate constant based on the lifetimes of binary collisions and initialize three-body collisions by sampling the arrival time of a third body within the lifetimes of pre-simulated binary collisions. We use this method to calculate distributions of recombined product energies, probabilities of recombination, and recombination rate constants through different collision pathways. Long-lived binary atom-diatom collisions are observed, but are too rare to play a dominant role in the recombination process for shock-heated air near the equilibrium conditions studied. The resulting recombination rate constants are within an order of magnitude of the predictions of detailed balance. Notably, the recombination simulation framework does not appeal to the principle of detailed balance and could be useful for studying conditions far from equilibrium. [ABSTRACT FROM AUTHOR]

The demand for reliable memory devices capable of operating in harsh environments, such as space and vehicles, necessitates the development of high-temperature-resistant technologies. In this study, we propose a novel ferroelectric domain wall (DW) memory utilizing BiFeO3 thin films, which exhibit exceptional retention and fatigue properties at 135 °C. Achieving this performance was made possible through precise control of the oxygen vacancy density in the epitaxial thin films induced by a post-annealing procedure conducted under an appropriate oxygen pressure of 10 Pa. Initially, prototype nano-memory devices lacking post-annealing treatment demonstrated resistive switching behavior at room temperature, with a current rectification ratio of 100:1, achieved by manipulating the uncompensated DW induced by polarization switching. With the additional annealing procedure in lower oxygen pressure, the wall current magnitude of the devices increased significantly, indicating the critical role of the oxygen vacancies in modulating the DW conductivity. Moreover, the nanodevices exhibited improved polarization retention due to oxygen vacancy-mediated charge injection that can be further enhanced at the elevated temperature. The electrons trapped deeply at the artificial DW were found to stabilize the switched polarization at the expense of reduced DW conductivity, emphasizing the importance of precise control over oxygen vacancy density for achieving a balance between high DW conductivity and excellent polarization retention. [ABSTRACT FROM AUTHOR]

Carbon monoxide poisoning is one of the most common forms of poisoning in the world. Although the primary mode of treatment, oxygen therapy, is highly effective in many cases, there are instances in which it is inadequate or inappropriate. Whereas oxygen therapy relies on high levels of a low-affinity ligand (O2) to displace a high-affinity ligand (CO) from metalloproteins, an antidote strategy relies on introducing a molecule with a higher affinity for CO than native proteins (Kantidote,CO > Kprotein,CO). Based on the fundamental chemistry of CO, such an antidote is most likely required to be an inorganic compound featuring an electron-rich transition metal. A review is provided of the protein-, supramolecular complex-, and small molecule-based CO poisoning antidote platforms that are currently under investigation.

The ability to anticipate marine habitat shifts responding to climate variability has high scientific and socioeconomic value. Here we quantify interannual-to-decadal predictability of habitat shifts by combining trait-based aerobic habitat constraints with a suite of initialized retrospective Earth System Model forecasts, for diverse marine ecotypes in the North American Large Marine Ecosystems. We find that aerobic habitat viability, defined by joint constraints of temperature and oxygen on organismal energy balance, is potentially predictable in the upper-600 m ocean, showing a substantial improvement over a simple persistence forecast. The skillful multiyear predictability is dominated by the oxygen component in most ecosystems, yielding higher predictability than previously estimated based on temperature alone. Notable predictability differences exist among ecotypes differing in temperature sensitivity of hypoxia vulnerability, especially along the northeast coast with predictability timescale ranging from 2 to 10 years. This tool will be critical in predicting marine habitat shifts in face of a changing climate.

BACKGROUND: Standard high-flow nasal cannula (HFNC) is a respiratory support device widely used to manage post-extubation hypoxemic acute respiratory failure (hARF) due to greater comfort, oxygenation, alveolar recruitment, humidification, and reduction of dead space, as compared to conventional oxygen therapy. On the contrary, the effects of the new asymmetrical HFNC interface (Optiflow® Duet system (Fisher & Paykel, Healthcare, Auckland, New Zealand) is still under discussion. Our aim is investigating whether the use of asymmetrical HFNC interface presents any relevant difference, compared with the standard configuration, on lung aeration (as assessed by end-expiratory lung impedance (EELI) measured by electrical impedance tomography (EIT)), diaphragm ultrasound thickening fraction (TFdi) and excursion (DE), ventilatory efficiency (estimated by corrected minute ventilation (MV)), gas exchange, dyspnea, and comfort. METHODS: Pilot physiological crossover randomized controlled study enrolling 20 adults admitted to the Intensive Care unit, invasively ventilated for at least 24 h, and developing post-extubation hARF, i.e., PaO2/set FiO2

Large-scale shifts in marine species biogeography have been a notable impact of climate change. An effective explanation of what drives these species shifts, as well as accurate predictions of where they might move, is crucial to effectively managing these natural resources and conserving biodiversity. While temperature has been implicated as a major driver of these shifts, physiological processes suggest that oxygen, prey, and other factors should also play important roles. We expanded upon previous temperature-based distribution models by testing whether oxygen, food web productivity, salinity, and scope for metabolic activity (the Metabolic Index) better explained the changing biogeography of Black Sea Bass (Centropristis striata) in the Northeast US. This species has been expanding further north over the past 15 years. We found that oxygen improved model performance beyond a simple consideration of temperature (ΔAIC = 799, ΔTSS = 0.015), with additional contributions from prey and salinity. However, the Metabolic Index did not substantially increase model performance relative to temperature and oxygen (ΔAIC = 0.63, ΔTSS = 0.0002). Marine species are sensitive to oxygen, and we encourage researchers to use ocean biogeochemical hindcast and forecast products to better understand marine biogeographic changes.

BackgroundDespite evidence associating inflammatory biomarkers with worse outcomes in hospitalized adults with COVID-19, trials of immunomodulatory therapies have met with mixed results, likely due in part to biological heterogeneity of participants. Latent class analysis (LCA) of clinical and protein biomarker data has identified two subtypes of non-COVID acute respiratory distress syndrome (ARDS) with different clinical outcomes and treatment responses. We studied biological heterogeneity and clinical outcomes in a multi-institutional platform randomized controlled trial of adults with severe COVID-19 hypoxemic respiratory failure (I-SPY COVID).MethodsClinical and plasma protein biomarker data were analyzed from 400 trial participants enrolled from September 2020 until October 2021 with severe COVID-19 requiring ≥ 6 L/min supplemental oxygen. Seventeen hypothesis-directed protein biomarkers were measured at enrollment using multiplex Luminex panels or single analyte enzyme linked immunoassay methods (ELISA). Biomarkers and clinical variables were used to test for latent subtypes and longitudinal biomarker changes by subtype were explored. A validated parsimonious model using interleukin-8, bicarbonate, and protein C was used for comparison with non-COVID hyper- and hypo-inflammatory ARDS subtypes.ResultsAverage participant age was 60 ± 14 years; 67% were male, and 28-day mortality was 25%. At trial enrollment, 85% of participants required high flow oxygen or non-invasive ventilation, and 97% were receiving dexamethasone. Several biomarkers of inflammation (IL-6, IL-8, IL-10, sTNFR-1, TREM-1), epithelial injury (sRAGE), and endothelial injury (Ang-1, thrombomodulin) were associated with 28- and 60-day mortality. Two latent subtypes were identified. Subtype 2 (27% of participants) was characterized by persistent derangements in biomarkers of inflammation, endothelial and epithelial injury, and disordered coagulation and had twice the mortality rate compared with Subtype 1. Only one person was classified as hyper-inflammatory using the previously validated non-COVID ARDS model.ConclusionsWe discovered evidence of two novel biological subtypes of severe COVID-19 with significantly different clinical outcomes. These subtypes differed from previously established hyper- and hypo-inflammatory non-COVID subtypes of ARDS. Biological heterogeneity may explain inconsistent findings from trials of hospitalized patients with COVID-19 and guide treatment approaches.

Background: Since publication of the 2012 Berlin definition of acute respiratory distress syndrome (ARDS), several developments have supported the need for an expansion of the definition, including the use of high-flow nasal oxygen, the expansion of the use of pulse oximetry in place of arterial blood gases, the use of ultrasound for chest imaging, and the need for applicability in resource-limited settings. Methods: A consensus conference of 32 critical care ARDS experts was convened, had six virtual meetings (June 2021 to March 2022), and subsequently obtained input from members of several critical care societies. The goal was to develop a definition that would 1) identify patients with the currently accepted conceptual framework for ARDS, 2) facilitate rapid ARDS diagnosis for clinical care and research, 3) be applicable in resource-limited settings, 4) be useful for testing specific therapies, and 5) be practical for communication to patients and caregivers. Results: The committee made four main recommendations: 1) include high-flow nasal oxygen with a minimum flow rate of ⩾30 L/min; 2) use PaO2:FiO2 ⩽ 300 mm Hg or oxygen saturation as measured by pulse oximetry SpO2:FiO2 ⩽ 315 (if oxygen saturation as measured by pulse oximetry is ⩽97%) to identify hypoxemia; 3) retain bilateral opacities for imaging criteria but add ultrasound as an imaging modality, especially in resource-limited areas; and 4) in resource-limited settings, do not require positive end-expiratory pressure, oxygen flow rate, or specific respiratory support devices. Conclusions: We propose a new global definition of ARDS that builds on the Berlin definition. The recommendations also identify areas for future research, including the need for prospective assessments of the feasibility, reliability, and prognostic validity of the proposed global definition.

The impurity or alloying atoms in YH 2 can alter the local electronic structure and so the hydrogen defect stability, as well as the H migration barrier energy. Thus, DFT calculations were employed to determine the effect of foreign elements from alkali and alkaline earth metals to transition metals and one critical impurity element, O, on H vacancy stability and retention characteristics in YH 2. Results revealed that alloying elements act as hydrogen vacancy sinks by reducing the vacancy formation energy at neighboring sites. The implantation of non-magnetic foreign elements (s1, s2, and d10 valence electrons) in hydrogen energy landscape was calculated to be minor; while the hydrogen vacancy formation energy was reduced from 1.37 eV to 1.00 eV, the migration energy barrier of hydrogen was increased from 0.87 eV to 1.15 eV for non-magnetic foreign elements. The migration energy barrier monotonically decreased with increasing d-shell occupancy, reaching as low as 0.4 eV for Cr, Mo(d4), and Fe (d4). Alloying with late transition metals (d8 and d9) moderately impacted the hydrogen vacancy formation. Finally, it was found to be O addition into the YH 2- lattice did not alter the energy landscape of hydrogen vacancies. Since alloyed YH 2 has not been studied extensively, this study provides an atomistic understanding how alloying elements and impurities trap vacancies and affects hydrogen mobility YH 2. Meanwhile, the main findings of this study may serve as guidelines for introducing alloying elements in ZrH 2 as well. [Display omitted] • Effect of impurities, including O, on H vacancy stability and mobility in YH 2 were investigated. • Impurities acted as H vacancy sinks by reducing the vacancy formation energy at neighboring sites. • Effect of the impurities were restricted to its immediate neighborhood. • An atomistic understanding was provided to relate impurities, vacancy trapping, and H mobility in YH 2. [ABSTRACT FROM AUTHOR]

In order to extend the photo-shielding range of ceria from the ultraviolet (UV) region (≤400 nm) to the high-energy short-wave blue light (BL) region (400–450 nm), three groups of ceria-based materials, including ceria nanoparticles (nano-CeO 2), cerium-oxygen-sulfur (Ce-O-S) composites and samarium-cerium-oxygen-sulfur (Sm-Ce-O-S) composites, were prepared from the perspectives of improving the preparation method, non-metal doping and metal/non-metal co-doping. Although the three groups of as-prepared samples have similar phase composition, morphology and pore structure, the Sm-Ce-O-S composites show remarkable double shielding performance for UV light and short-wave BL. Compared with nano-CeO 2 and Ce-O-S composites, Sm-Ce-O-S composites that retains the characteristics of n-type semiconductor exhibits a greater degree of lattice distortion, higher concentrations of Ce3+ (41.17 %) and oxygen vacancy (77.29 %), and narrower band gap (2.71 eV). Through the comparison of the three groups of samples, the order of modification degree from high to low is as follows: metal/non-metal co-doping > non-metal doping > improving the preparation method. This paper provides experimental and theoretical support for breaking through the bottleneck of ceria in the fields of UV shielding agents and catalysts. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A greener and more convenient alternative to traditional methods for the generation of thiyl radical as hydrogen atom transfer (HAT) catalyst is developed, using molecular oxygen to oxidize thiol without the need for chemical initiators or light irradiation. The thiol/oxygen catalysis enables selective and efficient difunctionalization of borane. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A greener and more convenient alternative to traditional methods for the generation of thiyl radical as hydrogen atom transfer (HAT) catalyst is developed, using molecular oxygen to oxidize thiol without the need for chemical initiators or light irradiation. The thiol/oxygen catalysis enables selective and efficient difunctionalization of borane. [ABSTRACT FROM AUTHOR]

Underground coal gasification is a complex physico-chemical process. UCG thermodynamic equilibrium model was established and validated, and the effects of the steam-to-oxygen ratio (RH2O/O2) and the equivalence ratio (ER) on the gasification temperature and the gaseous products were investigated. At low ER (0.08–0.14), coal is incompletely gasificated when the gasification temperature is less than the corresponding peak temperature. At high ER (0.16–0.30), coal is completely gasificated. With the increase of RH2O/O2, the gasification temperature decreases monotonically and finally tends to approach 850°C at RH2O/O2 = 4.5. H2 reaches high concentration at ER = 0.18–0.24 and RH2O/O2 = 1–3, but the change of CH4 concentration is just the opposite. CO concentration is high at RH2O/O2<1.5. In order to reach high the utilization effectiveness of oxygen, RH2O/O2 has the corresponding optimum value where the utilization effectiveness of oxygen reaches peak value at ER = 0.08–0.2. [ABSTRACT FROM AUTHOR]

Background: Current diving physiology postulates that SCUBA divers' arterial blood gas (ABG) levels vary proportionally to environmental pressure, but, to date, ABGs have only been obtained during simulated dives. Also, recent evidence supports the use of the arterial/alveolar (a:A) partial pressures of oxygen (PO2) ratio to predict the arterial PO2 (PaO2) under hyperbaric conditions from measurements obtained at 1 atmosphere absolute (ATA). This work summarizes ABGs obtained in SCUBA divers in real underwater conditions and aims to validate the a:A ratio in predicting PaO2 in this subset of individuals at depth. Methods: The study was approved by the local ethics committee. After cannulating the radial artery of the non-dominant limb, ABGs were sampled at the surface before the dive (A), at depth (15 meters of freshwater (mfw) or 42 mfw) before (B) and after (C) pedaling on a submersed bicycle for 10 minutes, and back at surface (D). After calculating the surface alveolar PO2 for each subject, the a:A ratio was obtained and used to predict PaO2 at depth. A linear regression between measured and predicted PaO2 was reported, along with the goodness-of-fit F test. Results: Six subjects performed the dive at 15 mfw, and four others at 42 mfw. The PaO2 proportionally increased at both depths, remaining stable before and after pedaling. The a:A calculated from the baseline ABG obtained at rest, out of the water, adequately predicted the PaO2 at depth (R2 = 0.97, p<0.001), better at 15 mfw but losing accuracy at 42 mfw. Conclusions: The ABGs confirmed the proportional rise of PaO2 in SCUBA divers underwater. The a:A ratio could be used to predict the magnitude of PaO2 rise at depth to limit exposure to hyperoxia, especially in repetitive recreational dives and professional divers. [ABSTRACT FROM AUTHOR]

In this work, ZrW2O8‐coated ZrC composite powders are synthesized by solid‐state reaction method using ZrC and WO3 powders. Thermodynamic analysis shows that when the molar ratio of ZrC to WO3 is larger than 5:4, ZrW2O8 cannot be synthesized by solid reaction of ZrC and WO3. The favorable molar ratio of ZrC to WO3 for solid reaction synthesis ZrW2O8 is 1:2. After reacted below 800°C for 8 hours, only ZrC in the ZrC and WO3 mixture powders partially reacts with oxygen to form ZrO2. And there is no detectable reaction between WO3 and the formed ZrO2 to produce ZrW2O8. ZrC and WO3 can synthesize ZrW2O8 at 900°C. ZrW2O8‐coated ZrC composite powders can be synthesized using powder mixtures with molar ratio of ZrC:WO3 = 1:1.7 and ZrC:WO3 = 1:1.9 after heat treatment at 1000°C for 4 hours. The synthesized ZrW2O8‐coated ZrC particles show cubic shape with obvious particles growth. The exothermic oxidation reaction of ZrC leads to a significant increase in local temperature, which is believed to trigger partial reaction between ZrO2 and WO3 to form ZrW2O8. [ABSTRACT FROM AUTHOR]

Using density functional theory (DFT) calculations, we investigated the dissociative mechanism of H 2 S adsorption and its dissociation on both clean and oxygen covered Pd (100) surface. For adsorption mechanism, the site preference was considered for H 2 S and HS monomers on both surfaces. The results suggest that H 2 S is energetically adsorbed on high symmetry sites, particularly the hollow site, on clean surface and top site on O-covered Pd (100) surface. Chemisorption of HS is stronger than H 2 S at the favorable hollow site on clean surface and O-covered surface. The energy barriers for S–H bond-breaking during the first H 2 S dehydrogenation are 0.35, 0.07, 0.32, and 0.16 eV, while for second dehydrogenation are 0.32 and 0.30 eV, respectively. On the oxygen-covered surface, the H 2 S adsorption site transitions from bridge to the top site and their energy barrier for first-order decomposition is 0.05 eV, significantly lesser than that observed on a clean surface. To examine more, the electronic densities of states as well as d-band center model were used to characterize the interaction of adsorbed H 2 S with the surfaces. Overall, our findings show that H 2 S decomposition on these surfaces is exothermic and relatively easy, but the presence of surface oxygen hinders the breaking process of H–S bond due to kinetic and thermodynamic factors. • Explored poisoning mechanism via H 2 S adsorption and dissociation on clean & O–Pd (100). • H 2 S favors hollow sites on clean Pd (100) and top sites on O–Pd (100) during adsorption. • The H 2 S adsorption site near atomic oxygen shifts to the top site from bridge site. • The potential energy profile for H 2 S decomposition was mapped on both surfaces. • H 2 S decomposition on clean and O–Pd (100) surface is a facile process. [ABSTRACT FROM AUTHOR]

The functionalization of ZnO nanoparticles has proven to be an effective alternative to avoid agglomeration and improve their physic-chemical properties. In this work, we studied the functionalization of ZnO nanoparticles using citric acid (CA) through two methods: in situ functionalization and sonochemical functionalization to compare the effects on the physicochemical and antimicrobial properties of functionalized commercial ZnO nanoparticles with those synthesized and functionalized at the same time. Both methods are considered environmentally friendly (green chemistry) since the use of chemical toxic agents was avoided and the reaction medium was water. The in situ method demonstrated the ability of CA to act as a reducing and stabilizing agent. Fourier transform infrared spectroscopy (FTIR) and RAMAN spectroscopy analyses confirmed the functionality of ZnO nanoparticles, through the formation of the COO−/ZnO complex. The wurtzite-type hexagonal crystalline structure of the ZnO nanoparticles was confirmed by X-ray diffraction (XRD). The thermogravimetric analysis (TGA) analysis showed that in situ functionalization was more favored than sonochemical functionalization since 46.66 % and 27.22 % of the organic ligand were obtained on the surface of the nanoparticles, respectively. X-ray photoelectron spectroscopy (XPS) results revealed the chemical and electronic state of the zinc which was 2+ and atomic percentages of carbon of 40.64 % and 38.35 %, as well as atomic percentages of oxygen of 38.67 and 36.78 % for ZnO-AC and ZnO-AC-R1 nanoparticles, respectively. The evaluation of the antibacterial efficiency of the nanoparticles functionalized by both methods demonstrated that they possess a superior antimicrobial activity when compared with non-fuctionalized nanoparticles. The ZnO nanoparticles synthesized and functionalized via in situ showed an efficiency of 99.99 % starting concentrations of 200 ppm. [ABSTRACT FROM AUTHOR]

Low dissolved oxygen (hypoxia) poses significant challenges to aquatic ecosystems, affecting the behavior, reproduction, and survival of aquatic organisms. Some fishes respond to hypoxia by changes in gene expression, which may be regulated by the hypoxia inducible factor (HIF) family of transcription factors. HIF abundance and activity depends upon the post-translational modification of the alpha protein subunit, although several studies indicate that HIFA mRNA abundance increases in tissues of fishes exposed to hypoxia. This study reviewed reports of laboratory exposures of adult ray-finned fishes to hypoxia and used generalized linear mixed effects models to examine the influence of HIFA gene, tissue sampled, and exposure conditions in explaining the diversity of responses seen in HIFA mRNA abundance. The frequency of hypoxia-induced increases in HIFA mRNA was poorly explained by gene, tissue, or the severity of the hypoxic exposure. Rather, the frequency of reported increases was strongly related to the extent to which studies adhered to guidelines for documenting quantitative real-time PCR methods: the frequency of hypoxia-induced increases in HIFA mRNA decreased sharply in studies with more thorough description of experimental design. Future research should (a) adhere to stringent reporting of experimental design, (b) address the relative paucity of data on HIF2A and HIF3A , and (c) determine levels of HIF alpha protein subunits. By following these recommendations, it is hoped that a more complete understanding will be gained of the role of the HIF family of transcription factors in the response of fish to hypoxia. [ABSTRACT FROM AUTHOR]

This work focused on the physico-chemical, biochemical and microbiological characterization of a new organic fertilizer based on fermented forest litter (FFL) mixed with agro-industrial by-products, on the culture realized in airtight glass bottle. Under strict anaerobiosis (0% initial oxygen concentration (IOC)), after a 16-day batch culture, the bottle-headspace analysis showed that the specific CO2 production rate was low (0.014 mL/h.g dry matter) compared to those reached under aerobic conditions (e.g. 0.464 mL/h.g dm at 21% IOC). Moreover, the culture displayed a slight fermented fruity odour, mainly due to ethanol and ethyl acetate detected in the headspace (335 µL and 58.6 µL accumulated, respectively). The FFL organic matter degradation followed by infrared spectroscopy and catabolic potential and diversity characterized by BIOLOG® EcoPlates were poor and pH dropped to 4.54. The microbiome's metabolism was oriented toward lactic fermentation with medium acidification, enrichment in lactic acid bacteria (LAB), depletion in fungi and absence of pathogens. By increasing IOC from 0 to 21%, the respirometric activity, and the catabolic potential and diversity increased. However, some enterobacteria were detected above 5% IOC. Ethanol and ethyl acetate decreased strongly with IOC, and aromatics and proteins contained in the solid matrix remained in the culture. This study showed the importance of oxygen on the final product. A 2% IOC was found to ensure an optimal balance between LAB development, preservation of functional catabolic diversity and bio-product free of microbial pathogens. [ABSTRACT FROM AUTHOR]

Background: Aging is associated with cellular and tissue responses that collectively lead to functional and structural deterioration of tissues. Poor tissue oxygenation, or hypoxia, is involved in such responses and contributes to aging. Consequently, it could be speculated that living at higher altitude, and therefore in hypoxic conditions, accelerates aging. This assumption is indeed supported by evidence from populations residing at very high altitudes (>3,500 m). In contrast, accumulating evidence suggests that living at moderate altitudes (1,500–2,500 m) is protective rather than injurious, at least for some body systems. Summary: In this review, we critically evaluate the hypothesis that the physiological responses to mild hypoxic stress associated to life at moderate altitudes provide protection from many hypoxia-related diseases through hormesis. Hormesis means that a low dose of a stressor (here hypoxia) elicits beneficial outcomes, while a higher dose can be toxic and might explain at least in part the dose-dependent contrasting effects of hypoxia on the aging processes. The lack of well-designed longitudinal studies focusing on the role of the altitude of residence, and difficulties in accounting for potentially confounding factors such as migration, ethnicity/genetics, and socioeconomic and geoclimatic conditions, currently hampers translation of related research into uncontroversial paradigms. Key Messages: Deeper investigations are required to understand the impact of altitude-related hypoxia on age-related diseases and to develop molecular markers of ageing/senescence in humans that are linked to hypoxia. However, the presented emerging evidence supports the view that hypoxia conditioning has the potential to improve life quality and expectancy. [ABSTRACT FROM AUTHOR]

Theoretical investigations for the adsorption behavior of O atoms on both Ga‐polar (+c) surface and N‐polar (−$-$c) GaN surfaces using ab initio calculations to clarify the influence of adsorption behavior on oxygen incorporation are presented. The calculations demonstrate that the O atom is stabilized by forming Ga−$-$OH bond on the flat +c plane GaN(0001) surface, while the topmost N atom is replaced by the O atom on the flat −$-$c plane GaN(0001¯$\bar{1}$) surface. The calculations using the nudged elastic band method also reveal that the energy barriers for oxygen incorporation on the flat −$-$c plane surface are comparable to that on the flat +c plane surface. Furthermore, the adsorption energy on the −$-$c plane surface drastically increases on the vicinal surface with step edges and kinks, indicating that step edges and kinks enhance the incorporation of O atoms on the −$-$c plane surfaces. The calculated results offer better understanding of the atom‐scale mechanisms for the orientation dependence of oxygen concentrations in GaN. [ABSTRACT FROM AUTHOR]

In this study, Y2O3-based resistive random-access memory (RRAM) devices with a mono-ethanolamine (MEA) stabilizer fabricated using the sol–gel process on indium tin oxide/glass substrates were investigated. The effects of MEA content on the structural, optical, chemical, and electrical characteristics were determined. As the MEA content increased, film thickness and crystallite size decreased. In particular, the increase in MEA content slightly decreased the oxygen vacancy concentration. The decreased film thickness decreased the physical distance for conductive filament formation, generating a strong electric field. However, owing to the lowest oxygen vacancy concentration, a large electrical field is required. To ensure data reliability, the endurance cycles across several devices were measured and presented statistically. Additionally, endurance performance improved with the increase in MEA content. Reduced oxygen vacancy concentration can successfully suppress the excess formation of the Ag conductive filament. This simplifies the transition from the high- to the low-resistance state and vice versa, thereby improving the endurance cycles of the RRAM devices. [ABSTRACT FROM AUTHOR]

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]

We examined the extent to which apnoea‐induced extremes of oxygen demand/carbon dioxide production impact redox regulation of cerebral bioenergetic function. Ten ultra‐elite apnoeists (six men and four women) performed two maximal dry apnoeas preceded by normoxic normoventilation, resulting in severe end‐apnoea hypoxaemic hypercapnia, and hyperoxic hyperventilation designed to ablate hypoxaemia, resulting in hyperoxaemic hypercapnia. Transcerebral exchange of ascorbate radicals (by electron paramagnetic resonance spectroscopy) and nitric oxide metabolites (by tri‐iodide chemiluminescence) were calculated as the product of global cerebral blood flow (by duplex ultrasound) and radial arterial (a) to internal jugular venous (v) concentration gradients. Apnoea duration increased from 306 ± 62 s during hypoxaemic hypercapnia to 959 ± 201 s in hyperoxaemic hypercapnia (P ≤ 0.001). Apnoea generally increased global cerebral blood flow (all P ≤ 0.001) but was insufficient to prevent a reduction in the cerebral metabolic rates of oxygen and glucose (P = 0.015–0.044). This was associated with a general net cerebral output (v > a) of ascorbate radicals that was greater in hypoxaemic hypercapnia (P = 0.046 vs. hyperoxaemic hypercapnia) and coincided with a selective suppression in plasma nitrite uptake (a > v) and global cerebral blood flow (P = 0.034 to <0.001 vs. hyperoxaemic hypercapnia), implying reduced consumption and delivery of nitric oxide consistent with elevated cerebral oxidative–nitrosative stress. In contrast, we failed to observe equidirectional gradients consistent with S‐nitrosohaemoglobin consumption and plasma S‐nitrosothiol delivery during apnoea (all P ≥ 0.05). Collectively, these findings highlight a key catalytic role for hypoxaemic hypercapnia in cerebral oxidative–nitrosative stress. Key points: Local sampling of blood across the cerebral circulation in ultra‐elite apnoeists determined the extent to which severe end‐apnoea hypoxaemic hypercapnia (prior normoxic normoventilation) and hyperoxaemic hypercapnia (prior hyperoxic hyperventilation) impact free radical‐mediated nitric oxide bioavailability and global cerebral bioenergetic function.Apnoea generally increased the net cerebral output of free radicals and suppressed plasma nitrite consumption, thereby reducing delivery of nitric oxide consistent with elevated oxidative–nitrosative stress.The apnoea‐induced elevation in global cerebral blood flow was insufficient to prevent a reduction in the cerebral metabolic rates of oxygen and glucose.Cerebral oxidative–nitrosative stress was greater during hypoxaemic hypercapnia compared with hyperoxaemic hypercapnia and coincided with a lower apnoea‐induced elevation in global cerebral blood flow, highlighting a key catalytic role for hypoxaemia.This applied model of voluntary human asphyxia might have broader implications for the management and treatment of neurological diseases characterized by extremes of oxygen demand and carbon dioxide production. [ABSTRACT FROM AUTHOR]

Lowlanders sojourning for more than 1 day at high altitude (HA) experience a reduction in plasma volume (PV) that increases haemoglobin concentration and thus restores arterial oxygen content. If the sojourn extends over weeks, an expansion of total red cell volume (RCV) occurs and contributes to the haemoconcentration. While the reduction in PV was classically attributed to an increased diuretic fluid loss, recent studies support fluid redistribution, rather than loss, as the underlying mechanism. The fluid redistribution is presumably driven by a disappearance of proteins from the circulation and the resulting reduction in oncotic pressure exerted by the plasma, although the fate of the disappearing proteins remains unclear. The RCV expansion is the result of an accelerated erythropoietic activity secondary to enhanced renal erythropoietin release, but a contribution of other mechanisms cannot be excluded. After return from HA, intravascular volumes return to normal values and the normalisation of RCV might involve selective destruction of newly formed erythrocytes, although this explanation has been strongly challenged by recent studies. In contrast to acclimatised lowlanders, native highlanders originating from the Tibetan and the Ethiopian plateaus present with a normal or only mildly elevated haemoglobin concentration. Genetic adaptations blunting the erythropoietic response to HA exposure have been proposed as an explanation for the absence of more pronounced haemoconcentration in these populations, but new evidence also supports a contribution of a larger than expected PV. The functional significance of the relatively low haemoglobin concentration in Tibetan and Ethiopian highlanders is incompletely understood and warrants further investigation. [ABSTRACT FROM AUTHOR]