Concentration Of Molecular Oxygen Research Articles

Efficient degradation of ciprofloxacin by innovative VUV/BN system: Kinetics, mechanism and toxicity assessment

Given the increasing emergence of widespread fluoroquinolones (FQs) in natural water environments and the limitations of traditional vacuum ultraviolet (VUV) systems for water decontamination, an innovative VUV/BN system was developed for the degradation and detoxification of ciprofloxacin (CIP) in this work. Unlike the VUV system, which primarily relies on hydroxyl radicals (·OH), the VUV/BN system significantly enhances the concentration of singlet molecular oxygen (1O2) to target the piperazine ring of CIP, achieving a defluorination efficiency of 98.88 % within 60 min. The degradation rate constant for CIP was found to be 2.76 times greater than that of the traditional VUV system. Additionally, varying concentrations of reactive species (RSs) in the VUV and VUV/BN systems resulted in distinct CIP degradation pathways. Due to the high selective oxidation capacity and environmental compatibility of 1O2, the VUV/BN system demonstrated excellent adaptability to environmental factors, maintaining stable operation in complex water matrices. Furthermore, the system exhibited high degradation capacity for CIP even in the fifth cycle, confirming its exceptional stability and reusability. The economic feasibility of the VUV/BN system was confirmed by its low electrical energy per order (EEO). This study underscores the potential of VUV/BN systems and enhances the understanding of CIP photodegradation.

Characterization and evaluation of photolabile (µ-peroxo)(µ-hydroxo)bis[bis(bipyridyl)cobalt caged oxygen compounds to facilitate time-resolved crystallographic studies of cytochrome c oxidase

Photolabile (µ-peroxo)(µ-hydroxo)bis[bis(bipyridyl)-cobalt-based caged oxygen compounds have been synthesized and characterized by optical absorbance spectroscopy, X-ray crystallography. and the quantum yield and redox stability were investigated. Furthermore, conditions were established where redox incompatibilities encountered between caged oxygen compounds and oxygen-dependant cytochrome c oxidase (CcO) could be circumvented. Herein, we demonstrate that millimolar concentrations of molecular oxygen can be released from a caged oxygen compound with spatio-temporal control upon laser excitation, triggering enzymatic turnover in cytochrome c oxidase. Spectroscopic evidence confirms the attainment of a homogeneous reaction initiation at concentrations and conditions relevant for further crystallography studies. This was demonstrated by the oxidizing microcrystals of reduced CcO by liberation of millimolar concentrations of molecular oxygen from a caged oxygen compound. We believe this will expand the scope of available techniques for the detailed investigation of oxygen-dependant enzymes with its native substrate and facilitate further time-resolved X-ray based studies such as wide/small angle X-ray scattering and serial femtosecond crystallography.Graphical abstract

Could the Length of the Alkyl Chain Affect the Photodynamic Activity of 5,10,15,20-Tetrakis(1-alkylpyridinium-4-yl)porphyrins?

Photodynamic therapy (PDT) is a minimally invasive treatment that uses the combination of a photosensitizing agent (PS) and light to selectively target solid tumors, as well as several non-neoplastic proliferating cell diseases. After systemic administration, PSs are activated by localized irradiation with visible light; in the presence of adequate concentrations of molecular oxygen, this causes the formation of reactive oxygen species (ROS) and subsequent tissue damage. In this study, two series of tetrakis(N-alkylpyridinium-4-yl)porphyrins were synthesized, differing in the presence or absence of a zinc ion in the tetrapyrrole nucleus, as well as in the N-alkyl chain length (from one to twelve carbon atoms). The compounds were chemically characterized, and their effect on cell viability was evaluated using a panel of three tumor cell lines to determine a possible relationship between photodynamic activity and Zn presence/alkyl chain length. The types of cell death mechanisms involved in the effect of the various PSs were also evaluated. The obtained results indicate that the most effective porphyrin is the Zn-porphyrin, with a pendant made up of eight carbon atoms (Zn-C8).

Effect of terahertz radiation on the transport properties of albumin: binding with metal ions

The effect of terahertz radiation on clusterization of bovine serum albumin (BSA) molecules and on BSA binding with nickel, cobalt and cadmium ions is investigated by means of high performance liquid chromatography and EPR spectroscopy under variation of the concentration of molecular oxygen in solution. Irradiation is detected to remove steric hindrance for oxygen adsorption. The degree of nickel and cobalt ion binding with irradiated BSA samples is substantially higher than with non-irradiated ones, while for cadmium the binding degree is the same and rather low in both cases. The functional groups in BSA molecule participating in metal ion binding are revealed by means of modeling.

Respiration is essential for aerobic growth of Zymomonas mobilis ZM4.

A key to producing next-generation biofuels is to engineer microbes that efficiently convert non-food materials into drop-in fuels, and to engineer microbes effectively, we must understand their metabolism thoroughly. Zymomonas mobilis is a bacterium that is a promising candidate biofuel producer, but its metabolism remains poorly understood, especially its metabolism when exposed to oxygen. Although Z. mobilis respires with oxygen, its aerobic growth is poor, and disruption of genes related to respiration counterintuitively improves aerobic growth. This unusual result has sparked decades of research and debate regarding the function of respiration in Z. mobilis. Here, we used a new set of mutants to determine that respiration is essential for aerobic growth and likely protects the cells from damage caused by oxygen. We conclude that the respiratory pathway of Z. mobilis should not be deleted from chassis strains for industrial production because this would yield a strain that is intolerant of oxygen, which is more difficult to manage in industrial settings.

Organic Solvent Contamination in Groundwater Around Natural Gas Plants

Alberta is a province that has vast deposits of natural gas. However, in its natural form it is considered sour in that it has impurities, i.e., it contains hydrogen sulphide (H2S), carbonyl sulfide (COS), carbon dioxide (CO2), mercaptans and organic sulphides. To enable the marketing of the natural gas these impurities must be removed using organic compounds and solvents. As a result of spills, leakage during processes, seepage from unlined storage ponds some of these solvents have contaminated groundwater around natural gas processing facilities. Remediation of the organic solvents is a difficult problem. To achieve an understanding of the processes involved in their degradation, a hydrogeochemical assessment of a site can be done using existing data from the site to track the development of groundwater redox zones across the different hydrostratigraphic units (HSU). This is relevant because the oxidation is hypothesized to have contributed to the biodegradation of the compounds. The objective of this global assessment is to assign a groundwater redox zone for each sample, with special emphasis placed on defining the oxidative groundwater zone (OGZ) due to its relevance to biodegradation. Ideally, the oxic groundwater zone would be defined based on the concentration of molecular oxygen (i.e., dissolved ) in groundwater (McMahon and Chapelle 2008). However, molecular oxygen, normally measured as ‘dissolved oxygen’, was not routinely measured as a field parameter in this study and therefore was unavailable to define the OGZ. The scheme adopted considers the concentrations of terminal electron acceptors (TEA) present in groundwater and measured in commonly measured parameters including oxygen, nitrate, and sulphate and dissolved metals (manganese and iron). These TEA's are consumed under progressively more reducing conditions after oxygen reduction is complete in the order: nitrate reduction, manganese reduction, iron reduction, sulphate reduction, and finally carbonate reduction (one form of methanogenesis). The results show that redox zonation is heterogeneously distributed across the site, both within and between HSUs. Multiple lines of hydrogeochemical evidence support buffered aerobic biodegradation at the site.

Detection of molecular oxygen using nanosecond-laser-induced plasma.

Molecular oxygen (O2) concentration is measured by employing nanosecond laser-induced plasmas (ns-LIP) over a broad temperature spectrum ranging from 300 K to 1000 K, in the presence of an additional oxygen-containing molecule, CO2. Typically, emission spectra emanating from ns-LIP are devoid of molecular information, as the ns-LIP causes the dissociation of molecular species within the plasma. However, atomic oxygen absorption lines that momentarily appear at 777 nm in the broadband emission from the early-stage plasma are determined to be highly sensitive to the O2 mole fraction but negligibly affected by the CO2 mole fraction. The atomic O absorbing the plasma emission originates from the O2 adjacent to the plasma: robust UV radiation from the early-stage plasma selectively dissociates adjacent O2, exhibiting a relatively low photodissociation threshold, thus generating the specific meta-stable oxygen capable of absorbing photons at 777 nm. A theoretical model is introduced, explicating the formation of the meta-stable O atom from adjacent O2. To sustain the UV radiation from the plasma under high-temperature and low-density ambient conditions, a preceding breakdown is triggered by a split laser pulse (532 nm). This breakdown acts as a precursor, seeding electrons to intensify the inverse-Bremsstrahlung photon absorption of the subsequent laser pulse (1064 nm). Techniques such as proper orthogonal decomposition (POD) and support vector regression (SVR) are employed to precisely evaluate the O2 mole fraction (<1% uncertainty), by analyzing the short-lived (<10 ns) O2-indicator depicted in the early-stage plasma.

Copper-Catalyzed Enantioselective Aerobic Alkene Aminooxygenation and Dioxygenation: Access to 2-Formyl Saturated Heterocycles and Unnatural Proline Derivatives.

Alkene aminooxygenation and dioxygenation reactions that result in carbonyl products are uncommon, and protocols that control absolute stereochemistry are rare. We report herein catalytic enantioselective alkene aminooxygenation and dioxygenation that directly provide enantioenriched 2-formyl saturated heterocycles under aerobic conditions. Cyclization of substituted 4-pentenylsulfonamides, catalyzed by readily available chiral copper complexes and employing molecular oxygen as both oxygen source and stoichiometric oxidant, directly provides chiral 2-formyl pyrrolidines efficiently. Reductive or oxidative workup of these aldehydes provides their respective amino alcohols or amino acids (unnatural prolines). Enantioselective synthesis of an indoline and isoquinolines is also demonstrated. Concurrently, cyclization of various alkenols under similar conditions provides 2-formyl tetrahydrofurans, phthalans, isochromans, and morpholines. The nature of the copper ligands, the concentration of molecular oxygen, and the reaction temperature all impact the product distribution. Chiral nitrogen and oxygen heterocycles are common components of bioactive small molecules, and these enabling technologies provide access to saturated heterocycles functionalized with ready-to-use carbonyl electrophiles.

Fluorescence Lifetime Macro Imager for Biomedical Applications

This paper presents a new photoluminescence lifetime imager designed to map the molecular oxygen (O2) concentration in different phosphorescent samples ranging from solid-state, O2-sensitive coatings to live animal tissue samples stained with soluble O2-sensitive probes. In particular, the nanoparticle-based near-infrared probe NanO2-IR, which is excitable with a 625 nm light-emitting diode (LED) and emits at 760 nm, was used. The imaging system is based on the Timepix3 camera (Tpx3Cam) and the opto-mechanical adaptor, which also houses an image intensifier. O2 phosphorescence lifetime imaging microscopy (PLIM) is commonly required for various studies, but current platforms have limitations in their accuracy, general flexibility, and usability. The system presented here is a fast and highly sensitive imager, which is built on an integrated optical sensor and readout chip module, Tpx3Cam. It is shown to produce high-intensity phosphorescence signals and stable lifetime values from surface-stained intestinal tissue samples or intraluminally stained fragments of the large intestine and allows the detailed mapping of tissue O2 levels in about 20 s or less. Initial experiments on the imaging of hypoxia in grafted tumors in unconscious animals are also presented. We also describe how the imager can be re-configured for use with O2-sensitive materials based on Pt-porphyrin dyes using a 390 nm LED for the excitation and a bandpass 650 nm filter for emission. Overall, the PLIM imager was found to produce accurate quantitative measurements of lifetime values for the probes used and respective two-dimensional maps of the O2 concentration. It is also useful for the metabolic imaging of ex vivo tissue models and live animals.

Evaluation of Probes to Measure Oxidizing Organic Triplet Excited States in Aerosol Liquid Water.

Oxidizing triplet excited states of organic matter (3C*) drive numerous reactions in fog/cloud drops and aerosol liquid water (ALW). Quantifying oxidizing triplet concentrations in ALW is difficult because 3C* probe loss can be inhibited by the high levels of dissolved organic matter (DOM) and copper in particle water, leading to an underestimate of triplet concentrations. In addition, illuminated ALW contains high concentrations of singlet molecular oxygen (1O2*), which can interfere with 3C* probes. Our overarching goal is to find a triplet probe that has low inhibition by DOM and Cu(II) and low sensitivity to 1O2*. To this end, we tested 12 potential probes from a variety of compound classes. Some probes are strongly inhibited by DOM, while others react rapidly with 1O2*. One of the probe candidates, (phenylthiol)acetic acid (PTA), seems well suited for ALW conditions, with mild inhibition and fast rate constants with triplets, but it also has weaknesses, including a pH-dependent reactivity. We evaluated the performance of both PTA and syringol (SYR) as triplet probes in aqueous extracts of particulate matter. While PTA is less sensitive to inhibition than SYR, it results in lower triplet concentrations, possibly because it is less reactive with weakly oxidizing triplets.

Structural insight into polyphenol oxidation during black tea fermentation

Polyphenol oxidation during fermentation plays a critical role in the formation of flavor and function of black tea. However, how the specific structures of tea polyphenols affect their oxidation kinetics during black tea fermentation is still unknown. Here, we found that the oxidations of tea polyphenols, including 7 catechins, 4 phenolic acids and 11 flavonoid glycosides followed pseudo-first-order kinetics during fermentation. Molecular structure and oxygen concentration collaboratively regulated the oxidation rate of different polyphenols. Pyrogallol structure was more easily to be oxidized than catechol and monophenol structure in B-ring, the gallic group in C-ring could inhibit oxidation of catechins, while the role of sugar moiety of flavonoid glycosides was differentiating. In addition, oxygen was found to be the key factor limiting the oxidation rate of polyphenols in regular black tea fermentation, and the oxidation rate constants of tea polyphenols were linearly and positively correlated with oxygen concentration.

Triplet exciton reactions in MEH-PPV films registered by accompanying magneto-sensitive photoluminescence

Magneto-sensitive delayed photoluminescence (DPL) of the deaerated MEH-PPV films in the presence of an external magnetic field is investigated. The obtained results have shown that the sign of the magnetic field effect on DPL can be inverted by varying molecular oxygen concentration in the films. For explaining the “sign-inversion” of the magnetic field effect on DPL, the mathematical model based on the superposition of exciton-initiated reactions was proposed. The magnetic field dependencies of DPL based on the theoretical model were calculated. The calculations of the magnetic field effects on DPL confirm the “sign-inversion effect”. Also, the critical molecular oxygen concentration when the magnetic field effect on DPL disappears was determined theoretically. The obtained results can be used for the detection of spin-selective exciton-initiated reactions as well as for the determination of molecular oxygen concentration in MEH-PPV films.

Validation of Atmospheric Absorption Models within the 20–60 GHz Band by Simultaneous Radiosonde and Microwave Observations: The Advantage of Using ECS Formalism

The precise calculation of atmospheric absorption in a microwave band is highly important for atmospheric remote-sensing with ground-based and satellite-borne radiometers, as it is a key element in procedures for temperature, humidity or trace gas concentration retrieval. The accuracy of the absorption model directly affects the accuracy of the retrieved information and reliability of the resulting forecasts. In this study, we analyze the difference between observed and simulated microwave spectra obtained from more than four years of microwave and radiosonde observations over Nizhny Novgorod (56.2°N, 44°E). We focus on zenith-measured microwave data in the 20–60 GHz frequency range in clear-sky conditions. The use of a conventional absorption model in simulations leads to a significant difference in frequency channels within the 51–54 GHz range, while calculations employing a more accurate model based on the Energy Corrected Sudden (ECS) formalism for molecular oxygen absorption reduces the difference several-fold.

Spectroscopy of triplet-excited complexes of oxygen with spruce cone molecules extract from picea abies in AOT micelles under combined photoexcitation

The paper presents a method for obtaining an extract from the cones of Picea Abies spruce and fabrication a microemulsion based on it, which has an absorption spectrum in the UV region and luminescence in the red region (680-720 nm). A spectral study of a microemulsion with an extract containing polyphenols and phenolic acids (vanillic, protocatechuic, oxybenzoic) in the visible and IR spectral regions has been carried out. On the basis of time-resolved spectral data, the possibility of formation of reactive oxygen species, in particular, singlet oxygen, in a microemulsion under the action of UV radiation has been proved. A technique for oxygen saturation of microemulsions with an extract has been developed. The quantum efficiency of singlet oxygen generation upon absorption of light at a wavelength of 400 nm by an extract with different concentrations of molecular oxygen inside reverse micelles has been determined. It has been established that the quantum yield of singlet oxygen (1Δg) in a microemulsion with an extract can be increased by a factor of 9.5 and this value can be controlled by changing the oxygen accumulation time inside the micelle. It was found that with the oxygen concentration grow, both extract fluorescence intensity and optical density increase, and long-lived delayed fluorescence appears. A controlled concentration process of oxygen complexation with extract molecules accompanied by chemiluminescence in the red region of the spectrum has been studied. The rate constants of energy deactivation in the contact complex after photoexcitation during quenching of triplet states of the extract molecules have been determined

Production and loss of O2(1Δ g ) at atmospheric pressure using microwave-driven microplasmas

We have used arrays of microwave-generated microplasmas operating at atmospheric pressure to generate high concentrations of singlet molecular oxygen, O2(1Δ g ), which is of interest for biomedical applications. The discharge is sustained by a pair of microstrip-based microwave resonator arrays which force helium/oxygen gas mixtures through a narrow plasma channel. We have demonstrated the efficacy of both NO and less-hazardous N2O additives for suppression of ozone and associated enhancement of the O2(1Δ g ) yield. Quenching of O2(1Δ g ) by ozone is sufficiently suppressed such that quenching by ground state molecular oxygen becomes the dominant loss mechanism in the post-discharge outflow. We verified the absence of other significant gas-phase quenching mechanisms by measuring the O2(1Δ g ) decay along a quartz flow tube. These measurements indicated a first-order rate constant of (1.2 ± 0.3) × 10−24 m3 s−1, slightly slower than but consistent with prior measurements of singlet oxygen quenching on ground state oxygen. The discharge-initiated reaction mechanisms and data analysis are discussed in terms of a chemical kinetics model of the system.

Simultaneous Infrared Spectroscopy, Raman Spectroscopy, and Luminescence Sensing: A Multispectroscopic Analytical Platform.

Scientific questions in fields such as catalysis, monitoring of biological processes, or environmental chemistry demand analytical technologies combining orthogonal spectroscopies. Combined spectroscopic concepts facilitate in situ online monitoring of dynamic processes providing a better understanding of the involved reaction pathways. In the present study, a low-liquid-volume multispectroscopic platform was developed based on infrared attenuated total reflection (IR-ATR) spectroscopy combined with Raman spectroscopy and luminescence sensing. To demonstrate the measurement capabilities, exemplary analyte systems including water/heavy water and aqueous solutions of ammonium sulfate were analyzed as proof-of-principle studies. It was successfully demonstrated that three optical techniques may be integrated into a single analytical platform without interference providing synchronized and complementary data sets by probing the same minute sample volume. In addition, the developed assembly provides a gastight lid sealing the headspace above the probed liquid for monitoring the concentration of molecular oxygen also in the gas phase via luminescence quenching. Hence, the entire assembly may be operated at inert conditions, as required, for example, during the analysis of photocatalytic processes.

The role of AUX1 during lateral root development in the domestication of the model C4 grass Setaria italica.

C4 photosynthesis increases the efficiency of carbon fixation by spatially separating high concentrations of molecular oxygen from Rubisco. The specialized leaf anatomy required for this separation evolved independently many times. The morphology of C4 root systems is also distinctive and adapted to support high rates of photosynthesis; however, little is known about the molecular mechanisms that have driven the evolution of C4 root system architecture. Using a mutant screen in the C4 model plant Setaria italica, we identify Siaux1-1 and Siaux1-2 as root system architecture mutants. Unlike in S. viridis, AUX1 promotes lateral root development in S. italica. A cell by cell analysis of the Siaux1-1 root apical meristem revealed changes in the distribution of cell volumes in all cell layers and a dependence of the frequency of protophloem and protoxylem strands on SiAUX1. We explore the molecular basis of the role of SiAUX1 in seedling development using an RNAseq analysis of wild-type and Siaux1-1 plants and present novel targets for SiAUX1-dependent gene regulation. Using a selection sweep and haplotype analysis of SiAUX1, we show that Hap-2412TT in the promoter region of SiAUX1 is an allele which is associated with lateral root number and has been strongly selected for during Setaria domestication.

Quantifying Molybdenum Isotopic Speciation in Sulfidic Water: Implications for the Paleoredox Proxy

Molybdenum (Mo) isotopic signature and concentrations can be a geologic indicator of changes in molecular oxygen concentrations in Earth’s oceans and atmosphere. However, in natural waters that are weakly to strongly sulfidic, few studies have been able to determine the exact mechanisms controlling partitioning and speciation related to isotopic fractionation of Mo. To understand the isotopic contribution of each Mo species to the overall bulk Mo isotope signature, we report a method that measures both the concentration and the isotopic composition of each Mo-bearing species during thiolation using synthesized sulfidic water. We accomplish this by using reversed-phase ion chromatography to isolate individual Mo species and then measure the isotopic ratio of each species with a multicollector inductively coupled plasma mass spectrometer. Our findings show that progressively thiolated species contribute to an increasingly negative isotopic value (i.e., −3.16 to +3.14) compared to the precursor stock solution. Additionally, these results corroborate Tossell’s theoretical predictions, where lower Mo isotope values correlate to increasing sulfide presence. Furthermore, the formation of thiolated species and evolution of Mo isotopic signatures in our experiments do not occur via a stepwise formation or a quantitative conversion model for molybdate to tetrathiomolybdate. Overall, our study improves our understanding of Mo systematics, shows the potential of measuring specific Mo species, and thereby strengthens the application of Mo paleoproxy through consideration of all Mo species.

Muonium response to low oxygen levels in haemoglobin and other biological aqueous solutions and potential application towards monitoring hypoxia

Low oxygen concentration or hypoxia plays a crucial role in the diagnosis and treatment of tumours and cancer. Although there are some existing techniques, such as proton magnetic resonance imaging (MRI), for the detection of molecular oxygen in tissues, new non-invasive techniques for directly measuring the extent and spatial distribution of hypoxia in cancerous or tumorous tissues are still needed. In this study, we propose a new non-invasive method using muons that are available in accelerator facilities, such as the Japan Proton Accelerator Research Complex in Japan and the Rutherford Appleton Laboratory in the UK. Unlike existing MRI methods, the proposed muon-based method can be applied without any external magnetic field. With the help of muonium response in solutions, we measured oxygen concentration in the aqueous solutions of various biological materials, such as haemoglobin, albumin, serum, and tris-buffered saline, under controlled molecular oxygen concentrations. The observed relaxation rate pattern of muonium through a fixed oxygen concentration sample and that with a sample concentration of less than 1% oxygen shows that this method may be applicable in detecting molecular oxygen levels in various tissues of the human body. Based on our experimental results, we have estimated the expected muonium spectra in normal physiological concentrations of haemoglobin in blood. Further systematic studies on other biological solutions are required before a potential clinical application of the method is devised.

Effect of Mechanical Shaking on the Physicochemical Properties of Aqueous Solutions.

Long-lived luminescence in the blue region was found to occur in deionized water saturated with atmospheric gases following mechanical shaking. Luminescence intensity decreased exponentially after the cessation of stress. During vigorous mechanical shaking, we observed gas bubbles in solution, and the liquid–gas interface area increased noticeably. At the same time, the concentration of molecular oxygen decreased, which could not be attributed to the water warming up with exposure to mechanical stress. However, deaerated water rapidly became saturated with gases following mechanical stress. The recommendation that cell culture media should be mixed after they are removed from the fridge in order to allow saturation with oxygen is probably misleading. It was shown that gases existed in water both in the form of individual molecules and nanobubbles. Mechanical stress did not influence the number or size of nanobubbles. While gas nanobubbles were absent in freshly prepared deaerated water, they appeared following exposure to mechanical stress. In addition, in mechanically treated gas-saturated water, there was seemingly an equilibrium shift towards the decomposition of carbonic acid to water and carbon dioxide. At the same time, the pH of water tended to increase immediately after mechanical stress. It was demonstrated that reactive oxygen species (ROS) form in gas-saturated water under mechanical stress (30 Hz, amplitude of 5 mm). The relative generation rate of hydrogen peroxide and of the hydroxyl radical was 1 nM/min and 0.5 nM/min, respectively. It was found that with an increase in the frequency of mechanical action (f), the rate of ROS generation increased in proportion to f 2. The major pathways for hydrogen peroxide generation are probably associated with the formation of singlet oxygen and its further reduction, and the alternative pathway is the formation of hydrogen peroxide as a result of hydroxyl radical recombination.