Changes In Oxygen Concentration Research Articles

Gas Tunnel Engineering of Prolyl Hydroxylase Reprograms Hypoxia Signaling in Cells

AbstractCells have evolved intricate mechanisms for recognizing and responding to changes in oxygen (O2) concentrations. Here, we have reprogrammed cellular hypoxia (low O2) signaling via gas tunnel engineering of prolyl hydroxylase 2 (PHD2), a non‐heme iron dependent O2 sensor. Using computational modeling and protein engineering techniques, we identify a gas tunnel and critical residues therein that limit the flow of O2 to PHD2’s catalytic core. We show that systematic modification of these residues can open the constriction topology of PHD2’s gas tunnel. Using kinetic stopped‐flow measurements with NO as a surrogate diatomic gas, we demonstrate up to 3.5‐fold enhancement in its association rate to the iron center of tunnel‐engineered mutants. Our most effectively designed mutant displays 9‐fold enhanced catalytic efficiency (kcat/KM=830±40 M−1 s−1) in hydroxylating a peptide mimic of hypoxia inducible transcription factor HIF‐1α, as compared to WT PHD2 (kcat/KM=90±9 M−1 s−1). Furthermore, transfection of plasmids that express designed PHD2 mutants in HEK‐293T mammalian cells reveal significant reduction of HIF‐1α and downstream hypoxia response transcripts under hypoxic conditions of 1 % O2. Overall, these studies highlight activation of PHD2 as a new pathway to reprogram hypoxia responses and HIF signaling in cells.

Gas Tunnel Engineering of Prolyl Hydroxylase Reprograms Hypoxia Signaling in Cells.

Cells have evolved intricate mechanisms for recognizing and responding to changes in oxygen (O2) concentrations. Here, we have reprogrammed cellular hypoxia (low O2) signaling via gas tunnel engineering of prolyl hydroxylase 2 (PHD2), a non-heme iron dependent O2 sensor. Using computational modeling and protein engineering techniques, we identify a gas tunnel and critical residues therein that limit the flow of O2 to PHD2's catalytic core. We show that systematic modification of these residues can open the constriction topology of PHD2's gas tunnel. Using kinetic stopped-flow measurements with NO as a surrogate diatomic gas, we demonstrate up to 3.5-fold enhancement in its association rate to the iron center of tunnel-engineered mutants. Our most effectively designed mutant displays 9-fold enhanced catalytic efficiency (kcat/KM=830±40 M-1 s-1) in hydroxylating a peptide mimic of hypoxia inducible transcription factor HIF-1α, as compared to WT PHD2 (kcat/KM=90±9 M-1 s-1). Furthermore, transfection of plasmids that express designed PHD2 mutants in HEK-293T mammalian cells reveal significant reduction of HIF-1α and downstream hypoxia response transcripts under hypoxic conditions of 1 % O2. Overall, these studies highlight activation of PHD2 as a new pathway to reprogram hypoxia responses and HIF signaling in cells.

CELL-INTRINSIC METABOLIC PHENOTYPES IDENTIfiED IN GLIOBLASTOMA PATIENTS USING MASS SPECTROMETRY IMAGING OF 13C-LABELED GLUCOSE METABOLISM

Abstract AIMS Glioblastoma (GB) is an inherently heterogenous and invasive primary brain tumour. Genetic and transcriptomic studies have attempted to classify GB into subtypes that can identify therapeutic vulnerabilities and predict survival. An outstanding question and technical challenge is to visualise the metabolism of a tumour within its native microenvironment and understand to what extent its metabolism is driven by the microenvironment. METHOD Patients with GB tumours were infused with [U-13C]glucose and intra-operative multi-regional tumour samples were rapidly snap frozen for metabolic tracing analysis using mass spectrometry imaging (MSI). Tissue microenvironment was assessed using multiplexing of antibodies on immunocytochemistry (IMC) of parallel sections. Isotope tracing in human derived neurospheres and patient derived xenografts were used to confirm the presence of metabolic phenotypes detected in the human samples and to test susceptibility of each phenotype to a panel of drugs targeting cellular metabolism. RESULTS Three metabolic signatures were identified in patient GB tumours: glycolytic, oxidative and a mixed glycolytic/oxidative phenotype. The phenotypes did not correlate with microenvironmental features, including proliferation rate, immune cell infiltration, and vascularisation. The phenotypes were retained when patient derived cells were grown in vitro, or as orthotopically implanted xenografts, and were robust to changes in oxygen concentration, demonstrating their cell intrinsic nature. The spatial extent of the regions occupied by cells displaying these distinct metabolic phenotypes are large enough to be detected using clinically applicable metabolic imaging techniques. The phenotypes also demonstrate differential drug sensitivities. CONCLUSION This is the first report to demonstrate high resolution imaging of metabolic fluxes in a human tumour in vivo. In conjunction with studies on patient-derived neurospheres and orthotopically implanted xenografts we have demonstrated the presence of different metabolic phenotypes within GB that are tumour cell intrinsic and largely independent of the tumour microenvironment. These can be imaged clinically and used to stratify patients for personalised therapy.

The Inclusion Characteristics and Mechanical Properties of M2 High-Speed Steel Treated with a Vacuum Carbon Deoxidation Process

The oxygen content of M2 high-speed steel has not been intentionally controlled in industrial production through secondary refinement in vacuum furnaces. However, a lower oxygen content has a significant effect on the cleanliness, toughness, and addition of rare-earth elements to M2 high-speed steel. The changes in total oxygen content controlled by vacuum carbon deoxidation (VCD) treatment and inclusion evolution were investigated in M2 high-speed steel to understand the effects of carbon on dissolved oxygen and oxides in the carbon–oxygen (C-O) reaction process. Furthermore, the microstructure and properties of M2 high-speed steel caused by vacuum insulation and the role of reducing oxygen content in rare-earth alloying were briefly demonstrated. The results showed that the [O%] decreased from 30 ppm to 3 ppm in a vacuum at holding times above 25 min through the C-O reaction, leading to an inclusion reduction of approximately 70%. In the case of [O%] = 3 ppm in M2 high-speed steel, the addition of rare-earth elements has a greater effect on the inclusion characteristics. Lowering the oxygen content of M2 high-speed steel improves cleanliness and plays a significant role in rare-earth alloying.

Numerical Analysis on Influence of Double-Sided 3D-Patterned Cathode Catalyst Layers on Polymer Electrolyte Fuel Cell Performance

Abstract An optimized cathode catalyst layer (CCL) design can improve fuel cell performance. In this study, we tried to optimize the structure by investigating the electrochemical properties of ion and mass transport through various CCL structures with ionomer layer (IL) added using simulation numerical analysis. In the simulation, an electrochemical calculation was performed on the structure with polymer electrolyte membrane (PEM) and IL of CCL using multi-block model. The simulation was conducted by changing the aspect ratio (AR) structure of width and height of IL to five conditions so that IL is evenly distributed in catalyst layer (CL). The result confirmed that CL 3D IL AR 4.9 structure with the highest aspect ratio showed good performance. In addition, cell performance improved as the uniform reaction area with protons conducting through IL increased and the resistance of protons decreased. Finally, cell performance was predicted based on changes in oxygen concentration (OC), relative humidity (RH), and ionomer/carbon (I/C) ratio. This numerical analysis can show the reaction according to environmental and structural changes and design an optimized structure to improve cell performance.

Transient hypoxia drives soil microbial community dynamics and biogeochemistry during human decomposition.

Human decomposition in terrestrial ecosystems is a dynamic process creating localized hot spots of soil microbial activity. Longer-term (beyond a few months) impacts on decomposer microbial communities are poorly characterized and do not typically connect microbial communities to biogeochemistry, limiting our understanding of decomposer communities and their functions. We performed separate year-long human decomposition trials, one starting in spring, another in winter, integrating bacterial and fungal community structure and abundances with soil physicochemistry and biogeochemistry to identify key drivers of microbial community change. In both trials, soil acidification, elevated microbial respiration, and reduced soil oxygen concentrations occurred. Changes in soil oxygen concentrations were the primary driver of microbial succession and nitrogen transformation patterns, while fungal community diversity and abundance was related to soil pH. Relative abundance of facultative anaerobic taxa (Firmicutes and Saccharomycetes) increased during the period of reduced soil oxygen. The magnitude and timing of the decomposition responses were amplified during the spring trial relative to the winter, even when corrected for thermal inputs (accumulated degree days). Further, soil chemical parameters, microbial community structure, and fungal gene abundances remained altered at the end of 1 year, suggesting longer-term impacts on soil ecosystems beyond the initial pulse of decomposition products.

Reliability and Convergent Validity of Endurance Indices Derived from Near-Infrared Spectroscopy and Electromyography during a Bilateral Hanging Task in Amateur Rock Climbers.

Background: The ability to hang for a long time before forearm muscle fatigue is a crucial element of successful rock climbing. Electromyography (EMG) and near-infrared spectroscopy (NIRS) are also useful for measuring hemoglobin oxygenation for determining muscle endurance. In the present study, we aimed to evaluate the reliability and validity of muscle endurance indices derived using EMG and NIRS during a hanging task. Methods: A bilateral hanging task was designed to compare rock climbers and non-climbers in terms of the slopes of changes in the median frequency (MDF) and tissue oxygenation index (TOI) of forearm muscles. Results: A total of 17 participants were included in each of the two groups. The intraclass correlation coefficient (3,1) values derived for the MDF slope, TOI slope, ΔTOI, percentage change in oxygen concentration, and ΔHbt were 0.85, 0.73, 0.65, 0.75, and 0.65, respectively. The MDF slope, TOI slope, and ΔHbt differed significantly between the groups (p < 0.05). The MDF slope, TOI slopes, and ΔHbt were significantly correlated with V-scale levels for climbing (p < 0.05). Conclusions: The satisfactory reliability and observed distinctions between climbers and non-climbers imply that these indices are a valuable tool for assessing muscle endurance.

How substrate surface area and surface curvature determine kinetics and titanate formation during non-hydrothermal alkali treatment of titanium microspheres

Titanium surface nanostructuring using alkali treatment gains significant attention in a wide range of fields, such as biomaterials, (photo)catalysis, (metal/ion) sorption, CO2 capture, electrochromism and sodium-ion batteries. Even though the physicochemical properties and application potentials of the surface nanostructures are fairly well understood, there is still debate about their exact formation mechanism, limiting knowledge based structural control through altered synthesis conditions. Moreover, this knowledge is largely focused on hydrothermal synthesis conditions, whereas non-hydrothermal conditions might provide benefits towards industrial application. Also the impact of substrate properties, rather than chemical reaction conditions, on the nanostructure formation is only limitedly reported in literature. This work reveals new fundamental knowledge of non-hydrothermal alkali treatment of titanium, using microspheres by implementing, for the first time, in-situ hydrogen measurement during alkali treatment in combination with the ex-situ determination of the sodium and oxygen content in the recovered alkali treated samples, providing critical information on the role of dissolution apart from the precipitation process. The effect of surface area and surface curvature on the dissolution and precipitation process, and the resulting impact on the physicochemical properties of the obtained titanate layer is studied. This shows the much larger impact on dissolution in contrast to precipitation, knowledge that is lacking in literature, but important when implementing alkali surface nanostructuring on complex (e.g. 3D printed) substrates, and considering the prospective shift from lab-scale to industry. The Ti dissolution step was found to be mainly controlled by the total surface area, while the rate determining step was found to be the titanate precipitation, not influenced by either surface area or particle size.The changes in oxygen content in the samples after transformation of titanate into TiO2 provided a novel method for its quantification. The microspheres were analysed chemically (Raman), structurally (XRD) and morphologically (SEM, MIP), screening the effect of surface area, particle size and reaction time on the growth behaviour of the titanate layer. The porous layer structurally corresponds to Na2Ti2O4(OH)2 for all evaluated conditions, with pores in the range of 10–600 nm. Increasing surface area and particle size results in local and non-uniform titanate growth, while titanate nanowire and strut formation between the microspheres were enhanced by reduced microsphere size and prolonged reaction times.

Stage development characteristics of oxygen-lean combustion of coal in fire zone: Leap-migration mechanism, kinetic transition mechanism, and critical oxygen concentration

Effectively preventing the re-ignition of fire zones and safely unsealing enclosed fire zones are challenging. To address these issues, a thermogravimetric analysis technique was used to explore the leap-migration mechanism of the characteristic parameters (burnout index (H), comprehensive combustion performance parameters (Cb, S, and HF), and maximum combustion mass loss rate (dWmax))/temperatures (maximum pyrolysis mass loss rate point temperature (TVmax), pyrolysis endpoint temperature (Td), thermal polycondensation endpoint temperature (Tp), maximum combustion mass loss rate point temperature (TWmax), burnout temperature (Th), and combustion half-peak width (ΔT1/2)) of low-rank coal oxygen-lean combustion under different time-scale effects (TSEs). The sensitivity of characteristic parameters/temperatures to changes in oxygen concentration under coal rank transition was analyzed. Simultaneously, the kinetic real-time transformation mechanism during the oxygen-lean combustion stage progression was investigated. The results revealed that because of the competition between oxidation and pyrolysis, the leap-migration interval of characteristic parameters/temperatures for oxygen-lean combustion of low-rank coals is in the range of 5 %–3% oxygen concentration. This feature was less affected by the coal rank but is not affected by the TSE. In the low oxygen-lean range (5 %-1%), a change of oxygen concentration was more sensitive to the coal rank, and the high sensitivity of the oxygen concentration change reduced the influence of the coal rank on coal combustion performance. In addition, the apparent activation energy (Eα) curves during the early stage of combustion were relatively concentrated with the change of oxygen concentration, but relatively dispersed during the late stage of combustion. At 3 % oxygen concentration, the Eα values of different coals began to continuously decrease with increasing conversion rate, approaching the spontaneous reaction activation energy value of 40 kJ/mol. At oxygen concentration of 1 % reflected the complete limitation of the oxidation consumption reaction. Therefore, the critical oxygen concentration of typical low-rank coal oxygen-lean combustion was determined below 3 % oxygen concentration. The results of this study can provide scientific guidance for the unsealing of fire zones, and the effective prevention and control of the formation of new fire zone disasters.

Microphysiological system with integrated sensors to study the effect of pulsed electric field

This study focuses on the use of pulsed electric fields (PEF) in microfluidics for controlled cell studies. The commonly used material for soft lithography, polydimethylsiloxane (PDMS), does not fully ensure the necessary chemical and mechanical resistance in these systems. Integration of specific analytical measurement setups into microphysiological systems (MPS) are also challenging. We present an off-stoichiometry thiol-ene (OSTE)-based microchip, containing integrated electrodes for PEF and transepithelial electrical resistance (TEER) measurement and the equipment to monitor pH and oxygen concentration in situ. The effectiveness of the MPS was empirically demonstrated through PEF treatment of the C6 cells. The effects of PEF treatment on cell viability and permeability to the fluorescent dye DapI were tested in two modes: stop flow and continuous flow. The maximum permeability was achieved at 1.8 kV/cm with 16 pulses in stop flow mode and 64 pulses per cell in continuous flow mode, without compromising cell viability. Two integrated sensors detected changes in oxygen concentration before and after the PEF treatment, and the pH shifted towards alkalinity following PEF treatment. Therefore, our proof-of-concept technology serves as an MPS for PEF treatment of mammalian cells, enabling in situ physiological monitoring.

Dynamic transition of internal oxides during high dew point heat treatment in Fe-2.4Mn-0.4Si-0.13C alloy

The origin of the dynamic transition of internal oxides was clarified in Fe‐2.4Mn‐0.4Si‐0.13C‐based steel during decarburization annealing at 1073 K. High dew point with H2 gas leads to the formation of deep decarburized ferrite layers containing grain boundary internal oxides. Microstructural characterization reveals the oxide transition from Mn2SiO4 to α-SiO2 at the tip of the internal oxidation layer and from α-SiO2 to Mn2SiO4 at the middle range of the internal oxidation layer. The dynamic transition between Mn2SiO4 and α-SiO2 is understood by the depletion in Mn contents and change of oxygen content, which change the normalized driving force of both oxides. The study gives a detailed mechanism of internal oxide formation and growth in multi-phase steel during high dew point annealing. Impact statementDuring high dew-point decarburization annealing, the fluctuation of Mn contents affects the driving force to form an internal oxide, resulting in the dynamic transition between Mn2SiO4 and α-SiO2.

Oxygen Microenvironments in E. coli Biofilm Nutrient Transport Channels: Insights from Complementary Sensing Approaches.

Chemical gradients and the emergence of distinct microenvironments in biofilms are vital to the stratification, maturation and overall function of microbial communities. These gradients have been well characterised throughout the biofilm mass but the microenvironment of recently discovered nutrient transporting channels in Escherichia coli biofilms remains unexplored. This study employs three different oxygen sensing approaches to provide a robust quantitative overview of the oxygen gradients and microenvironments throughout the biofilm transport channel networks formed by E. coli macrocolony biofilms. Oxygen nanosensing combined with confocal laser scanning microscopy established that the oxygen concentration changes along the length of biofilm transport channels. Electrochemical sensing provided precise quantification of the oxygen profile in the transport channels, showing similar anoxic profiles compared with the adjacent cells. Anoxic biosensing corroborated these approaches, providing an overview of the oxygen utilisation throughout the biomass. The discovery that transport channels maintain oxygen gradients contradicts the previous literature that channels are completely open to the environment along the apical surface of the biofilm. We provide a potential mechanism for the sustenance of channel microenvironments via orthogonal visualisations of biofilm thin sections showing thin layers of actively growing cells. This complete overview of the oxygen environment in biofilm transport channels primes future studies aiming to exploit these emergent structures for new bioremediation approaches.

Triphasic Oxygen Storage in Wet Nanoparticulate Polymer of Intrinsic Microporosity (PIM-1) on Platinum: An Electrochemical Investigation.

The triphasic interaction of gases with electrode surfaces immersed in aqueous electrolyte is crucial in electrochemical technologies (fuel cells, batteries, sensors). Some microporous materials modify this interaction locally via triphasic storage capacity for gases in aqueous environments linked to changes in apparent oxygen concentration and diffusivity (as well as activity and reactivity). Here, a nanoparticulate polymer of intrinsic microporosity (PIM-1) in aqueous electrolyte is shown to store oxygen gas and thereby enhance electrochemical signals for oxygen reduction in aqueous media. Oxygen reduction current transient data at platinum disk electrodes suggest that the reactivity of ambient oxygen in aqueous electrolyte (typically Doxygen = 2.8 × 10-9 m2 s-1; coxygen = 0.3 mM) is substantially modified (to approximately Dapp,oxygen = 1.6 (±0.3) × 10-12 m2 s-1; capp,oxygen = 50 (±5) mM) with important implications for triphasic electrode processes. The considerable apparent concentration of oxygen even for ambient oxygen levels is important. Potential applications in oxygen sensing, oxygen storage, oxygen catalysis, or applications associated with other types of gases are discussed.

Monte Carlo simulations of microdosimetry and radiolytic species production at long time post proton irradiation using GATE and Geant4-DNA.

Radiobiological effectiveness of radiation in cancer treatment can be studied at different scales (molecular till organ scale) and different time post irradiation. The production of free radicals and reactive oxygen species during water radiolysis is particularly relevant to understand the fundamental mechanisms playing a role in observed biological outcomes. The development and validation of Monte Carlo tools integrating the simulation of physical, physico-chemical and chemical stages after radiation is very important to maintain with experiments. Therefore, in this study, we propose to validate a new Geant4-DNA chemistry module through the simulation of water radiolysis and Fricke dosimetry experiments on a proton preclinical beam line. In this study, we used the GATE Monte Carlo simulation platform (version 9.3) to simulate a 67.5 MeV proton beam produced with the ARRONAX isochronous cyclotron (IBA Cyclone 70XP) at conventional dose rate (0.2Gy/s) to simulate the irradiation of ultra-pure liquid water samples and Fricke dosimeter. We compared the depth dose profile with measurements performed with a plane parallel Advanced PTW 34045 Markus ionization chamber. Then, a new Geant4-DNA chemistry application proposed from Geant4 version 11.2 has been used to assess the evolution of , , , , , , and reactive species along time until 1-h post-irradiation. In particular, the effect of oxygen and pH has been investigated through comparisons with experimental measurements of radiolytic yields for and Fe3+. GATE simulations reproduced, within 4%, the depth dose profile in liquid water. With Geant4-DNA, we were able to reproduce experimental radiolytic yields 1-h post-irradiation in aerated and deaerated conditions, showing the impact of small changes in oxygen concentrations on species evolution along time. For the Fricke dosimeter, simulated G(Fe3+) is 15.97±0.2 molecules/100eV which is 11% higher than the measured value (14.4±04 molecules/100 eV). These results aim to be consolidated by new comparisons involving other radiolytic species, such as or to further study the mechanisms underlying the FLASH effect observed at ultra-high dose rates (UHDR).

Hyperbaric Oxygenation Maintains Elevated Stromal Oxygen Availability During Corneal Collagen Crosslinking with and Without Epithelial Removal

Purpose Corneal collagen cross-linking (CXL) can halt corneal ectasia. Leaving corneal epithelium intact during treatment may reduce the incidence of complications. However, it is under debate whether this reduces efficacy and if oxygen supplementation may be necessary to optimize the cross-linking effect. This study aimed to investigate the impact of hyperbaric oxygenation (HBO) on intracorneal oxygen concentrations during epi-off and epi-on CXL. Methods CXL was performed using riboflavin and ultraviolet-A (UV-A) irradiance (3 mW/cm2 for 30 min) on porcine corneas under normobaric and hyperbaric conditions, with and without supplemented oxygen, with and without epithelium. Intracorneal oxygen concentrations were continuously monitored before and during irradiation. Biomechanical properties were assessed through tensile strength testing. Results HBO alone did not cause perceivable changes in stromal oxygen concentrations. Oxygen supplementation resulted in higher oxygen concentration in corneal stroma during CXL. HBO may cause a further increase in oxygen levels, although this was not statistically significant in this study. Notably, a tendency of oxygen levels to rise continuously during UV-irradiation was observed using HBO. Biomechanical properties showend no statistically significant differences between any groups. Conclusions In this ex-vivo model, HBO increased stromal oxygen levels during CXL, regardless of the presence of corneal epithelium. The dynamics in oxygen concentrations in corneal stromal tissue during CXL suggest that time is an important factor to consider in modifications of established protocols. Also, we hypothesize that stromal levels of riboflavin and UV-A irradiance may be more critical to the CXL effect when oxygen is supplemented and epithelium is not removed.

Analysis of Oxygen Concentration in the Oral Cavity During Intravenous Sedation with Intranasal Oxygen Administration for Dental Treatment.

Intravenous sedation (IVS) with propofol (PPF) is commonly performed in dental treatment, particular in patients with dentophobia, with gag reflex, or undergoing implant surgeries, as PPF has the advantages of rapid induction and recovery. However, PPF and other intravenous sedatives may cause respiratory depression. Thus, IVS with PPF requires oxygen administration. But airway burn may occur when high-concentration oxygen is stored in the oral cavity and catches fire. For these reasons, the present study aimed to elucidate the changes in oxygen concentration (OC) under IVS with PPF and oxygen administration. Nineteen healthy male volunteers participated in the study. None of them had missing teeth, nasal congestion, or temporomandibular joint dysfunction. They were sedated with a continuous PPF infusion dose of 6 mg/kg/hr for 25 min, followed by administration of 3 L/min oxygen via a nasal cannula. The OC was measured at two sites, namely, the median maxillary anterior teeth (MMAT) and median maxillary soft palate (MMSP), before PPF infusion (baseline) and 14, 15-18 (Term 1), 19, and 20-23 (Term 2) min after the start of infusion. Compared with the values at baseline, the OC in the MMSP significantly increased at each time point, whereas the OC in the MMAT significantly increased at Term 2. Furthermore, in the comparison of the OC before and after the use of a mouth prop, the OC exhibited an upward trend, but no statistically significant differences were observed between the two time points in the MMAT and MMSP. In IVS with PPF and oxygen administration, the OC in the pharynx increases as the sedative level deepens. Oxygen administration should be temporarily discontinued, and suction should be performed to decrease the OC in the oral cavity when sparking procedures during IVS with PPF and oxygen administration are performed.

Simulation on the effect of oxygen concentration on the positive secondary streamer generated in oxygen-rich nitrogen–oxygen mixtures under atmospheric pressure

In this study, we investigated the effect of various O2 concentrations, from 20% to 90%, in nitrogen–oxygen ( N2/O2 ) mixtures on the characteristics of secondary streamers. As oxygen molecules have different molecular characteristics from nitrogen molecules in terms of ionisation threshold and electron attachment property, streamer discharges generated under various nitrogen–oxygen ratios may exhibit differing characteristics such as electron density, electric field, and radical formation. We focused on the changes in these parameters in secondary streamers using simulations. Simulations were first performed under the same conditions as those in previous experiments to compare the results of the ozone production, discharge current, and discharge emission characteristics. To compare the ozone production characteristics, simulated O radicals–the precursor of ozone–were used in the simulation for simplicity. This comparison showed that, although the absolute values of each parameter were different, the simulation exhibited a similar trend in the case of the experimentally obtained oxygen concentration dependence. After the validity of the simulation was verified to some extent via a comparison with the experiment, the results obtained from the simulation were analysed in detail. The results showed that, although the electric field strength in the secondary streamer did not change much as the oxygen concentration increased, the decrease rate of the electron density was greatly accelerated by the electron attachment reaction of oxygen. As a result, many of the electrons had already dissipate during the development of the primary streamer, and few electrons remained when the secondary streamer was formed. This effect suggests that the ratio of the amount of O radicals produced in the primary streamer to that produced in the secondary streamer changes as the oxygen concentration changes.

In Ukrainian

The CMs were obtained in argon in three stages: 1) heating (4 grad/min) to the specified temperature t in the range of 350–825 °С; 2) isothermal exposure 1 h; 3) cooling, washing from alkali and drying. Samples are denoted as CM(t). The CM yield (Y, %) and CMs elemental composition are determined. Based on low-temperature (77 K) nitrogen adsorption-desorption isotherms, integral and differential dependences of the specific surface area SDFT (m2/g) and pore volume V (cm3/g) on the average pore diameter (D, nm) were calculated by 2D-NLDFT-НS method (SAIEUS program). They were used to define volumes of ultramicropores (Vumi), supermicropores (Vsmi) and micropores (Vmi). The total pore volume V was calculated from the nitrogen amount adsorbed at a relative pressure p/p0 ~ 1.0. The S values of ultramicropores (Sumi), supermicropores (Ssmi) and micropores (Smi) were similarly determined. The CM yield was established to decrease linearly (R2 = 0.979) from 70.2 to 45.3 % with an increase in temperature from 350 to 825 °С. The carbon content decreases to a minimum value at 500 °С (72.6 %), and then increases to a maximum value (87.5 %) at 825 °С; the oxygen content changes antibatically. Two temperature regions were identified: region I (≤ 500 °С) of increasing the oxygen content due to reactions in which KOH acts as a donor of O atoms; region II (≥ 500 °C) of dominating the thermal destruction of functional groups (carboxyl, lactone, ester) with the release of CO and CO2, and condensation increasing the size of polyarenes of the CM secondary framework and formsng single Сar-Саr bonds between them. The CM(350) sample was found to contain only mesopores (D ≥ 10 nm) and macropores. An activation temperature increase to 400 °C initiates the additional formation of small-diameter micropores and mesopores. In samples CM(400) - CM(825), the main portion of newly formed pores falls on pores with D ≤ 5 nm. With increasing temperature, the micropores volume increases almost linearly (R2 = 0.992). The Vumi and Vsmi volumes increase up to 600 °C. At higher temperatures the ultramicropores volume decreases due to transforming ultramicropores (D ≤ 0.7 nm) into supermicropores (D = 0.7–2.0 nm). Portion of the ultramicropores volume changes with a maximum (23.9 %) in the CM(600) sample. The SBET specific surface area linearly (R2 = 0.992) increases with temperature up to 1729 m2/g. The SDFT values are close to SBET, but noticeably lower (1514–1530 m2/g) for CM(785)-CM(825). The micropores specific surface area increases to 1415 m2/g, and ultramicropore surface Sumi changes extremely with a maximum (526 m2/g) for the CM(600) sample, which should be expected based on the temperature dependence of the Vumi parameter. The decrease in Sumi values after the maximum is compensated by an increase in the supermicropore surface. Such an effect - the redistribution of pores by size in the microporous range (D ≤ 2 nm) with an increase in the alkaline activation temperature is not described in the literature. The portion of the micropores surface is dominant (92.6–97.0 %) in samples prepared at t ≥ 450 °C. The portion of the ultramicropore surface is maximum (56.3 %) in CM(500). Pores are revealed that do not form at all at 450–750 °C. These are supermicropores (D = 0.96–2.00 nm) and mesopores of small diameters (D = 2.0–2.82 nm). This effect was assumed to be due to the properties of the CM supramolecular framework, which is formed from polyarene fragments of the initial and activated coals having polyarenes with diameters of the same order (1.68–2.54 nm).

Modeling of the multi-cycle deep charge and discharge attenuation mechanism of non-aqueous Li–O2 batteries

Due to the high energy density, non-aqueous lithium-oxygen (Li–O2) batteries attract significant attention. However, batteries' high capacity attenuation rate under deep charge and discharge conditions remains a significant challenge. This paper presents a multi-cycle deep charge and discharge model for non-aqueous lithium-oxygen batteries, which predicts the performance of the battery during multiple deep charge and discharge cycles at high and low discharge-specific capacities. The parameter states during different discharge stages in different discharge cycles are investigated by analyzing the battery's cathode porosity, product volume fraction, and oxygen concentration changes. The study shows that as the number of cycles increases, the deposition of a small number of discharge products in the cathode altered the distribution of the newly generated products, thereby affecting the cathode structure and oxygen transport in the subsequent discharge. Moreover, depositing a small amount of discharge products can result in significant capacity attenuation in the battery. This model can accurately evaluate the deep charge and discharge performance attenuation process of non-aqueous Li–O2 batteries, which helps improve the understanding of the deep discharge attenuation mechanism of non-aqueous Li–O2 batteries.

Structure-electrochemical performance relationship in Sr2(Fe1-xVx)MoO6 anode

Structural property is becoming a powerful tool to manipulate oxygen vacancy concentration and electrochemical performance of electrode material. In this work, the structure-electrochemical performance relationship of Sr2(Fe1-xVx)MoO6 (x = 0, 0.1, 0.2 and 0.25) anode is investigated based on X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Energy Dispersive Spectrometer (EDS), BET surface area, DC four-point probe, I–V and electrochemical impedance spectra (EIS). XRD results show that all the compounds are of single phase, the tetragonal to cubic phase transition occurs at x = 0.1, which plays important role in its electrochemical performance. Firstly, the disappeared structural distortion in Sr2(Fe1.8V0.2)MoO6 and Sr2(Fe1.75V0.25)MoO6 anodes benefits electron hopping between Fe–O–Mo–O–Fe, so electron transfer processes (high-frequency semicircle) in their EIS are facilitated. Secondly, both XPS survey and EDS spectrum confirm the change in oxygen content with structural transition, Sr2(Fe1.9V0.1)MoO6 anode own higher concentration of oxygen vacancy, thus the oxygen surface exchange and diffusion process (low-frequency arc) of the corresponding cell is reduced significantly. Consequently, Sr2(Fe1.9V0.1)MoO6-based cell exhibits the highest power output (810 mW cm−2) at 850 °C. For Sr2(Fe1.8V0.2)MoO6 anode, BET surface area test reveals the slightly higher value, while its lower power density indicates that the influence of oxygen vacancy prevails over that of microstructure. Combining with EIS results, it can be deduced that Sr2(Fe1-xVx)MoO6 anodes with tetragonal symmetry own higher concentration of oxygen vacancy, thus the expected electrochemical performance is better than that of other cells. Understanding the critical role of structure is important for achieving highly active electrode material.