Excited State Oxygen Research Articles

Degradation of n-hexane by the high-throughput double dielectric barrier discharge: Influencing factors, degradation mechanism and pathways

The emission of volatile organic compounds (VOCs) is known to be a source of various environmental problems. N-hexane is a saturated aliphatic hydrocarbon that is a major precursor of ozone. For the decomposition of n-hexane, a novel double dielectric barrier discharge (DDBD) reactor design is developed and tested on a pilot scale. The factors influencing the plasma degradation of n-hexane have been thoroughly investigated. The degradation efficiency, carbon balance and nitrogen oxide concentration were measured and analysed. Through experiments, it was found that the maximum removal of n-hexane at an initial concentration of 2000 ppm and a flow rate of 5 L/min was 1544 ppm. The associated energy efficiency reached 67.71 ppm/J. The excited states of oxygen and nitrogen (O2+, O(3 s5S-3p5P), N2(C3Πu-B3Πg), N2+(B2Σu+-X2Σg+)) during n-hexane degradation were observed. Possible degradation pathways of n-hexane are proposed, and it is revealed that the active species play an important role in the formation of oxygen and nitrogen-containing volatile organic by-products. The results show that the pilot-scale design of the DDBD system provides a feasible way for the industrial treatment of n-hexane, and provides fundamental insights into the mechanism of plasma catalytic system operation.

Generating a Sustained Oxygen-Stable Atomic Concentration in a High-Temperature Gas Effect Investigation.

Modulated laser absorption spectroscopy is an ideal technique for evaluating flow-field parameters and determining flow-field quality by measuring the atoms dissociated in high-temperature environments. However, to obtain the absolute number density of atoms in the flow field, it is necessary to compare the measured modulated absorption spectroscopy signal with a known atomic concentration and establish a quantitative relationship through concentration calibration. Nevertheless, it remains a challenging task to prepare transient atomic samples with known concentrations that meet the calibration requirements. This study utilized the alternating-current glow discharge technique to dissociate oxygen in the air flow, resulting in the continuous generation of oxygen atoms. The absolute number densities of the generated oxygen atoms were determined by measuring the direct absorption spectra of centered on 777 nm for oxygen atoms. The number densities of the generated atoms were finely tuned by adjusting the discharge parameters. Throughout the 120-min continuous operation of the discharge system, the concentration of excited-state oxygen atoms remained stable within the range of (2.51 ± 0.02) × 108 cm-3, demonstrating the remarkable stability of the transient atomic concentration generated by the glow discharge plasma. This observation suggests that the generated atoms can be utilized as a standardized atomic sample of known concentration for absolute concentration calibration purposes.

Computer-simulated degradation of CF3Cl, CF2Cl2, and CFCl3 under electron beam irradiation

Abstract Electron beam treatment technologies should be versatile in the removal of chlorofluorocarbons (CFCs) owing to their exceptional cross sections for the thermal electrons generated in the radiolysis of air. Humidity, dose rates, O2 concentration, and CFC concentration influence the efficiency of the destruction process under electron beam treatment. Computer simulations have been used to theoretically demonstrate the destruction of chlorotrifluoromethane (CF3Cl), dichlorodifluoromethane (CF2Cl2), and trichlorofluoromethane (CFCl3) in the air (N2 + O2: 80% + 20%) in room temperature up to a dose of 13 kGy. Under these conditions, it is predicted that the removal efficiency is in the order CF3Cl (0.1%) < CF2Cl2 (7%) < CFCl3 (34%), which shows the dependence of the process on the number of substituted Cl atoms. Dissociative electron attachment with the release of Cl– is the primary process initiating the destruction of CFCs from the air stream. Reactions with the first excited state of oxygen, namely, O(1D), and charge-transfer reactions further promote the degradation process. The degradation products can be further degraded to CO2, Cl2, and F2 by prolonged radiation treatment. Other predicted products can also be removed through chemical processes.

A New Insight into the Singlet Oxygen Mechanism for Photodynamic Therapy.

Modern photodynamic therapy has been built on the mechanism of the interaction between the photosensitizer (porphyrin derivatives) and oxygen to produce singlet oxygen, which relies on energy transfer from the triplet excited state (T1) of porphyrin to the excited state of oxygen. In this process, the energy transfer from the singlet excited state (S1) of porphyrin to oxygen is believed to be not pronounced as the rapid decay of S1 and the large energy mismatch. Here, we have evidenced the existence of an energy transfer between S1 and oxygen, which can contribute to the production of singlet oxygen. For hematoporphyrin monomethyl ether (HMME), the Stern-Volmer constant of S1 (KSV') is 0.023 kPa-1, according to the oxygen concentration-dependent steady fluorescence intensities. In addition, fluorescence dynamic curves of S1 under various oxygen concentrations have also been measured through ultrafast pump probe experiments to further verify our results.

Singlet O2 from Ultraviolet Excitation of the Quinoline-O2 Complex.

We report results from experiments with the quinoline-O2 complex, which was photodissociated using light near 312 nm. Photodissociation resulted in formation of the lowest excited state of oxygen, O2 a 1Δg, which we detected using resonance enhanced multiphoton ionization and velocity map ion imaging. The O2+ ion image allowed for a determination of the center-of-mass translational energy distribution, P(ET), following complex dissociation. We also report results of electronic structure calculations for the quinoline singlet ground state and lowest energy triplet state. From the CCSD/aug-cc-pVDZ//(U)MP2/cc-pVDZ calculations, we determined the lowest energy triplet state to have ππ* electronic character and to be 2.69 eV above the ground state. We also used electronic structure calculations to determine the geometry and binding energy for several quinoline-O2 complexes. The calculations indicated that the most strongly bound complex has a well depth of about 0.11 eV and places the O2 moiety above and approximately parallel to the quinoline ring system. By comparing the experimental P(ET) with the energy for the singlet ground state and the lowest energy triplet state, we concluded that the quinoline product was formed in the lowest energy triplet state. Finally, we found the experimental P(ET) to be in agreement with a Prior translational energy distribution, which suggests a statistical dissociation for the complex.

Hierarchically Structured Molecularly Imprinted Nanotransducers for Truncated HER2-Targeted Photodynamic Therapy of Therapeutic Antibody-Resistant Breast Cancer.

Antibodies have been a mainstream class of therapeutics for clinical treatment of various diseases, especially cancers. However, mutation in cancer cells leads to resistance to therapeutic antibodies, hyperactivity of proliferation of cancer cells, and difficulty in the development of therapeutic antibodies. Herein, we present a strategy termed molecularly imprinted nanotransducer (MINT) for targeted photodynamic therapy (PDT) of mutated cancers. The MINT is a rationally engineered nanocomposite featuring a core of an upconversion nanoparticle, a shell of a thin layer of molecularly imprinted polymer, and a photosensitizer modified on the surface. As a proof-of-principle, truncated HER2 (P95HER2) overexpressed breast cancer, a challenging cancer lacking effective targeted therapeutics, was used as the cancer model. The designed structure, properties, functions, and anticancer efficacy of MINT were systematically investigated and experimentally confirmed. The MINT could not only specifically target P95HER2+ cancer cells in vitro and in vivo but also efficiently transfer the irradiated light and generate excited-state oxygen, resulting in efficient targeted cancer killing. Therefore, the MINT strategy provides a promising therapeutic for targeted PDT of drug-resistant cancers caused by target mutation.

Development of a Stark shift measurement technique using excited-state oxygen atoms to determine electron number density in shock heated O2/Ar above 10 000 K

We present measurements of electron number density, n e, in partially ionized gases containing electronically excited atomic oxygen, at nominal translational temperatures between 10 100–11 200 K. The measurements were based on the Stark shift of the O() to O() transition at 926 nm. The current work scanned the laser across the transition and utilized the Stark shift of the absorbance for robust determination of n e. The measurements were conducted in a shock-heated 1% O2/Ar mixture, with a measurement time resolution of 20 μs. A line-center shift of −0.06 cm−1 was observed within around 500 μs of the test time after the mixture was instantaneously heated to 11 200 K by the reflected shock wave, which corresponded to an electron number density increase from 0 to 2 × 1021 m−3 due to collisional ionization. The measurement method and resulting data may be of interest in future studies of high-temperature air flows.

The role of O(1D) in the oxidation mechanism of ethylene by iodosobenzene and other hypervalent molecules.

The role of the first excited state of oxygen (1D) is proven essential for the description of terminal iodine-oxygen chemical bonds. The description of the I-O bond as a dative one from iodine to O(1D) provides a simple and accurate picture which explains the oxidation properties of iodosobenzene and similar in nature molecules.

Low-temperature formation of high-quality gate oxide by ultraviolet irradiation on spin-on-glass

Although a UV cure was found to effectively convert a perhydropolysilazane (PHPS) spin-on-glass film into a dense SiOx film at low temperature, the electrical characteristics were never reported in order to recommend the use of PHPS as a gate-oxide material that can be formed at low temperature. We have formed a high-quality gate oxide by UV irradiation on the PHPS film, and obtained an interface midgap trap density of 3.4 × 1011 cm−2 eV−1 by the UV wet oxidation and UV post-metallization annealing (PMA), at a temperature as low as 160 °C. In contrast to the UV irradiation using short-wavelength UV light, which is well known to enhance oxidation by the production of the excited states of oxygen, the UV irradiation was carried out using longer-wavelength UV light from a metal halide lamp. The UV irradiation during the wet oxidation of the PHPS film generates electron-hole pairs. The electrons ionize the H2O molecules and facilitate dissociation of the molecules into H and OH−. The OH− ions are highly reactive with Si and improve the stoichiometry of the oxide. The UV irradiation during the PMA excites the electrons from the accumulation layer, and the built-in electric field makes the electron injection into the oxide much easier. The electrons injected into the oxide recombine with the trapped holes, which have caused a large negative flat band voltage shift after the UV wet oxidation, and also ionize the H2O molecules. The ionization results in the electron stimulated dissociation of H2O molecules and the decreased interface trap density.

Excited oxygen states in the Venus nightglow 1This article is part of a Special Issue that honours the work of Dr. Donald M. Hunten FRSC who passed away in December 2010 after a very illustrious career.

In the absence of solar radiation, the most common photoexcitation process in the terrestrial planets results from atom recombination. Thus, in the Mars and Venus atmospheres recombination of O(3P) + O(3P) and O(3P) + N(4S) leads to emissions of excited states of O2 and NO, respectively. However, in the Earth’s atmosphere there are ionospheric emissions that depend on interactions of charged species, for example, the oxygen red and green lines arising from dissociative recombination (DR) of [Formula: see text]. In the case of the CO2 planets, the predominant ionospheric ion is also [Formula: see text], so that in principle DR is important in that environment, where the markers would also be the red and green lines. Whether these can be detected depends on DR rates and the radiating efficiencies of these species. In this report we discuss the history of green line detection in the Venus nightglow as well as the observations of excited O2 molecules, and the lack of appearance of the O2 (b–X) Atmospheric 0–0 band.

Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production

Carotenoids, natural pigments widely distributed in algae and plants, have a conjugated double bond system. Their excitation energies are correlated with conjugation length. We hypothesized that carotenoids whose energy states are above the singlet excited state of oxygen (singlet oxygen) would possess photosensitizing properties. Here, we demonstrated that human skin melanoma (A375) cells are damaged through the photo-excitation of several carotenoids (neoxanthin, fucoxanthin and siphonaxanthin). In contrast, photo-excitation of carotenoids that possess energy states below that of singlet oxygen, such as β-carotene, lutein, loroxanthin and violaxanthin, did not enhance cell death. Production of reactive oxygen species (ROS) by photo-excited fucoxanthin or neoxanthin was confirmed using a reporter assay for ROS production with HeLa Hyper cells, which express a fluorescent indicator protein for intracellular ROS. Fucoxanthin and neoxanthin also showed high cellular penetration and retention. Electron spin resonance spectra using 2,2,6,6-tetramethil-4-piperidone as a singlet oxygen trapping agent demonstrated that singlet oxygen was produced via energy transfer from photo-excited fucoxanthin to oxygen molecules. These results suggest that carotenoids such as fucoxanthin, which are capable of singlet oxygen production through photo-excitation and show good penetration and retention in target cells, are useful as photosensitizers in photodynamic therapy for skin disease.

Mechanically induced generation of highly reactive excited-state oxygen molecules in cluster scattering

Molecular electronic excitation in (O(2))(n) clusters induced by mechanical collisions via the "chemistry with a hammer" is investigated by a combination of molecular dynamics simulations and quantum chemistry calculations. Complete active space self-consistent field augmented with triple-zeta polarizable basis set quantum chemistry calculations of a compressed (O(2))(2) cluster model in various configurations reveal the emergence of possible pathways for the generation of electronically excited singlet O(2) molecules upon cluster compression and vibrational excitation, due to electronic curve-crossing and spin-orbit coupling. Extrapolation of the model (O(2))(2) results to larger clusters suggests a dramatic increase in the population of electronically excited O(2) products, and may account for the recently observed cluster-catalyzed oxidation of silicon surfaces, via singlet oxygen generation induced by cluster impact, followed by surface reaction of highly reactive singlet O(2) molecules. Extensive molecular dynamics simulations of (O(2))(n) clusters colliding onto a hot surface indeed reveal that cluster compression is sufficient under typical experimental conditions for nonadiabatic transitions to occur. This work highlights the importance of nonadiabatic effects in the "chemistry with a hammer."

Autoionization dynamics and Feshbach resonances: Femtosecond EUV study of O2 excitation and dissociation

In this work, we present a time-domain study of the complex, multi-step, evolution of highly excited states of oxygen (O2) that result from EUV photoionization. By monitoring the dissociation of molecular oxygen ions, we show that autoionization cannot occur until the internuclear separation is 30 Å or greater. As the ion and excited neutral atom separate, we directly observe the transformation of electronically bound states of the molecular ion into Feshbach resonances of the neutral oxygen atom. We achieve this by using laser high-harmonics in a femtosecond EUV-IR pump-probe scheme, combined with a triple coincidence reaction microscope measurement. Finally, we show control of the dissociation pathway through IR pulse induced ionization.

Auger decays of doubly excited states of oxygen, carbon, and nitrogen ions

The probabilities and energies of Auger transitions in doubly excited 3l i 3l j , 3l i 4l j , and 4l i 4l j states of oxygen, carbon, and nitrogen ions have been calculated using the Hartree-Fock approximation. The emission spectra are determined and changes in the spectral characteristics depending on the charge multiplicity and the number of additional electrons in the ground state of the initial ion are analyzed. The data obtained are used to interpret the spectra of Auger electron emission in the atmospheres of planets and comets.

Radiative decays of doubly excited states of oxygen, carbon, and nitrogen ions

Systematic calculations of the probabilities and energies of radiative transitions in doubly excited 3l3l′, 3l4l′, and 4l4l′ states of oxygen, carbon, and nitrogen ions have been carried out within the Hartree-Fock approximation. The emission spectra are obtained, and analysis of the changes in the spectral characteristics with a change in the charge and the number of additional electrons in the ground state of the initial ion is performed. The data obtained are used to interpret the X-ray spectra of the atmospheres of planets and comets.

Effect of laser-induced excitation of oxygen on ignition in HCCI engines analysed by numerical simulations

Lack of proven means to control ignition impedes practical implementation of homogenous charge compression ignition (HCCI) engines. In the present paper, we investigate if laser-induced excitation of oxygen might aid solution of the ignition control problem in HCCI engines. Simulations by previous researchers showed laser-induced excitation of oxygen enhances ignition in supersonic combustion. Based on this previous research, we extend a chemical kinetic mechanism for propane autoignition to include reactions for two excited oxygen states, O2(a1Δ g ) and O2(b1Σ g +). Simulations examined the effect of each of these excited O2 states upon ignition timing in an HCCI engine. Results indicate that achieving useful control of the combustion process requires substantial conversion of O2 to either of the excited states. At the required level of excitation, the power required for the laser may lower engine efficiency.

MAGNETOPOLARON EFFECT ON SILICON AND OXYGEN DONORS IN GAN

Luminescence experiments in magnetic fields up to 28 T on a freestanding gallium nitride ( GaN ) sample and a heteroepitaxial GaN layer lightly doped with silicon are presented. In these samples, the principal D0X recombination channel is accompanied by two electron satellites (TES), which involve the excited donor states as well as by the longitudinal-optic (LO) phonon replica of the principal transitions. When the internal donor excitations are magnetically tuned into resonance with the LO-phonon excitation, the intensity of TES is strongly enhanced and clear avoided-crossings between the LO-phonon replica of the principal D0X transition and TES involving highly excited states of oxygen and silicon are resolved. The observed behavior is explained in terms of resonant interaction between LO-phonons and donor-bound electrons. It is found that the resonant magnetopolaron interaction is stronger for the oxygen as compared to the silicon donor.

Electronically excited oxygen states in exoemission and heterogeneous catalytic oxidation reactions

The role played by electronically excited oxygen in exoemission and heterogeneous catalysis is considered. The results obtained in a study of thermally stimulated exoemission from the surface of Al2O3 and SiO2 are compared with data of temperature-programmed desorption of singlet oxygen O2(1Δg) from the surface of Al2O3 and HZSM-5 zeolites with different SiO2/Al2O3 ratios. The role played by electronically excited oxygen states in heterogeneous catalysis is discussed on the basis of our own and literature data. Thermally stimulated exoemission after the action of an electron flow is considered taking into account electron-stimulated desorption and the available data on electron bombardment in catalysis.

Resonant charge exchange and relevant transport cross sections for excited states of oxygen and nitrogen atoms

Resonant charge-exchange cross sections and the relevant transport (diffusion) cross sections for excited states of nitrogen and oxygen atoms have been calculated. The calculation is performed using the asymptotic approach, based on the single-electron asymptotic representation of the electron wave function. The ground-state cross sections are in a good agreement with those calculated via comprehensive quantum chemical approach. The results of calculations demonstrate a reasonable accuracy and a high convenience of this approach in determination of cross sections for the manifold of excited states of atoms.

The Excited States of Molecular Oxygen

Identifies a mistake in the electronic structure of the first two excited states of oxygen.