Molecular Oxygen Research Articles

Expanded scope of chitin-derived nitrogen scaffolds enabled by the 3-acetamido-5-furfurylaldehyde (3A5F) platform

The chitin-derived platform 3-acetamido-5-furfurylaldehyde (3A5F) undergoes organocatalyzed oxidative esterification with various alcohols to produce 4-acetamidofuran-2-carboxylates, enabling streamlined access to this previously unexplored chemical space. The reaction proceeds under mild conditions, using an affordable thiazolium catalyst, molecular oxygen as the oxidant, and ethyl acetate as the solvent (if necessary). Additionally, 3A5F facilitates access to a 3-acetamidobutenolide and 5-vinylfuran-3-acetamide, valuable biogenic platforms with a broad range of potential applications. All the products contain biogenic nitrogen and have been synthesized without using building blocks derived from ammonia produced via the energy-intensive Haber process.

Photo-induced hydroxypentafluorosulfanylation of alkenes with SF5Cl and oxygen gas and their further derivatization

Fluorinated or fluoroalkylated alcohols are common structural motifs in biologically active molecules, natural products, and pharmaceuticals. However, pentafluorosulfanyl (SF5) alcohols, a unique class of SF5 compounds that serve as synthetically valuable building blocks, are difficult to prepare with current methodologies. In this article, we present a single-step, metal-free, and photo-induced hydroxypentafluorosulfanylation of styrenes or α,β-unsaturated esters/amide, producing a series of structurally diverse pentafluorosulfanyl alcohols with up to 89% yields. This reaction is mild and operationally simple, using molecular oxygen as the hydroxy source. The protocol is suitable for a wide range of alkenes, including natural products and drug molecule derivatives. The formed SF5 alcohol units can be readily converted into diverse functionalized SF5 compounds, such as α-SF5 ketones, SF5 diols, and SF5 cyclic carbonates. The potential applications of these SF5 compounds in pharmaceutical and material sciences are vast, making this research a step forward in the field.

Visible‐Light‐Driven Oxidation of Benzene to Phenol with O2 over Photoinduced Oxygen‐Vacancy‐Rich WO3

AbstractDirect photocatalytic conversion of benzene to phenol with molecular oxygen (O2) is a green alternative to the traditional synthesis. The key is to find an effective photocatalyst to do the trick. Defect engineering of semiconductors with oxygen vacancies (OVs) is an emerging strategy for catalyst fabrication. OVs can trap electrons to promote charge separation and serving as adsorption sites for O2 activation. However, the randomly distribution of OVs on the semiconductor surface often results in mismatching the charge carrier dynamics under irradiation, thus failing to fulfill the unique advantages of OVs for photoredox functions. Herein, we demonstrate that abundant OVs can be facilely generated and precisely located adjacent to the reductive sites on reducible oxide semiconductors such as tungsten oxide (WO3) via a simple photochemistry strategy. Such photoinduced OVs are well suited for photocatalytic benzene oxidation with O2 as they readily capture photogenerated electrons from the reductive sites of WO3 to activate adsorbed O2. The oxygen‐isotope‐labeling experiments further confirm that the OVs also facilitate the integration of oxygen atoms from O2 into phenol, revealing in detail the pathway for photocatalytic benzene hydroxylation. This study demonstrates that the photochemistry approach is an appealing strategy for the synthesis of high‐performance OVs‐rich photocatalysts for solar‐induced chemical conversion.

Instrumentation prospects for rocky exoplanet atmospheres studies with high resolution spectroscopy

Studying the atmospheres of exoplanets is one of the most promising ways to learn about distant worlds beyond our solar system. The composition of an exoplanet’s atmosphere can provide critical insights into its geology and potential habitability. For instance, the presence of certain molecules such as water vapor, oxygen, or methane have been proposed to indicate the possibility of life. From an observation point of view, over the past fifteen years, significant progress has been made in characterizing exoplanetary atmospheres. This work reviews recent developments in ground-based high-resolution spectroscopic instruments that make it possible to analyze distant atmospheres in great detail. High-resolution transmission spectroscopy, one of the most effective methods used, has examined the atmospheres of Jupiter-like and is pushing towards the smaller, sub-Neptunian exoplanets. Numerous molecules have been detected using this technique, including CO,H2O,TiO,HCN,CH4,NH3,C2H2,OH\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathrm {CO, H_2O, TiO, HCN, CH_4, NH_3, C_2H_2, OH}$$\\end{document}. We explore the intriguing possibilities that lie ahead for future ground-based instrumentation, particularly in the context of detecting biologically relevant molecules within Earth-analog exoplanetary atmospheres including molecular oxygen (O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathrm {O_2}$$\\end{document}). With detailed exposure time calculations for detecting O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mathrm {O_2}$$\\end{document} we find that at the same exposure time spectral resolution of 300,000 reaches higher significance compared to 100,000. The exposure time and therefore the needed number of transits is reduced by a factor of 4 in challenging haze and cloud scenarios.

Photo-Induced Aerobic Oxidation of C–H Bonds

The photo-induced aerobic oxidation of C–H bonds has become an increasingly valuable strategy in organic synthesis, offering a green and efficient method for introducing oxygen into organic molecules. The utilization of molecular oxygen as an oxidant, coupled with visible-light photocatalysis, has gained significant attention due to its sustainability, atom economy, and environmentally benign nature. This review highlights the recent advancements in the field, focusing on the development of metal-free and transition-metal-based photocatalytic systems and novel photosensitizers capable of promoting selective C–H bond oxidation. The mechanistic pathways involved in various substrate oxidations, including benzylic, alkyl, alkene, and alkyne C–H bond transformations, are discussed. This review concludes with insights into the potential for integrating photocatalysis with renewable energy sources, positioning photo-induced aerobic oxidation as a cornerstone of sustainable chemical processes.

ER Oxidoreductin 1-Like Activity of Cyclic Diselenides Drives Protein Disulfide Isomerase in an Electron Relay System.

Disulfide formation generally involves a two-electron oxidation reaction between cysteine residues. Additionally, disulfide formation is an essential post-translational modification for the structural maturation of proteins. This oxidative folding is precisely controlled by an electron relay network constructed by protein disulfide isomerase (PDI), with a CGHC sequence as the redox-active site, and its family enzymes. Creating reagents that mimic the functions of these enzymes facilitates folding during chemical protein synthesis. In this study, we aimed to imitate a biological electron relay system using cyclic diselenide compounds as surrogates for endoplasmic reticulum oxidoreductin 1 (Ero1), which is responsible for the re-oxidation of PDI. Oxidized PDI (PDIox) introduces disulfide bonds into substrate proteins, resulting in its conversion to reduced PDI (PDIred). The PDIred is then re-oxidized to PDIox by a coexisting cyclic diselenide compound, thereby restoring the function of PDI as a disulfide-forming agent. The produced diselenol state is readily oxidized to the original diselenide state with molecular oxygen, continuously sustaining the PDI catalytic cycle. This artificial electron relay system regulating enzymatic PDI function effectively promotes the oxidative folding of disulfide-containing proteins, such as insulin-a hypoglycemic formulation-by enhancing both yield and reaction velocity.

Polarized electric field-mediated graphitic carbon nitride-based S-scheme heterostructure for efficient photocatalytic removal of bisphenol A

Tuning interface charge transfer is considered as a feasible way to promote electron migration and separation in heterojunction system, but the role of in-plane electron behavior in single phase has received little attention. Here, a carboxyl functionalized graphitic carbon nitride (CCN) coupled PbBiO2Br (PBOB) S-scheme heterostructure is elaborately designed for investigation. Compared with pristine CN/PBOB, although the existence of carboxyl group weakens the built-in electric field strength of CCN/PBOB (ΔΦ = 0.44 eV), the formed polarized electric field (µ = 3.18 Debye) is conducive to the pre-separation of photogenerated electrons and holes in CCN, thereby improving interface charge transfer. In addition, the introduced carboxyl group can also serve as an O2 adsorption site to enhance its activation, and generate reactive oxygen species (ROS) through a two-step single-electron O2 reduction route. Thus, the optimized CCN/PBOB exhibits excellent photocatalytic ROS generation ability, which can remove 88.7 % of bisphenol A and significantly reduce the acute toxicity of the formed intermediates. This work provides a new perspective for the development of advanced heterojunction photocatalyst by regulating in-plane/interface charge dynamics, and helps to fully understand the pollutant detoxification/degradation process initiated by molecular oxygen activation.

Bioenergetic suppression by redox-active metabolites promotes antibiotic tolerance in Pseudomonas aeruginosa

The proton-motive force (PMF), consisting of a pH gradient and a membrane potential (ΔΨ) underpins many processes essential to bacterial growth and/or survival. Yet bacteria often enter a bioenergetically diminished state characterized by a low PMF. Consequently, they have increased tolerance for diverse stressors, including clinical antibiotics. Despite the ubiquity of low metabolic rates in the environment, the extent to which bacteria have agency over entry into such a low-bioenergetic state has received relatively little attention. Here, we tested the hypothesis that production of redox-active metabolites (RAMs) could drive such a physiological transition. Pseudomonas aeruginosa is an opportunistic pathogen that produces phenazines, model RAMs that are highly toxic in the presence of molecular oxygen (O2). Under oxic conditions, the phenazines pyocyanin and phenazine-1-carboximide, as well as toxoflavin-a RAM produced by Burkholderia species-suppress the ΔΨ in distinct ways across distributions of single cells, reduce the efficiency of proton pumping, and lower cellular adenosine-triphosphate (ATP) levels. In planktonic culture, the degree and rate by which each RAM lowers the ΔΨ correlates with the protection it confers against antibiotics that strongly impact cellular energy flux. This bioenergetic suppression requires the RAM's presence and corresponds to its cellular reduction rate and abiotic oxidation rate by O2; it can be reversed by increasing the ΔΨ with nigericin. RAMs similarly impact the bioenergetic state of cells in (hyp)oxic biofilm aggregates. Collectively, these findings demonstrate that bacteria can suppress their bioenergetic state by the production of endogenous toxins in a manner that bolsters stress resilience.

Cross-Coupling of Mo- and V-Nitrogenases Permits Protein-Mediated Protection from Oxygen Deactivation.

Nitrogenases catalyze dinitrogen (N2) fixation to ammonia (NH3). While these enzymes are highly sensitive to deactivation by molecular oxygen (O2) they can be produced by obligate aerobes for diazotrophy, necessitating a mechanism by which nitrogenase can be protected from deactivation. In the bacterium Azotobacter vinelandii, one mode of such protection involves an O2-responsive ferredoxin-type protein ("Shethna protein II", or "FeSII") which is thought to bind with Mo-dependent nitrogenase's two component proteins (NifH and NifDK) to form a catalytically stalled yet O2-tolerant tripartite protein complex. This protection mechanism has been reported for Mo-nitrogenase, however, in vitro assays with V-nitrogenase suggest that this mechanism is not universal to the three known nitrogenase isoforms. Here we report that the reductase of the V-nitrogenase (VnfH) can engage in this FeSII-mediated protection mechanism when cross-coupled with Mo-nitrogenase NifDK. Interestingly, the cross-coupling of the Mo-nitrogenase reductase NifH with the V-nitrogenase VnfDGK protein does not yield such protection.

Transport properties of high Mach number hypersonic air plasmas

Abstract The collisional and transport properties of hypersonic plasmas have been simulated by an air plasma chemistry model, which includes collisions with electrons, ions and neutral species, elastic scattering, vibrational relaxation and a transport model. Species and thermal fluxes at the surface of the vehicle have been investigated as a function of post-shock gas temperature and species sticking coefficient for a fixed altitude of 50 km. At temperatures below about 5,000 K, the leading species are vibrationally excited nitrogen molecules, while at higher temperatures the molecular nitrogen and atomic oxygen dominate. Large fluxes of oxygen atoms have been observed in the simulations, on the order of 10^20 cm^-2s^ -1, which may lead to high rates of surface oxidation. Another subject of this study is temperature equilibration. For electrons, equilibration takes tens of microseconds, while the vibrational temperature equilibration time vary widely; from a few microseconds to hundreds of microseconds, depending on the gas temperature. Finally, the adiabatic parameter  was calculated for post-shock gas temperatures 5,000 K and 10,000 K and total gas density 1.2×10^17 cm^(-3). For post-shock gas temperature 5,000 K, only a slight reduction of gamma from the ideal gas value of ~1.4 is observed, while for 10,000 K it drops to ~1.26, which has a considerable impact on plasma properties. It was further established that the vibrational kinetics plays a leading role. While a single excited vibrational level of the N2 molecule captures the salient properties of the plasma, a detailed vibration kinetics is required for high-fidelity simulations.

Flavin–Iodine‐Catalyzed Aerobic Oxidative Tandem C(sp3)−H Imination and Amination: Synthesis of Fluorescent Imidazo[1,5‐a]pyridines from Pyridylmethanes and Aminomethanes

AbstractAerobic oxidative tandem C(sp3)−H imination and amination between pyridylmethane and aminomethane derivatives was demonstrated using a flavin–iodine‐coupled catalyst. This method provides a simple and atom‐economical synthesis of various 1,3‐substituted imidazo[1,5‐a]pyridines with fluorescent properties. The flavin–iodine catalyst efficiently promoted multiple reactions, including the oxygenation of pyridylmethane and subsequent oxidative C−N bond formation, utilizing only molecular oxygen, which is a sustainable ideal oxidant. The resulting 1‐ester‐substituted imidazo[1,5‐a]pyridine derivatives exhibited dual‐state emission in both solution and solid states. In particular, imidazo[1,5‐a]pyridine with a bulky 2,6‐dichlorophenyl substituent showed an apparent blue emission with good photoluminescence (PL) quantum yields (0.49 in CH2Cl2 solution and 0.39 in the solid state), making it promising candidate for use in optoelectronic devices.

Photocatalytic Decarboxylative Cross-Coupling of α,β-Unsaturated Acids with Amines for α-Ketoamides via C-N Bond Formation.

An unprecedented oxidative decarboxylative chemical domain of α,β-unsaturated acids and amines for C-N cross-coupled α-ketoamidation is disclosed. Molecular oxygen as a source oxygen in amide and water oxygen in the ketone segment furnished a green and sustainable synthesis of α-ketoamide from feedstock acids and amines. Mechanistically, photocatalyst travels with reductive quenching cycle, whereas pallado-cycle proceeded through oxidative C-N bond formation. Broad substrate scope, functional group tolerance, and CO2 and H2O as traceless byproducts make the present methodology more efficient and attractive.

Electrochemical Synthesis of Nitrite and Nitrate via Cathodic Oxygen Activation in Liquefied Ammonia.

The electrochemical oxidation of ammonia (NH3) enables decentralized small-scale synthesis of nitrate (NO3-) and nitrite (NO2-) under ambient conditions by directly utilizing renewable energy. Yet, their electrosynthesis has been restricted to aqueous media and low ammonia concentrations. For the first time, we demonstrate here a strategy enabling the direct electrooxidation of liquefied NH3 to NO3- and NO2- by using molecular oxygen, achieving combined Faraday efficiencies above 40%.

Constructing frustrated Lewis pairs on Mo-doped Fe2O3 catalyst to enhance oxidative desulfurization efficiency

The emission of sulfur oxides will not only cause a series of environmental pollution but also threaten human health. At present, oxidative desulfurization is considered one of the technologies to achieve high-efficiency conversion of sulfur-containing compounds. Herein, the special frustrated Lewis pairs (FLPs) for efficient oxidative desulfurization are created by regulating surface doping in a redox iron-based oxide. According to experimental results, the Lewis acidic sites can be considered as the iron atoms adjacent to the molybdenum dopant, while the doped metal proximal to the oxygen vacancies serves as Lewis basic sites to create FLPs in redox iron-based oxide. This reactivity of FLPs is further adapted to the chemical activation of molecular oxygen and aromatic sulfur-containing compounds. The Fe2O3-FLP catalyst can achieve 100 % sulfur removal at 3 h and maintains 96.9 % after seven cycles, higher than other previously reported iron-based oxidative desulfurization catalysts. In addition, the design of FLPs offers a promising approach for developing high-efficiency catalysts in the oxidative desulfurization process.

Mechanistic Insights on Coverage-Dependent Selectivity Limitations in Vinyl Acetate Synthesis.

Developing improved catalysts for sustainable chemical processes often involves understanding atomistic origins of catalytic activity, selectivity, and stability. Using density functional theory and steady-state kinetic analyses, we probe the elementary steps that form decomposition products that limit selectivity in vinyl acetate (VA) synthesis on Pd surfaces covered with acetate species. Acetate formation and coupling with ethylene control the VA formation catalytic cycle and steady-state coverage, but acetate and ethylene can separately decompose to form CO2. Both decompositions involve initial C-H activations at acetate vacancies, followed by additional C-H activations and eventual C-O formations and C-C cleavages involving reactions with molecular oxygen. Acetate decomposition paths with non-oxidative kinetically-relevant steps exhibit similar free energy barriers to oxidative paths. In contrast, the non-oxidative ethylene path involving an ethylidyne intermediate exhibits a much lower barrier than paths with oxidative kinetically-relevant steps. Ethylene decomposition is very facile at low coverages but is more coverage-sensitive, leading to similar decomposition and VA formation barriers at coverages accessible at steady state, which is consistent with moderate VA selectivity in measurements and ethylene vs. acetate decomposition contributions assessed from regressed kinetic parameters. These insights provide a detailed framework for describing VA synthesis rates and selectivity on metallic catalyst surfaces.

Breakdown cost and recycling processes of Bentonite/TiO2 quantum dots of photo and solar degradation of Congo Red dye and industrial dyes wastes

This research presents the preparation, characterization, and application of a novel bentonite- TiO2 quantum dot (Bent/TQ) nanocomposite for the efficient photodegradation of Congo Red dye, a common pollutant in industrial wastewater. The composite was prepared via a co-precipitation method followed by calcination, which facilitated the uniform dispersion of TiO2 quantum dots within the bentonite matrix. The resulting material exhibited a high specific surface area of 205.45 m2/g and an optimized band gap of 3.15 eV, making it suitable for visible light photocatalysis. The photocatalytic efficiency of Bent/TQ was evaluated under both xenon lamp irradiation and natural sunlight. The composite demonstrated a significant degradation rate constant of 23.35 × 10⁻³ s⁻1, which is comparable to that of pure TiO2 quantum dots (28.86 × 10⁻³ s⁻1). Mechanistic studies revealed that the primary active species responsible for the degradation were hydroxyl radicals (•OH), generated through the interaction of photogenerated electron-hole pairs with H2O molecules and molecular oxygen. Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD) analyses were employed to assess the mineralization efficiency of the composite. The Bent/TQ catalyst achieved a COD removal efficiency of 84.5% and a TOC reduction of 76.2% after 240 minutes of irradiation under natural sunlight. Reusability tests indicated that the photocatalyst retained approximately 80% of its original efficiency after seven consecutive cycles, though a slight decline was observed due to particle agglomeration under prolonged light exposure. The economic analysis suggested that the use of Bent/TQ nanocomposites could reduce operational costs by 29.12% compared to conventional TiO2-based systems, making it a cost-effective solution for large-scale wastewater treatment. This work highlights the potential of Bent/TQ nanocomposites as sustainable and efficient photocatalysts for environmental remediation, with future efforts aimed at enhancing their long-term stability and expanding their applicability to a broader range of pollutants.

Carbon defect induced electron transfer promotes electrocatalytic activation of molecular oxygen to selectively generate singlet oxygen for pollutants removal

This study explored the design of heterojunctions incorporating defective graphene and boron nitride (BN) to activate molecular oxygen (O₂) and degrade sulfamethoxazole (SMX) by establishing efficient electron transport channels. These heterojunction catalysts, designed using theoretical predictions, were synthesized by controlling carbon defect concentration and pyrolysis temperature. The optimized GBN cathode achieved a maximum SMX degradation rate of 0.0252min⁻¹, with a total organic carbon (TOC) removal efficiency of 47.31%. Singlet oxygen (¹O₂) was identified as the primary reactive oxygen species, exhibiting a generation rate of 18.66μMmin⁻¹ and contributing 93.5% to SMX degradation. Results demonstrated that an optimal defect concentration enhances electron transfer, promoting the 2-electron reduction of O₂ to H₂O₂ and facilitating further H₂O₂ activation, thereby accelerating SMX degradation. This work advances the development of non-metallic cathodic catalysts and provides valuable insights into electrochemical degradation mechanisms for organic pollutants.

Reaction mechanism of pyridine radicals with molecular oxygen: A theoretical study

Pyridine is a suitable surrogate of the fuel-nitrogen in flame studies. The goal of the present work was to extend the analysis of reactions of pyridyl radicals with O2. All reactions proceed following similar mechanisms, through the barrier-free addition of an O2 molecule and further development along two main paths: through barrier-free abstraction of an oxygen atom and through the formation of a seven-membered ring. The energies of the main intermediates of all three reactions, calculated relative to the pyridyl + O2 system, have similar values. All three reactions are characterized by the formation of 1λ2-pyrrole, as well as HCO, HCN, C2H2 and CO.

In vitro/In vivo oxygen electrochemical nanosensor for bioanalysis

Direct in vivo monitoring of O2 is critical in the study of numerous biological processes, and the development of novel highly sensitive techniques for O2in vivo detection is of great potential importance. Electrochemical amperometric sensors are some of the most promising, easy to operate, inexpensive, sensitive and have a high temporal resolution. As part of this work, we have demonstrated a direct rapid method for molecular oxygen detection inside multicellular spheroids in vitro and rat brain in vivo. External and internal oxygen profiles in human adenocarcinoma MCF-7 spheroids were studied using developed nanoelectrode. The size of spheroids was shown to affect the level of hypoxia inside them, and also affected the oxygen consumption near spheroids in solution. To demonstrate the in vivo relevance of the novel sensor we used it to measure the oxygen concentrations in the superficial layers of the rat brain. This study demonstrates a minimally invasive electrochemical method for real-time oxygen profiling in vivo.

Design and testing of an (inert) gas cell for in situ polarization modulation infrared reflection absorption spectroscopic (PM-IRRAS) measurements under specific atmospheres.

Infrared reflection absorption spectroscopy (IRRAS) is a powerful surface-sensitive analytical technique to characterize the adsorbed molecules on metal surfaces down to (sub)monolayer coverage. In this paper, a new (inert) gas cell is presented that expands the scope of the commercially available Bruker PMA50 module. The cell is designed as a sample holder to measure thin films of molecules adsorbed on a metal substrate under a specific gaseous atmosphere. The dimensions of the cell are chosen in such a way that it can be transferred into a glovebox via the standard entrance port (Ø150mm), allowing the investigation of air-sensitive molecules under an inert-gas atmosphere. The cell has two hose connections through which the gas atmosphere can be varied as desired. This also allows for studying the reactivity of the adsorbed structures toward the surrounding gas in situ and in a (potentially) time-dependent fashion. Furthermore, the metal substrate can be irradiated via an exposure window to investigate the influence of light on the adsorbed molecules and/or their reactivity. Using the polarization-modulation (PM-) IRRAS technique along with the described gas cell, an air-sensitive molybdenum(0) tricarbonyl complex adsorbed on an Au(111) surface is investigated. This complex reacts with molecular oxygen to the molybdenum(VI) trioxo analog, and this conversion is accelerated by irradiation with light of 365 and 440nm.