O2 Atmosphere Research Articles

UV irradiation during fluorescence measurements affects the structures and fluorescence properties of isolated lignins in solution

There are no reports on the stability of autofluorescence, although lignins and their solutions are known to exhibit autofluorescence. An aim of this study is to investigate spectral change of lignin autofluorescence under prolonged excitation with ultraviolet (UV). Both fluorescence spectra of softwood milled wood lignin (MWL) and kraft lignin (SKL) in propylene glycol significantly changed upon an UV irradiation at 280 nm under O2 and Ar atmospheres even for 10 min. By the further irradiation, the autofluorescence intensities were remarkably changed together with the emission wavelengths. However, no tendency in the autofluorescence change was observed. The change varied between lignin preparations and gas atmosphere. These phenomena should be caused by autoxidation upon UV irradiation, and the reaction resulted in not only photodegradation but also photopolymerization.

First principles theoretical of designing Sandwich-like Metallic BP4 Monolayer as Anode for Alkali Metal-ion Batteries.

Phosphorene has been widely used as anode material for batteries. However, the huge volume change during charging and discharging process, the semiconductor properties, and the high open circuit voltage limit its application. Based on this, by introducing the electron-deficient boron atoms into blue phosphorene, we proposed a P-rich sandwich-like BP4 monolayer by density functional theory calculation and particle swarm optimization. The BP4 monolayer shows good thermodynamic and dynamic stability, as well as chemical stability in O2 atmosphere, mainly due to the strengthened P-P bond of the outer layer by the middle boron atoms adopting sp3 hybridization. According to the band structure, the BP4 monolayer shows metallic property, which is beneficial to electron conductivity. Furthermore, compared with blue phosphorene and black phosphorene, the P-rich BP4 monolayer shows higher theoretical capacity for Li, Na, and K of 1193.90, 1119.28, and 397.97 mA·h·g-1, respectively. The lattice constant of BP4 monolayer increases only 3.73 (Li), 2.52 (Na) after Li/Na fully adsorbed on the anode. More importantly, the wettability of BP4 monolayer in the electrolyte is comparable to that of graphene. These findings show that the stable sandwich-like BP4 monolayer has potential as a lightweight anode material.

Mineralisation controls for the diverse Cape manganese occurrences, South Africa

Abstract The Cape Fold Belt, comprising folded sedimentary sequences from predominantly the Palaeozoic Cape Supergroup, hosts a multitude of manganese occurrences and mineral deposits, many of which were subject to historical mining activity. Although size, grade and quality issues negate their modern-day exploitation for the steel-making process, the mechanisms by which Mn has enriched at these sites holds scientific value for our understanding of low-temperature Mn (bio-)geochemical cycling. Deposits located within the Cape Fold Belt comprise structure-hosted Mn deposits and a little described class of Mn mound deposits associated with chalybeate thermal springs (temperature = 41 to 48°C). Although the relationships between the two remain tenuous, detailed study of both classes provides insight into the conditions that favour Mn accumulation in the near-surface and sub-aerial environments. Comparisons between the physicochemistry of manganiferous- and non-manganiferous thermal springs suggest that manganese solubility is favoured by warm, acidic and slightly reducing fluids with elevated salinity. Transport, and associated fluid focusing typically within highly permeable sandstone units, serves to locate Mn mineralisation in near-surface structurally-complex trap sites that provide both accommodation space and conditions that are sufficiently oxidising. Where manganiferous spring waters spill out at surface, oxidation is caused by contact with atmospheric O2 to form Mn mound deposits, and ambient Mn-oxidising microbiota (e.g., genus Ramlibacter, and members of Burkholderiales, Rhodocyclaceae, and Oxalobacteraceae) are likely to play a role in enhancing the kinetics of this process. Relative to the structure-hosted deposits, these Mn mound deposits are typically lower grade (higher iron content) and relatively friable (high porosity and fine grain sizes). Supergene and diagenetic processes can lead to localised upgrade of the Mn mound material, although typically not to ore grade.

Hydrolysis of carbonyl sulfide using non-ionic surfactant-modified mesoporous γ-Al2O3 catalysts with high efficiency

Carbonyl sulfur (COS) was difficult to be removed by conventional desulfurization technologies because of its stable chemical properties. Mesoporous γ-Al2O3 (MA) showed excellent potential for hydrolysis of COS, but the catalyst life was greatly shortened with the progress of the reaction. Therefore, improving the catalyst life is the key to MA which can apply to hydrolysis of COS. In this study, P123 modified mesoporous γ-Al2O3 (P-MA) catalyst was prepared by sol–gel method, and it was regulated by template agent and acidity regulator. These preparation conditions of P-MA were optimized to improve the hydrolysis efficiency of COS. The effects of temperature, space velocity, relative humidity and oxygen concentration for the hydrolysis efficiency of COS were studied. The results show that the optimized P-MA catalyst is suitable for COS low-temperature hydrolysis reaction, and it can maintain 99 % for 10 h under the tough reaction conditions. The only crystal of P-MA was γ-Al2O3 with large specific surface area and uniform distribution pore, which are beneficial to the COS hydrolysis. In addition, the hydrolysis efficiency of COS can also remain 97 % for 10 h in the O2 and CO2 atmosphere, indicating that the P-MA catalyst has a specific anti-poisoning ability. The kinetics and reaction mechanism of COS catalytic hydrolysis were studied, which showed that the adsorption of H2S was the key to hindering the continuous reaction. The P-MA can effectively inhibit the adsorption of H2S, which greatly improved COS hydrolysis life of P-MA. This study provided a theoretical basis for the application of Al2O3 catalyst in the COS hydrolysis.

Influence of the atmosphere on the phosphorescence of a brominated diphenylphosphine oxide-ethyl naphthaleneimide dyad.

The molecular dyad diphenylphosphine-ethyl bromine naphthaleneimide (Br-DPPENI) emits strong fluorescence and phosphorescence. We studied the intensity and lifetime of the phosphorescence of Br-DPPENI embedded in PMMA films in atmospheres of air, He, Ar, N2, and O2 as a function of pressure between vacuum and ambient pressure (1 bar). The experiment was performed in the frequency domain with a two-channel lock-in amplifier, and the data were analyzed with the polar plot or phasor technique. Reversible shortening of the lifetime due to triplet-triplet annihilation was found in the presence of atmospheric or pure oxygen. With small modulation frequencies, an additional slow component of the phosphorescence dynamics is observed, which is ascribed to the diffusion of oxygen into the sample films.

Regulation of Rubisco activity by interaction with chloroplast metabolites.

Rubisco activity is highly regulated and frequently limits carbon assimilation in crop plants. In the chloroplast, various metabolites can inhibit or modulate Rubisco activity by binding to its catalytic or allosteric sites, but this regulation is complex and still poorly understood. Using rice Rubisco, we characterised the impact of various chloroplast metabolites which could interact with Rubisco and modulate its activity, including photorespiratory intermediates, carbohydrates, amino acids; as well as specific sugar-phosphates known to inhibit Rubisco activity - CABP (2-carboxy-d-arabinitol 1,5-bisphosphate) and CA1P (2-carboxy-d-arabinitol 1-phosphate) through in vitro enzymatic assays and molecular docking analysis. Most metabolites did not directly affect Rubisco in vitro activity under both saturating and limiting concentrations of Rubisco substrates, CO2 and RuBP (ribulose-1,5-bisphosphate). As expected, Rubisco activity was strongly inhibited in the presence of CABP and CA1P. High physiologically relevant concentrations of the carboxylation product 3-PGA (3-phosphoglyceric acid) decreased Rubisco activity by up to 30%. High concentrations of the photosynthetically derived hexose phosphates fructose 6-phosphate (F6P) and glucose 6-phosphate (G6P) slightly reduced Rubisco activity under limiting CO2 and RuBP concentrations. Biochemical measurements of the apparent Vmax and Km for CO2 and RuBP (at atmospheric O2 concentration) and docking interactions analysis suggest that CABP/CA1P and 3-PGA inhibit Rubisco activity by binding tightly and loosely, respectively, to its catalytic sites (i.e. competing with the substrate RuBP). These findings will aid the design and biochemical modelling of new strategies to improve the regulation of Rubisco activity and enhance the efficiency and sustainability of carbon assimilation in rice.

Changes in raspberry sensory quality after harvest as affected by CO2 atmospheres

CO2 atmospheres have the potential to influence raspberry (Rubus idaeus L.) sensory quality after harvest. Our study determined the optimal postharvest atmosphere to extend shelf life without negatively impacting sensory quality. Raspberry fruit were stored at 5 ℃ in 15, 8, 5 or 0.03 kPa CO2 in combination with 6, 13, 16 or 21 kPa O2, respectively. A trained sensory panel conducted a descriptive sensory evaluation of the raspberry fruit after 5, 10, and 13 d of storage. Raspberries stored in 15 kPa CO2 with 6 kPa O2 (15 kPa) atmosphere followed by that in 8 kPa CO2 with 13 kPa O2 (8 kPa) atmosphere had higher firmness than that in 5 kPa CO2 with 16 kPa O2 (5 kPa) and 0.03 kPa CO2 with 21 kPa O2 (0.03 kPa) atmosphere. Panelists found that raspberries stored in 8 kPa and 15 kPa CO2 atmosphere had the least off-flavor and highest tartness. Raspberries stored in 8 kPa scored highest in raspberry flavor with substantial juiciness and sweetness scores. The fermentative volatiles acetaldehyde and ethanol were higher in raspberries stored in 15 kPa despite the low off-flavor scores, while most other raspberry volatiles decreased with increasing CO2 concentration, including flavor-related volatiles α-ionone, α-terpineol, limonene and linalool. After 10 d, the quality of raspberries stored in 0.03 kPa or 5 kPa atmosphere had degraded considerably. While 15 kPa atmosphere prolonged shelf life the longest, 8 kPa atmosphere prolonged shelf life to 10 d while maintaining sensory quality and was the best overall atmosphere.

Controlling Pericellular Oxygen Tension in Cell Culture Reveals Distinct Breast Cancer Responses to Low Oxygen Tensions.

In oxygen (O2)-controlled cell culture, an indispensable tool in biological research, it is presumed that the incubator setpoint equals the O2 tension experienced by cells (i.e., pericellular O2). However, it is discovered that physioxic (5% O2) and hypoxic (1% O2) setpoints regularly induce anoxic (0% O2) pericellular tensions in both adherent and suspension cell cultures. Electron transport chain inhibition ablates this effect, indicating that cellular O2 consumption is the driving factor. RNA-seq analysis revealed that primary human hepatocytes cultured in physioxia experience ischemia-reperfusion injury due to cellular O2 consumption. A reaction-diffusion model is developed to predict pericellular O2 tension a priori, demonstrating that the effect of cellular O2 consumption has the greatest impact in smaller volume culture vessels. By controlling pericellular O2 tension in cell culture, it is found that hypoxia vs. anoxia induce distinct breast cancer transcriptomic and translational responses, including modulation of the hypoxia-inducible factor (HIF) pathway and metabolic reprogramming. Collectively, these findings indicate that breast cancer cells respond non-monotonically to low O2, suggesting that anoxic cell culture is not suitable for modeling hypoxia. Furthermore, it is shown that controlling atmospheric O2 tension in cell culture incubators is insufficient to regulate O2 in cell culture, thus introducing the concept of pericellular O2-controlled cell culture.

Electrochemical Hydrogen Peroxide Generation and Activation Using a Dual-Cathode Flow-Through Treatment System: Enhanced Selectivity for Contaminant Removal by Electrostatic Repulsion.

To oxidize trace concentrations of organic contaminants under conditions relevant to surface- and groundwater, air-diffusion cathodes were coupled to stainless-steel cathodes that convert atmospheric O2 into hydrogen peroxide (H2O2), which then was activated to produce hydroxyl radicals (·OH). By separating H2O2 generation from its activation and employing a flow-through electrode consisting of stainless-steel fibers, the two processes could be operated efficiently in a manner that overcame mass-transfer limitations for O2, H2O2, and trace organic contaminants. The flexibility resulting from separate control of the two processes made it possible to avoid both the accumulation of excess H2O2 and the energy losses that take place after H2O2 has been depleted. The decrease in treatment efficacy occurring in the presence of natural organic matter was substantially lower than that typically observed in homogeneous advanced oxidation processes. Experiments conducted with ionized and neutral compounds indicated that electrostatic repulsion prevented negatively charged ·OH scavengers from interfering with the oxidation of neutral contaminants. Energy consumption by the dual-cathode system was lower than values reported for other technologies intended for small-scale drinking water treatment systems. The coordinated operation of these two cathodes has the potential to provide a practical, inexpensive way for point-of-use drinking water treatment.

The Influence of Annealing on the Compositional and Crystallographic Properties of Sputtered Li–Al–O Thin Films

Li–Al–O materials are interesting for several applications. Herein, a Li–Al–O thin‐film materials library, deposited by inert magnetron sputtering and postdeposition annealing in O2 atmosphere, is used to study the effects of different annealing temperatures (300–850 °C) and durations (1 min to 7 h) on crystallinity and composition of the films. X‐ray photoelectron spectroscopy depth profiling reveals inhomogeneous compositional depth profiles of conventionally annealed films (300–650 °C, 3–7 h) with increased Li contents toward the film surface and increased Al contents toward the film–substrate interface, as confirmed by a combination of Rutherford backscattering spectrometry and deuteron‐induced nuclear reaction analysis. The minimum temperature for the formation of crystalline LiAlO2 in the otherwise amorphous films is 550 °C. The undesired inhomogeneous depth profiles are transformed into homogeneous ones by rapid thermal annealing (750–850 °C, 1–10 min), while simultaneously causing the formation of crystalline LiAlO2. Therefore, rapid thermal annealing is shown to be more suitable than conventional annealing for the thermal processing of Li–Al–O thin films. Moreover, this conclusion is expected to have broader relevance beyond Li–Al–O materials, as it is likely to apply to other Li metal oxides, of which there are many technologically relevant ones.

User-friendly carbon-cycle modelling and aspects of Phanerozoic climate change

Carbon-cycle modelling is essential for testing the main carbon sources and sinks as climate forcings, and we introduce and describe GEOCARB_NET, a graphical user interface for the geologic carbon and sulfur cycle model GEOCARBSULFvolc. The software system is menu-driven, user-friendly, and the user is never far removed from the basic input parameters from which atmospheric CO2 and O2 concentrations can be derived. GEOCARB_NET is supplied with several published models and the user can easily test and refine these models with different parametrizations. GEOCARB_NET also contains libraries of models and proxy data, which easily can be compared with each other. Our examples focus on how to use GEOCARB_NET in the context of Phanerozoic climate change and highlights how certain key input parameters can seriously affect reconstructed CO2 levels.

Three enzymes governed the rise of O2 on Earth

Current views of O2 accumulation in Earth history depict three phases: The onset of O2 production by ∼2.4 billion years ago; 2 billion years of stasis at ∼1 % of modern atmospheric levels; and a rising phase, starting about 500 million years ago, in which oxygen eventually reached modern values. Purely geochemical mechanisms have been proposed to account for this tripartite time course of Earth oxygenation. In particular the second phase, the long period of stasis between the advent of O2 and the late rise to modern levels, has posed a puzzle. Proposed solutions involve Earth processes (geochemical, ecosystem, day length). Here we suggest that Earth oxygenation was not determined by geochemical processes. Rather it resulted from emergent biological innovations associated with photosynthesis and the activity of only three enzymes: 1) The oxygen evolving complex of cyanobacteria that makes O2; 2) Nitrogenase, with its inhibition by O2 causing two billion years of oxygen level stasis; 3) Cellulose synthase of land plants, which caused mass deposition and burial of carbon, thus removing an oxygen sink and therefore increasing atmospheric O2. These three enzymes are endogenously produced by, and contained within, cells that have the capacity for exponential growth. The catalytic properties of these three enzymes paved the path of Earth's atmospheric oxygenation, requiring no help from Earth other than the provision of water, CO2, salts, colonizable habitats, and sunlight.

Boosting the activity of BiVOx via vanadium-promotion for highly selective oxidation of biomass-derived xylose toward formic acid

Formic acid is a versatile and promising value-added chemical derived from the chemoselective transformation of renewable biomass resources. However, achieving a high production rate of formic acid remains a pivotal and enormous challenge. Herein, we synthesized a sequence of BiVOx catalysts based on vanadium-promotion by a facile and cost-effective strategy for selective oxidation of biomass-derived xylose in water under O2 atmosphere. Particularly, the resultant Bi1V2Ox exhibited a remarkably enhanced catalytic activity, higher selectivity toward formic acid, and excellent recyclability, giving a yield of 75.8 % and a production rate of formic acid (9.22 mol FA molV−1h−1) at 170 °C within only 20 min. Such pronounced improved performance was largely attributed to the synergistic effect between V and Bi species, with higher surface area, abundant surface acidity, as well as stronger adsorption energy, meanwhile efficiently suppressing the formation of undesired by-products. This study demonstrates that the promotion of V in BiVOx leads to more efficient catalytic oxidation of xylose to formic acid, and with further driven research that proved great potential for generating formic acid from renewable biomass resources for future industrial application.

Multimodal Insights of Regeneration Dynamics of Spent Bimetallic Catalysts by Full Field Hyperspectral Quick‐EXAFS Imaging and Environmental Transmission Electron Microscopy

AbstractMultimodal measurements involving time‐resolved Ni and Cu K edges Quick‐EXAFS, time‐resolved hyperspectral Full Field Quick‐EXAFS imaging with micrometer spatial resolution and aberration‐corrected Environmental Scanning Transmission Electron Microscopy have been performed over a NiCu catalyst used for the ethanol steam reforming reaction to establish structure‐activity relationships after regeneration. Activated catalysts are composed of 5–10 nm monometallic nickel nanoparticles and larger bimetallic randomly alloyed NiCu nanoparticles (NPs). After 3 h time on reactive stream, the monitoring of the regeneration of the coked deactivated catalyst at 500 °C by Full Field hyperspectral XAS imaging evidences that the oxidative propagation front affects faster metallic Ni species than metallic Cu ones as a result of the stronger oxophilic character of the former compared to the latter. Furthermore, ESTEM characterization of the deactivated catalyst when passing from H2 to O2 atmosphere at 500 °C for burning coke deposits evidences the fragmentation of the Ni and NiCu‐NPs driven by the Kirkendall effect in the encapsulated coked catalyst. The resulting increase of specific surface of active species is assumed to be responsible for the activity boost observed after regeneration.

Short-timescale Spatial Variability of Ganymede’s Optical Aurora

Ganymede’s auroras are the product of complex interactions between its intrinsic magnetosphere and the surrounding Jovian plasma environment and can be used to derive both atmospheric composition and density. In this study, we analyzed a time series of Ganymede’s optical auroras taken with Keck I/HIRES during eclipse by Jupiter on 2021 June 8 UTC, one day after the Juno flyby of Ganymede. The data had sufficient signal-to-noise in individual 5 minute observations to allow for the first high-cadence analysis of the spatial distribution of the optical aurora brightness and the ratio between the [O i] 630.0 and 557.7 nm disk-integrated auroral brightnesses—a quantity diagnostic of the relative abundances of O, O2, and H2O in Ganymede’s atmosphere. We found that the hemisphere closer to the centrifugal equator of Jupiter’s magnetosphere (where electron number density is highest) was up to twice as bright as the opposing hemisphere. The dusk (trailing) hemisphere, subjected to the highest flux of charged particles from Jupiter’s magnetosphere, was also consistently almost twice as bright as the dawn (leading) hemisphere. We modeled emission from simulated O2 and H2O atmospheres during eclipse and found that if Ganymede hosts an H2O sublimation atmosphere in sunlight, it must collapse on a faster timescale than expected to explain its absence in our data given our current understanding of Ganymede’s surface properties.

Comprehensive modeling of ignition and combustion of multiscale aluminum particles under various pressure conditions

The ignition and combustion of aluminum particles are crucial to achieve optimal energy release in propulsion and power systems within a limited residence time. This study seeks to develop theoretical ignition and combustion models for aluminum particles ranging from 10 nm to 1000 μm under wide pressure ranges of normal to beyond 10 MPa. Firstly, a parametric analysis illustrates that the convective heat transfer and heterogeneous surface reaction are strongly influenced by pressure, which directly affects the ignition process. Accordingly, the ignition delay time can be correlated with pressure through the pb relationship, with b increasing from –1 to –0.1 as the system transitions from the free molecular regime to the continuum regime. Then, the circuit comparison analysis method was used to interpret an empirical formula capable of predicting the ignition delay time of aluminum particles over a wide range of pressures in N2, O2, H2O, and CO2 atmospheres. Secondly, an analysis of experimental data indicates that the exponents of pressure dependence in the combustion time of large micron-sized particles and nanoparticles are –0.15 and –0.65, respectively. Further, the dominant combustion mechanism of multiscale aluminum particles was quantitatively demonstrated through the Damköhler number (Da) concept. Results have shown that aluminum combustion is mainly controlled by diffusion as Da > 10, by chemical kinetics when Da ≤ 0.1, and codetermined by both diffusion and chemical kinetics when 0.1 < Da ≤ 10. Finally, an empirical formula was proposed to predict the combustion time of multiscale aluminum particles under high pressure, which showed good agreement with available experimental data.

An insect lac blanket-mimetic and degradable shellac hydrogel/chitosan packaging film with controllable gas permeation for fresh-cut vegetables preservation

Fresh-cut products are extremely perishable due to the processing operations, and the atmosphere environment, especially CO2, O2 and H2O, could profoundly affect their shelf life. Herein, an insect “lac blanket”-mimetic and facile strategy was proposed for fresh-cut vegetables preservation, employing porous shellac hydrogel microparticles as gas “switches” in chitosan film to regulate CO2, O2 and H2O vapor permeability. Thus, the shellac hydrogel/chitosan hybrid film presented the controllable and wide range of gas permeability, compared with the chitosan film. The shellac-COOH nanoscale vesicles aggregated to form shellac hydrogel network via hydrophobic binding. The shellac hydrogel microparticles played a certain lubricating effect on the hybrid film casting solution. The hydrogen bond network between shellac hydrogel and chitosan contributed to the excellent mechanical properties of the hybrid film. The hybrid film also exhibited remarkable water-resistant, antifogging properties, optical transparency and degradability. The hybrid packaging films prepared through this strategy could adjust the internal gas (CO2, O2, H2O and ethylene) contents within the packages, and further exhibited admirable preservation performance on three fresh-cut vegetables with different respiratory metabolisms. This gas permeation-controlled strategy has great potential in fresh food preservation and various other applications that need a modified atmosphere.

Contribution of oxygen vacancies to phase transition and ferroelectricity of Al:HfO2 films

We investigate the effects of oxygen vacancies on the ferroelectric behavior of Al:HfO2 films annealed in O2 and N2 atmosphere. X-ray photoelectron spectroscopy results showed that the O/Hf atomic ratio was 1.88 for N2-annealed samples and 1.96 for O2-annealed samples, implying a neutralization of oxygen vacancies during O2 atmosphere annealing. The O2-annealed films exhibited an increasing remanent polarization from 23 μC cm−2 to 28 μC cm−2 after 104 cycles, with a negligible leakage current density of ∼2 μA cm−2, while the remanent polarization decreased from 29 μC cm−2 to 20 μC cm−2 after cycling in the N2-annealed films, with its severe leakage current density decreasing from ∼1200 μA cm−2 to ∼300 μA cm−2. A phase transition from the metastable tetragonal (t) phase to the low-temperature stable orthorhombic (o) phase and monoclinic (m) phase was observed during annealing. As a result of the fierce· competition between the t-to-o transition and the t-to-m transition, clear grain boundaries of several ruleless atomic layers were formed in the N2-annealed samples. On the other hand, the transition from the t-phase to the low-temperature stable phase was found to be hindered by the neutralization of oxygen vacancies, with almost continuous grain boundaries observed. The results elucidate the phase transformation caused by oxygen vacancies in the Al:HfO2 films, which may be helpful for the preparation of HfO2-based films with excellent ferroelectricity.

High Proton Conduction in the Octahedral Layers of Fully Hydrated Hexagonal Perovskite-Related Oxides.

Proton conductors have potential applications such as fuel cells, electrolysis cells, and sensors. These applications require new materials with high proton conductivity and high chemical stability at intermediate temperatures. Herein we report a series of new hexagonal perovskite-related oxides, Ba5R2Al2SnO13 (R = Gd, Dy, Ho, Y, Er, Tm, and Yb). Ba5Er2Al2SnO13 exhibited a high proton conductivity without chemical doping (e.g., 0.01 S cm-1 at 303 °C), which is attributed to its high proton concentration and diffusion coefficient. The high diffusion coefficient of Ba5Er2Al2SnO13 can be attributed to the fast proton migration in the octahedral layers. The high proton concentration is attributed to full hydration in hydrated Ba5Er2Al2SnO13 and the large amount of intrinsic oxygen vacancies in the dry sample, as evidenced by both neutron diffraction and thermogravimetric analysis. Ba5Er2Al2SnO13 was found to exhibit high chemical stability under wet atmospheres of O2, air, H2, and CO2. High proton conductivity and high chemical stability indicate that Ba5Er2Al2SnO13 is a superior proton conductor. Ba5R2Al2SnO13 (R = Gd, Dy, Ho, Y, Tm, and Yb) exhibited high electrical conductivity in wet N2, suggesting that these materials also exhibit high proton conductivity. These findings will open new avenues for proton conductors. The high proton conductivity via full hydration and fast proton migration in octahedral layers in highly oxygen-deficient hexagonal perovskite-related materials would be an effective strategy for developing next-generation proton conductors.

Characterisation of a microelectrochemical biosensor for real-time detection of brain extracellular d-serine

A modified development protocol and concomitant characterisation of a first generation biosensor for the detection of brain extracellular d-serine is reported. Functional parameters important for neurochemical monitoring, including sensor sensitivity, O2 interference, selectivity, shelf-life and biocompatibility were examined. Construction and development involved the enzyme d-amino acid oxidase (DAAO), utilising a dip-coating immobilisation method employing a new extended drying approach. The resultant Pt-based polymer enzyme composite sensor achieved high sensitivity to d-serine (0.76 ± 0.04 nA mm−2. μM−1) and a low μM limit of detection (0.33 ± 0.02 μM). The in-vitro response time was within the solution stirring time, suggesting potential sub-second in-vivo response characteristics. Oxygen interference studies demonstrated a 1 % reduction in current at 50 μM O2 when compared to atmospheric O2 levels (200 μM), indicating that the sensor can be used for reliable neurochemical monitoring of d-serine, free from changes in current associated with physiological O2 fluctuations. Potential interference signals generated by the principal electroactive analytes present in the brain were minimised by using a permselective layer of poly(o-phenylenediamine), and although several d-amino acids are possible substrates for DAAO, their physiologically relevant signals were small relative to that for d-serine. Additionally, changing both temperature and pH over possible in vivo ranges (34–40 °C and 7.2–7.6 respectively) resulted in no significant effect on performance. Finally, the biosensor was implanted in the striatum of freely moving rats and used to monitor physiological changes in d-serine over a two-week period.