Oxygen Source Research Articles

MODELING THE DYNAMICS OF DISSOLVED OXYGEN CONCENTRATION IN WATERS OF THE ANIVA BAY (THE SEA OF OKHOTSK)

To determine the risks for mariculture farms, the intra-annual change of dissolved О2 concentration was simulated for five zones in the Aniva Bay using the CNPSi model. Zone 1 differed sharply from other zones as the most shallow and freshened. Zone 2 is characterized by a pronounced water exchange with Zone 3 and Zone 4: during spring two layers were formed and stood out in these zones, in the summer the water column was homogeneous. Zone 3 has free water exchange with the open waters of the La Perouse Strait. An outstanding feature of Zone 4, in the deep-water part of the bay, was a distinctive subsidence of waters in the centre of the anticyclonic circulation and the maximum thermocline depth (up to 60-70 m). Zone 5 extends along the western coast of the Tonino-Aniva Peninsula and is characterized by the constant upwelling of waters during the icefree period, which is clearly expressed by lower water temperatures. The calculation showed that in the areas suitable for mariculture farms coastal waters were provided with oxygen throughout the year. Anaerobic conditions developed in spring only in the deepest parts of the bay. An additional source of oxygen in the Aniva Bay is natural thickets of macrophytes, among which the Japanese saccharin (Saccharina japonica) dominates in terms of biomass and area. Annually, Japanese saccharin itself absorbed at least 1200 tons of C in its biomass and supplied at least 3100 tons of О2. Unlike the artificially grown biomass, the biomass of all macrophytes would remain in the system and be destroyed during the life cycle, and the oxygen would be consumed for oxidation. The carbon accumulated in the biomass would again return to the rapid cycle, with the exception of the amount transported to the deep central part of the bay, where it would slowly decompose under nearly anaerobic conditions. It would be possible to place additional algae plantations in the bay, which could absorb up to 49 500 tons of C annually, while supplying up to 132 000 tons of О2. The obtained model estimates could be a starting point for determining the “baseline” of the content of dissolved oxygen and compiling balance equations for gas flows in the ocean-atmosphere system in the Aniva Bay before the development of seaweed plantations, which simultaneously act as carbon farms.

Weathering as a control on the triple oxygen isotopes of groundwater-associated ferromanganese deposits: lessons from the Grimlock Ni–Co–Mn prospect, Northern Territory, Australia

At the Grimlock laterite deposit (Northern Territory, Australia), Co and Ni mineralization occurs mainly in the Mn-oxide rich layers of the ferromanganese (Fe-Mn) crust overlying ultramafic bedrock. Groundwater-associated Fe-Mn crusts consist of mineral (e.g. Mn-oxide, Fe-oxyhydroxide and silicate) groups suitable for studying triple oxygen isotopes and present unique interpretative challenges (e.g. small Mn-oxide fractions relative to Fe-Mn precipitates from other formation environments and extensive weathering). We evaluate triple oxygen isotopes within the context of changes to properties (i.e. mineralogy, major and trace element geochemistry, and degree of weathering) of a lateritic profile. We use pre-existing mineral-water fractionation factors, meteoric water δ 18 O and temperature data to calculate δ 18 O values of fully altered mineralogical endmembers, then, using mass balance, discuss scenarios to elucidate measured whole-rock δ 18 O values. The δ ′ 18 O (′ denotes linearized notation) and Δ ′ 17 O of near-surface samples (0–8 m) are generally lower (mean of 8.892‰) and higher (mean of −0.141‰), respectively, than the δ ′ 18 O (mean of 12.767‰) and Δ ′ 17 O (mean of −0.176‰) of samples from greater depths (19–22 m). At 16–17 m depth, δ ′ 18 O and Δ ′ 17 O are relatively high (means of 17.509 and −0.118‰, respectively). The measured whole-rock δ 18 O values are explainable by substituting lower δ ′ 18 O values for the Mn-oxide and Fe-oxyhydroxide fractions, and higher δ ′ 18 O values for the aluminosilicate fraction, changes coinciding with greater alteration. These results suggest that mineral weathering is primarily responsible for observed variations in the triple oxygen isotopes of groundwater-associated Fe-Mn crusts, rather than variation in the initial source of oxygen incorporated into Mn-oxide. Supplementary material: Grimlock sample photographs, XRD patterns and supplementary figures and tables are available at https://doi.org/10.6084/m9.figshare.c.7071907

Light-Activated BF3·Et2O-Promoted Generation of Singlet Oxygen and Cascade Reaction of Unsaturated Amides.

Herein, BF3·Et2O-promoted O-insertion/spirocyclization/fluorination/ring-expansion of unsaturated amides to synthesis of spiro[benzo[b]-[1,4]dioxepine-3,5'-oxazole] skeletons in the presence of natural light and O2 (3Σg-) was reported. Air was the oxygen source of the 1O2-generation and O-insertion reaction under metal-free and mild conditions. BF3·Et2O played multiple roles, such as Lewis acid, activating reagent, and fluorine source in the reported cascade. A mechanism involving 1O2 generation/activation of double bond/O-insertion/spirocyclization/fluorination/ring expansion was supposed.

Copper-cobalt dual-site on N-doped carbon nanotube with dual-promoted synergy for glucose electrochemical detection

Doping specific active sites and accelerating the decisive step of glucose catalysis to construct highly active glucose sensing electrochemical catalysts remains a major challenge for glucose sensing. Herein, we report the detailed design of Cu–Co dual active site N-doped carbon nanotube (CuCo-NCNTs) obtained by electrodeposition modification, programmed warming and calcination for electrochemical glucose detection. In the CuCo-NCNTs material system, Cu serves as the main active site for glucose sensing. Co with good adsorption of hydroxyl groups acts as the site providing hydroxyl groups to provide oxygen source for Cu oxidized glucose sensing. The synergistic effect between the two active sites in the Cu–Co system and the abundant micro-reactive sites exposed by carbon nanotubes greatly ensure the excellent electrocatalytic performance of glucose oxidation reaction. Therefore, CuCo-NCNTs have good electrocatalytic performance with a sensitivity of 0.84 mA mM−1 cm−2 and a detection limit of 1 μM, and also have excellent stability and specificity. DFT calculations elucidate the decisive steps of H-atom removal in the oxidation of glucose by Cu active site N-doped carbon nanotube (Cu-NCNTs) and Co active site N-doped carbon nanotube (CuCo-NCNTs) materials, illustrating the role of oxygen source provided by hydroxyl group adsorption in the electrochemical sensing process of glucose, thus demonstrating that the electrochemical sensing signal of glucose can be effectively enhanced when cobalt species that readily adsorb hydroxyl groups are introduced into the materials.

ANALISIS KETERSEDIAAN RUANG TERBUKA HIJAU DI PUSAT KOTA KABUPATEN MARA ENIM DENGAN METODE NORMALIZED DIFFERENCE VEGETATION INDEX (NDVI)

The development of the city center in various forms can affect Green Open Space (GOS) as a source of oxygen, sports facilities, community recreation facilities, and regional income. This study was conducted at the City Center of Muara Enim Regency. Muara Enim Regency has experienced rapid development in recent years, so it is suspected that there has been a reduction in the area of GOS. This research aims to identify, analyze, and map the provision of GOS in the City Center of Muara Enim Regency. The main data in this research include Landsat 8 satellite image data for 2021-2023. The Normalized Difference Vegetation Index (NDVI) algorithm analysis method is the basis for determining the density of vegetation that makes up the green spaces. Law No. 26 of 2007 on spatial planning states that the proportion of green space in urban areas is at least 30% of the total area. The results showed that the area of dense vegetation in Muara Enim Regency City Center decreased, but the amount of green space in City Center of Muara Enim Regency was 73.57% of the area and still met the proportion of green space set by the government.

Electrocatalytic Epoxidation of Cyclooctene on Surface Modified Ni Foam Using Water as Oxygen Source.

Electrochemical epoxidation of olefins using water as an oxygen atom source is emerging as an alternative approach for an atom economic and sustainable method towards a highly selective synthesis of epoxides. We report an electrochemical procedure for epoxidation of cyclooctene using water as the sole oxygen atom source over a sodium dodecyl sulfonate (SDS) modified nickel hydroxide Ni(OH)2 catalyst directly grown on Ni foam. The SDS modification facilitates the mass transfer of cyclooctene towards the anode, thus achieving a 2.5-fold higher conversion with more than 90 % selectivity towards the corresponding epoxide compared with pure Ni(OH)2 catalyst.

An Open-Air Palladium-Catalyzed Stereoselective O-Glycosylation of Glycals via in-situ Generation of gem-Disubstituted Methanols from p-Quinone Methides.

We devised a palladium-catalyzed α-stereoselective glycosylation that incorporates oxygen via in-situ generation of gem-disubstituted methanols from p-quinone methides to access 2,3-unsaturated gem-diarylmethyl O-glycosides under open-air atmosphere at room temperature. Advantages of this environmentally friendly strategy include the absence of additives and ligands, using water as the green source of oxygen, mildest, operationally simple, exhibiting a wide functional group tolerance, and compatibility with a variety of glycal progenitors in appreciable yields. A mechanistic study has been verified via H2 18 O labeling, which validates that water (moisture) is a sole source of oxygen.

Photocatalytic Multicomponent Annulation of Amide-Anchored 1,7-Diynes Enabled by Deconstruction of Bromotrichloromethane.

We present the first example of visible-light-mediated multicomponent annulation of 1,7-diynes by taking advantage of quadruple cleavage olf carbon-halogen bonds of BrCCl3 to generate a C1 synthon, which was adeptly applied to the preparation of skeletally diverse 3-benzoyl-quinolin-2(1H)-one acetates in moderate to good yields. Controlled experiments demonstrated that H2O acted as both oxygen and hydrogen sources, and gem-dichlorovinyl carbonyl compound exhibited as a critical intermediate in this process. The mechanistic pathway involves Kharasch-type addition/6-exo-dig cyclization/1,5-(SN")-substitution/elimination/binucleophilic 1,6-addition/proton transfer/tautomerization sequence.

Nitrogen and oxygen isotope characteristics, formation mechanism, and source apportionment of nitrate aerosols in Wuhan, Central China

Understanding the sources and formation mechanisms of nitrate in PM2.5 is important for effective and precise prevention and control of particulate matter pollution. In this study, we detected stable nitrogen and oxygen isotope signatures of NO- 3 (expressed as δ15N-NO- 3 and δ18O-NO3−) in PM2.5 samples in Wuhan, the largest city in central China. The sources and formation pathways of NO3− were quantitatively analyzed using the modified version of the Bayesian isotope mixing (MixSIR) model, and the regional transport characteristics of NO3− were analyzed using the hybrid single-particle Lagrangian integrated trajectory (HYSPLIT) model and concentration-weighted trajectory (CWT) method. The results showed that NO3− significantly contributed to the ambient PM2.5 pollution and its driving effect increased with the gradient of pollution level. The average δ15N-NO3− and δ18O-NO3− values were 4.7 ± 0.9 ‰ and 79.7 ± 2.9 ‰, respectively. δ15N-NO3− and δ18O-NO3− were more enriched in winter and increased dramatically in heavily polluted days. The reaction pathway of NO2 + OH dominated nitrate formation in summer, while the reaction pathway of N2O5+ H2O dominated in other seasons and contributed more in polluted days than clean days. The contributions of vehicle emission, coal combustion, biomass burning, biogenic soil emission, and ship emission sources to NO3− were 26.4 %, 23.4 %, 22.8 %, 15.3 %, and 12.1 %, respectively. In addition to local emissions, air mass transport from the northern China had a significant impact on particulate NO3− in Wuhan. Overall, we should pay special attention to vehicle and ship emissions and winter coal combustion emissions in future policymaking.

Electron Aggregation and Oxygen Fixation Reinforced Microwave Dynamic and Thermal Therapy for Effective Treatment of MRSA-Induced Osteomyelitis.

Antibiotics are frequently used to clinically treat osteomyelitis caused by bacterial infections. However, extended antibiotic use may result in drug resistance, which can be life threatening. Here, a heterojunction comprising Fe2O3/Fe3S4 magnetic composite is constructed to achieve short-term and efficient treat osteomyelitis caused by methicillin-resistant Staphylococcus aureus (MRSA). The Fe2O3/Fe3S4 composite exhibits powerful microwave (MW) absorption properties, thereby effectively converting incident electromagnetic energy into thermal energy. Density functional theory calculations demonstrate that Fe2O3/Fe3S4 possesses significant charge accumulation and oxygen-fixing capacity at the heterogeneous interface, which provides more active sites and oxygen sources for trapping electromagnetic hotspots. The finite element analysis indicates that Fe2O3/Fe3S4 displays a larger electromagnetism field enhancement parameter than Fe2O3 owing to a significant increase in electromagnetic hotspots. These hotspots contribute to charge differential accumulation and depletion motions at the interface, thereby augmenting the release of free electrons that subsequently combine with the oxygen adsorbed by Fe2O3/Fe3S4 to generate reactive oxygen species (ROS) and heat. This research, which achieves extraordinary bacterial eradication through the synergistic effect of microwave thermal therapy (MWTT) and microwave dynamic therapy (MDT), presents a novel strategy for treating deep-tissue bacterial infections.

Oxygenation of Phenols with Water as the Oxygen Source and Oxoammonium Salt as the Oxidant.

Aromatic C-H oxygenation is important in both industrial production and organic synthesis. Here we report a metal-free approach for phenol oxygenation with water as the oxygen source using oxoammonium salts as the renewable oxidant. Employing this protocol, various alkyl-substituted phenols were converted into benzoquinones in yields of 59-98%. On the basis of 18O-labeling and kinetic studies, the hydroxy-oxoammonium adduct was proposed to attack the aromatic ring similarly to electrophilic aromatic substitution. We suppose that the findings described here not only provide an efficient and highly selective protocol for aromatic C-H oxygenation but also may encourage further developments of possible transition-metal-free catalytic methods.

Sustainable Electrochemical Benzylic C-H Oxidation Using MeOH as an Oxygen Source.

New methods and strategies for the direct oxidation of benzylic C-H bonds are highly desirable, owing to the importance of ketone motifs in significant organic transformations and the synthesis of valuable molecules, including pharmaceuticals, pesticides, and fine chemicals. Herein, we describe an electrochemical benzylic C-H oxidation strategy for the synthesis of ketones using MeOH as an oxygen source. Inexpensive and safe KBr serves as both an electrolyte and a bromide radical precursor in the reaction. This transformation also offers several advantages such as mild conditions, broad functional group tolerance, and operational simplicity. Mechanistic investigations by control experiments, radical scavenging experiments, electron paramagnetic resonance (EPR), kinetic studies, cyclic voltammetry (CV), and in-situ Fourier transform infrared (FTIR) spectroscopy support a pathway involving the formation and transformation of benzyl methyl ether via hydrogen atom transfer (HAT) and single-electron transfer (SET). The practical application of our strategy is highlighted by the successful synthesis of five pharmaceuticals, namely lenperone, melperone, diphenhydramine, cinnarizine, and flunarizine.

Catalytic Aerobic Photooxidation of Phosphines using Four-coordinated Organoboron Compounds as Photocatalysts

AbstractA photooxidation approach to the conversion of phosphines into the corresponding phosphine oxides is reported. By taking advantage of O2 in the air as an oxidant and oxygen source, phosphine oxides were obtained efficiently in moderate to excellent yields. A four-coordinated organoboron compound was used as the photocatalyst to activate O2 to its singlet state. This photooxidation method features mild reaction conditions, broad functional-group tolerance, and a wide substrate scope.

Role of H2O in Catalytic Conversion of C1 Molecules.

Due to their role in controlling global climate change, the selective conversion of C1 molecules such as CH4, CO, and CO2 has attracted widespread attention. Typically, H2O competes with the reactant molecules to adsorb on the active sites and therefore inhibits the reaction or causes catalyst deactivation. However, H2O can also participate in the catalytic conversion of C1 molecules as a reactant or a promoter. Herein, we provide a perspective on recent progress in the mechanistic studies of H2O-mediated conversion of C1 molecules. We aim to provide an in-depth and systematic understanding of H2O as a promoter, a proton-transfer agent, an oxidant, a direct source of hydrogen or oxygen, and its influence on the catalytic activity, selectivity, and stability. We also summarize strategies for modifying catalysts or catalytic microenvironments by chemical or physical means to optimize the positive effects and minimize the negative effects of H2O on the reactions of C1 molecules. Finally, we discuss challenges and opportunities in catalyst design, characterization techniques, and theoretical modeling of the H2O-mediated catalytic conversion of C1 molecules.

Non-cytochrome P450 enzyme aldehyde oxidase is involved in the oxidative metabolic pathway of diquat and its detoxification effect

Diquat (DQ) poisoning has garnered attention in recent years, primarily due to the rising incidence of cases worldwide, coupled with the absence of a viable antidote for its treatment. Despite the fact that diquat monopyridone (DQ-M) has been identified as a significant metabolite of DQ, the enzyme responsible for its formation remains unknown. In this study, we have identified aldehyde oxidase (AOX) as a vital enzyme involved in DQ oxidative metabolism. The metabolism of DQ to DQ-M was significantly inhibited by AOX inhibitors including raloxifene and hydralazine. The source of oxygen incorporated into DQ-M was proved to be from water through a H218O incubation experiment which further corroborated DQ-M formation via AOX metabolism. The product of DQ-M in vitro generated by fresh rat tissues co-incubation was consistent with its AOX expression. The result of the molecular docking analysis of DQ and AOX protein showed that DQ is capable of binding to AOX. Furthermore, the cytotoxicity of DQ was significantly higher than DQ-M at the same concentration tested in six cell types. This work is the first to uncover the involvement of aldehyde oxidase, a non-cytochrome P450 enzyme, in the oxidative metabolic pathway of diquat, thus providing a potential target for the development of detoxification treatment.

Efficient and eco-friendly preparation of N/P/O co-doped porous carbon electrode for zinc-ion hybrid supercapacitors by laser carbonization

The incorporation of heteroatoms into carbon materials confers advantages in the development of electrode materials for zinc-ion supercapacitors with superior electrochemical performance. However, the conventional carbonization process requires a large thermal power input and is characterized by complexity, high costs, and lengthy reaction times. In this work, the phytic acid-doped polypyrrole (P-PPy) was carbonized via laser irradiation to synthesize N, P, O co-doped porous carbon (P-NOPC), wherein phytic acid served as the source of phosphorus and oxygen, while PPy served as the porous carbon precursor and nitrogen source. The formation of porous carbon can provide a large specific surface area for ion adsorption. The doping of heteroatoms improves the hydrophilicity of porous carbon electrodes and also improves the chemisorption capacity of carbon materials. The aqueous zinc-ion hybrid supercapacitor (ZHSC) based on 0.6P-NOPC9 positive electrode and zinc foil negative electrode has a discharge capacity of 148.0 mAh g−1 in a voltage window of 0.2–1.8 V at 0.1 A g−1, a high energy density (118.2 Wh kg−1) and long cycle life (capacity retention of 98.5% after 10,000 cycles). In addition, the capacity retention of the flexible quasi-solid-state ZHSC is 97.8% after 10,000 cycles. This study can provide a reference for the feasible design of porous carbon electrodes with high performance.

Oxygen generating biomaterials at the forefront of regenerative medicine: advances in bone regeneration.

Globally, an annual count of more than two million bone transplants is conducted, with conventional treatments, including metallic implants and bone grafts, exhibiting certain limitations. In recent years, there have been significant advancements in the field of bone regeneration. Oxygen tension regulates cellular behavior, which in turn affects tissue regeneration through metabolic programming. Biomaterials with oxygen release capabilities enhance therapeutic effectiveness and reduce tissue damage from hypoxia. However, precise control over oxygen release is a significant technical challenge, despite its potential to support cellular viability and differentiation. The matrices often used to repair large-size bone defects do not supply enough oxygen to the stem cells being used in the regeneration process. Hypoxia-induced necrosis primarily occurs in the central regions of large matrices due to inadequate provision of oxygen and nutrients by the surrounding vasculature of the host tissues. Oxygen generating biomaterials (OGBs) are becoming increasingly significant in enhancing our capacity to facilitate the bone regeneration, thereby addressing the challenges posed by hypoxia or inadequate vascularization. Herein, we discussed the key role of oxygen in bone regeneration, various oxygen source materials and their mechanism of oxygen release, the fabrication techniques employed for oxygen-releasing matrices, and novel emerging approaches for oxygen delivery that hold promise for their potential application in the field of bone regeneration.

Copper/Iodine Co-catalyzed Oxygenative Transannulation of Tryptamines Enables Direct Synthesis of Donaxaridine and Its Derivatives.

We report a general copper/iodine co-catalyzed oxygenative transannulation strategy using readily available tryptamines. Molecular oxygen and water are used as oxygen sources and provide direct access to the donaxaridine scaffold and its derivatives. This methodology is applied to the efficient synthesis of the natural products donaxaridine, chimonamidine, donaxanine, donaxarine, and aline in just one or two steps. The tryptamines, albeit with oxy-sensitive dialkyl N-H groups, are selectively oxidized through a single-electron transfer dioxygenation process.

Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**

AbstractControl of CO emissions raises serious environmental concerns in the current chemical industry, as well as in nascent technologies based on hydrogen such as electrolyzers and fuel cells. As for now, Pt remains one of the state‐of‐the‐art catalysts for the CO oxidation reaction, but unfortunately, it suffers from CO self‐poisoning. Recently, Pt−Ge alloys were proposed to be an excellent alternative to reduce CO poisoning. This work investigates the impact of Ge content on the CO oxidation kinetics of Pt4Gen subnanoclusters supported on MgO. A Ge concentration dependence of the reaction kinetics is found due to a strong synergy between Pt and Ge. Pt−Ge nanoalloys act as a bifunctional catalyst by displaying dual adsorption sites; i. e., CO is adsorbed on Pt whereas oxygen binds to Ge, forming an alternative oxygen source GeOx. Besides, Ge alloying modifies the electronic structure of Pt (ligand effects) and reduces the affinity to CO. In this way, the competition between CO and O2 adsorption and the overbinding of CO is alleviated, achieving a CO poisoning‐free kinetic regime. Our calculations suggest that Pt4Ge3 is the optimal catalyst, evidencing that alloying composition is a parameter of extreme importance in nanocatalyst design. The work relies on global optimization search techniques to determine the accessibility of multiple structures at different conditions, mechanistic studies and microkinetic modeling.

Visible-Light-Mediated Selective Allylic C–H Oxygenation of Cycloalkenes

AbstractA visible-light-mediated selective allylic C–H bond oxygenation of cyclic olefins is presented. Hence, the selective, mild monooxygenation of simple cycloalkenes has been achieved using an acridinium photoredox catalyst in combination with a phosphate base and a disulfide HAT reagent under air atmosphere at room temperature. The combination of both photocatalyst and HAT reagent, which can operate through a single or two different concurrent mechanistic pathways for the formation of the allyl radical, proved highly efficient, while the reaction with exclusively one or the other mediator performs in significantly lower yields. The formed allyl radical further reacts with a molecule of oxygen to build the corresponding peroxyradical that can abstract a hydrogen atom of another cycloalkene substrate, generating the known hydroperoxide intermediate in the formation of the ketone moiety. The advantages of this method rely on the easy use of air as oxygen source, as well as the selective monooxygenation of cycloalkenes without substitution in one of the allylic positions. Besides simple cyclic olefins, the method was also successfully applied in the oxidation of natural products such as the terpene valencene or cholesterol derivatives.