Heliocentric distance dependencies of the C2 lifetime and C2 parent production rate in comet P/Brorsen-Metcalf (1989o)

NASA Technical Reports Server (NTRS)

Lazzarin, M.; Tozzi, Giau Paolo; Barbieri, C.; Festou, Michel C.

1992-01-01

Comet P/Brorsen-Metcalf (1989o) has been extensively observed in the visible and in the ultraviolet during its latest apparition of summer 1989. In this paper we report a preliminary determination of the C2 production rates and lifetimes and we compare those rates to the H2O production rates obtained from UV data.

Non-noble metal Cu-loaded TiO2 for enhanced photocatalytic H2 production.

PubMed

Foo, Wei Jian; Zhang, Chun; Ho, Ghim Wei

2013-01-21

Here we have demonstrated the preparation of high-quality, monodispersed and tunable phases of Cu nanoparticles. Structural and chemical composition studies depict the evolution of Cu-Cu(2)O-CuO nanoparticles at various process stages. The loading of Cu and Cu oxide nanoparticles on TiO(2) catalyst has enhanced the photocatalytic H(2) production. Comparatively, H(2) treatment produces well-dispersed Cu nanoparticles with thin oxide shells that show the highest H(2) production amongst the samples. The relatively higher photocatalytic performance is deemed to result from reduced structural defects, higher surface area and dispersivity as well as favorable charge transfer, which inhibits recombination. The Cu nanoparticles are shown to be a promising alternative to noble metal-loaded TiO(2) catalyst systems due to their low cost and high performance in photocatalytic applications.

Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yu-Heng; Pegis, Michael L.; Mayer, James M.

A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2more » was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.« less

Kinetics of Al + H2O reaction: theoretical study.

PubMed

Sharipov, Alexander; Titova, Nataliya; Starik, Alexander

2011-05-05

Quantum chemical calculations were carried out to study the reaction of Al atom in the ground electronic state with H(2)O molecule. Examination of the potential energy surface revealed that the Al + H(2)O → AlO + H(2) reaction must be treated as a complex process involving two steps: Al + H(2)O → AlOH + H and AlOH + H → AlO + H(2). Activation barriers for these elementary reaction channels were calculated at B3LYP/6-311+G(3df,2p), CBS-QB3, and G3 levels of theory, and appropriate rate constants were estimated by using a canonical variational theory. Theoretical analysis exhibited that the rate constant for the Al + H(2)O → products reaction measured by McClean et al. must be associated with the Al + H(2)O → AlOH + H reaction path only. The process of direct HAlOH formation was found to be negligible at a pressure smaller than 100 atm.

Enhanced H2O2 Production at Reductive Potentials from Oxidized Boron-Doped Ultrananocrystalline Diamond Electrodes.

PubMed

Thostenson, James O; Ngaboyamahina, Edgard; Sellgren, Katelyn L; Hawkins, Brian T; Piascik, Jeffrey R; Klem, Ethan J D; Parker, Charles B; Deshusses, Marc A; Stoner, Brian R; Glass, Jeffrey T

2017-05-17

This work investigates the surface chemistry of H 2 O 2 generation on a boron-doped ultrananocrystalline diamond (BD-UNCD) electrode. It is motivated by the need to efficiently disinfect liquid waste in resource constrained environments with limited electrical power. X-ray photoelectron spectroscopy was used to identify functional groups on the BD-UNCD electrode surfaces while the electrochemical potentials of generation for these functional groups were determined via cyclic voltammetry, chronocoulometry, and chronoamperometry. A colorimetric technique was employed to determine the concentration and current efficiency of H 2 O 2 produced at different potentials. Results showed that preanodization of an as-grown BD-UNCD electrode can enhance the production of H 2 O 2 in a strong acidic environment (pH 0.5) at reductive potentials. It is proposed that the electrogeneration of functional groups at oxidative potentials during preanodization allows for an increased current density during the successive electrolysis at reductive potentials that correlates to an enhanced production of H 2 O 2 . Through potential cycling methods, and by optimizing the applied potentials and duty cycle, the functional groups can be stabilized allowing continuous production of H 2 O 2 more efficiently compared to static potential methods.

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

NASA Astrophysics Data System (ADS)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar

A continuous [15O]H2O production and infusion system for PET imaging

NASA Astrophysics Data System (ADS)

Sajjad, Munawwar; Liow, Jeih-San

1999-06-01

A system for continuous production and infusion of [15O]H2O has been designed for PET cerebral blood flow studies. The injection system consists of a four-port-two-position valve, two Horizon Nxt infusion pumps, and a sterile 50 ml vial. The variation of the production of [15O]H2O was <1%. The variation of activity delivered measured by scanner counts during the steady state period was <2%.

Enhanced H2O2 Production at Reductive Potentials from Oxidized Boron-Doped Ultrananocrystalline Diamond Electrodes

PubMed Central

2017-01-01

This work investigates the surface chemistry of H2O2 generation on a boron-doped ultrananocrystalline diamond (BD-UNCD) electrode. It is motivated by the need to efficiently disinfect liquid waste in resource constrained environments with limited electrical power. X-ray photoelectron spectroscopy was used to identify functional groups on the BD-UNCD electrode surfaces while the electrochemical potentials of generation for these functional groups were determined via cyclic voltammetry, chronocoulometry, and chronoamperometry. A colorimetric technique was employed to determine the concentration and current efficiency of H2O2 produced at different potentials. Results showed that preanodization of an as-grown BD-UNCD electrode can enhance the production of H2O2 in a strong acidic environment (pH 0.5) at reductive potentials. It is proposed that the electrogeneration of functional groups at oxidative potentials during preanodization allows for an increased current density during the successive electrolysis at reductive potentials that correlates to an enhanced production of H2O2. Through potential cycling methods, and by optimizing the applied potentials and duty cycle, the functional groups can be stabilized allowing continuous production of H2O2 more efficiently compared to static potential methods. PMID:28471651

Tunable Syngas Production from CO2 and H2 O in an Aqueous Photoelectrochemical Cell.

PubMed

Chu, Sheng; Fan, Shizhao; Wang, Yongjie; Rossouw, David; Wang, Yichen; Botton, Gianluigi A; Mi, Zetian

2016-11-07

Syngas, the mixture of CO and H 2 , is a key feedstock to produce methanol and liquid fuels in industry, yet limited success has been made to develop clean syngas production using renewable solar energy. We demonstrated that syngas with a benchmark turnover number of 1330 and a desirable CO/H 2 ratio of 1:2 could be attained from photoelectrochemical CO 2 and H 2 O reduction in an aqueous medium by exploiting the synergistic co-catalytic effect between Cu and ZnO. The CO/H 2 ratio in the syngas products was tuned in a large range between 2:1 and 1:4 with a total unity Faradaic efficiency. Moreover, a high Faradaic efficiency of 70 % for CO was acheived at underpotential of 180 mV, which is the lowest potential ever reported in an aqueous photoelectrochemical cell. It was found that the combination of Cu and ZnO offered complementary chemical properties that lead to special reaction channels not seen in Cu, or ZnO alone. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The pH dependency of N-converting enzymatic processes, pathways and microbes: effect on net N2 O production.

PubMed

Blum, Jan-Michael; Su, Qingxian; Ma, Yunjie; Valverde-Pérez, Borja; Domingo-Félez, Carlos; Jensen, Marlene Mark; Smets, Barth F

2018-05-01

Nitrous oxide (N 2 O) is emitted during microbiological nitrogen (N) conversion processes, when N 2 O production exceeds N 2 O consumption. The magnitude of N 2 O production vs. consumption varies with pH and controlling net N 2 O production might be feasible by choice of system pH. This article reviews how pH affects enzymes, pathways and microorganisms that are involved in N-conversions in water engineering applications. At a molecular level, pH affects activity of cofactors and structural elements of relevant enzymes by protonation or deprotonation of amino acid residues or solvent ligands, thus causing steric changes in catalytic sites or proton/electron transfer routes that alter the enzymes' overall activity. Augmenting molecular information with, e.g., nitritation or denitrification rates yields explanations of changes in net N 2 O production with pH. Ammonia oxidizing bacteria are of highest relevance for N 2 O production, while heterotrophic denitrifiers are relevant for N 2 O consumption at pH > 7.5. Net N 2 O production in N-cycling water engineering systems is predicted to display a 'bell-shaped' curve in the range of pH 6.0-9.0 with a maximum at pH 7.0-7.5. Net N 2 O production at acidic pH is dominated by N 2 O production, whereas N 2 O consumption can outweigh production at alkaline pH. Thus, pH 8.0 may be a favourable pH set-point for water treatment applications regarding net N 2 O production. © 2018 Society for Applied Microbiology and John Wiley & Sons Ltd.

Photoproduction of One-Electron Reducing Intermediates by Chromophoric Dissolved Organic Matter (CDOM): Relation to O2- and H2O2 Photoproduction and CDOM Photooxidation.

PubMed

Zhang, Yi; Blough, Neil V

2016-10-06

A molecular probe, 3-amino-2,2,5,5,-tetramethy-1-pyrrolydinyloxy (3ap), was employed to determine the formation rates of one-electron reducing intermediates generated photochemically from both untreated and borohydride-reduced Suwanee River fulvic and humic acids (SRFA and SRHA, respectively). This stable nitroxyl radical reacts rapidly with reducing radicals and other one-electron reductants to produce a relatively stable product, the hydroxylamine, which can be derivatized with fluorescamine, separated by HPLC and quantified fluorimetrically. We provide evidence that O 2 and 3ap compete for the same pool(s) of photoproduced reducing intermediates, and that under appropriate experimental conditions, the initial rate of hydroxylamine formation (R H ) can provide an estimate of the initial rate of superoxide (O 2 - ) formation. However, comparison of the initial rates of H 2 O 2 formation (R H2O2 ) to that of R H show far larger ratios of R H /R H2O2 (∼6-13) than be accounted for by simple O 2 - dismutation (R H /R H2O2 = 2), implying a significant oxidative sink of O 2 - (∼67-85%). Because of their high reactivity with O 2 - and their likely importance in the photochemistry of CDOM, we suggest that coproduced phenoxy radicals could represent a viable oxidative sink. Because O 2 - /phenoxy radical reactions can lead to more highly oxidized products, O 2 - could be playing a far more significant role in the photooxidation of CDOM than has been previously recognized.

Reactions of electronically excited molecular nitrogen with H2 and H2O molecules: theoretical study

NASA Astrophysics Data System (ADS)

Pelevkin, Alexey V.; Sharipov, Alexander S.

2018-05-01

Comprehensive quantum chemical analysis with the usage of the second-order perturbation multireference XMCQDPT2 approach was carried out to study the processes in the   +  H2 and   +  H2O systems. The energetically favorable reaction pathways have been revealed based on the exploration of potential energy surfaces. It has been shown that the reactions   +  H2 and   +  H2O occur with small activation barriers and, primarily, lead to the formation of N2H  +  H and N2H  +  OH products, respectively. Further, the interaction of these species could give rise to the ground state and H2 (or H2O) products, however, the estimations, based on RRKM theory and dynamic reaction coordinate calculations, exhibited that the   +  H2 and   +  H2O reactions lead to the dissociative quenching predominately. Appropriate rate constants for revealed reaction channels have been estimated by using a canonical variational theory and capture approximation. Corresponding three-parameter Arrhenius expressions for the temperature range T  =  300  ‑  3000 K were reported.

The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

NASA Astrophysics Data System (ADS)

Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing

2018-07-01

The addition reaction of CH2OO + H2O → CH2(OH)OOH without and with X (X = H2CO3, CH3COOH and HCOOH) and H2O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH2OO + H2O → CH2(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2OO...H2O is favourable one. Water-assisted CH2OO + H2O → CH2(OH)OOH can occur by H2O moiety of (H2O)2 or the whole (H2O)2 forming cyclic structure with CH2OO, where the latter form is more favourable. Because the concentration of H2CO3 is unknown, the influence of CH3COOH, HCOOH and H2O were calculated within 0-30 km altitude of the Earth's atmosphere. The results calculated within 0-5 km altitude show that H2O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%-77.26% and 0.04%-1.76%. Within 5-30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%-98.28%. However, compared with the reaction of CH2OO + HCOOH, the rate of CH2OO...H2O + HCOOH is much slower.

Preparation and characterization of magnetic CsH{sub 2}PW{sub 12}O{sub 40}/Fe–SiO{sub 2} nanocatalysts for biodiesel production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feyzi, Mostafa, E-mail: Dalahoo2011@yahoo.com; Nanoscience and Nanotechnology Research Center; Nourozi, Leila

Graphical abstract: In this study, a series of magnetic CsH{sub 2}PW{sub 12}O{sub 40}/Fe–SiO{sub 2} nanocatalysts were prepared and tested for biodiesel production. The best operational conditions were CH3OH/oil = 12/1 at 60 °C with mechanical stirring, the biodiesel yield reaches to 81% in 4 h. Also notably, recovery of the catalyst can be achieved easily with the help of an external magnet with no need for expensive ultracentrifugation. - Highlights: • Effects of preparation conditions for biodiesel production were studied. • The CsH{sub 2}PW{sub 12}O{sub 40}/Fe–SiO{sub 2} catalyst is efficient catalyst for biodiesel production. • The reaction conditions were foundmore » methanol/oil = 12/1, T = 60 °C. - Abstract: The magnetic CsH{sub 2}PW{sub 12}O{sub 40}/Fe–SiO{sub 2} nanocatalysts were prepared via combination of sol–gel and impregnation methods. The effects of different H{sub 3}PW{sub 12}O{sub 40}/(Fe–SiO{sub 2}) weight percentage, loading of Cs as a promotor and calcination conditions on the catalytic performance has been studied. It was found that the catalyst with H{sub 3}PW{sub 12}O{sub 40}/Fe–SiO{sub 2} = 4 wt.% and Cs = 2 wt.% is an optimal catalyst for biodiesel production. The activity of optimal catalyst was studied in different operational conditions. The best operational conditions were CH{sub 3}OH/oil = 12/1 at 60 °C with mechanical stirring rate of 500 rpm and the biodiesel yield reaches to 81% in 4 h. Characterization of catalysts was carried out by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), N{sub 2} adsorption–desorption measurements methods, Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC)« less

OH and O radicals production in atmospheric pressure air/Ar/H2O gliding arc discharge plasma jet

NASA Astrophysics Data System (ADS)

N, C. ROY; M, R. TALUKDER; A, N. CHOWDHURY

2017-12-01

Atmospheric pressure air/Ar/H2O gliding arc discharge plasma is produced by a pulsed dc power supply. An optical emission spectroscopic (OES) diagnostic technique is used for the characterization of plasmas and for identifications of {{OH}} and {{O}} radicals along with other species in the plasmas. The OES diagnostic technique reveals the excitation T x ≈ 5550-9000 K, rotational T r ≈ 1350-2700 K and gas T g ≈ 850-1600 K temperatures, and electron density {n}{{e}}≈ ({1.1-1.9})× {10}14 {{{cm}}}-3 under different experimental conditions. The production and destruction of {{OH}} and {{O}} radicals are investigated as functions of applied voltage and air flow rate. Relative intensities of {{OH}} and {{O}} radicals indicate that their production rates are increased with increasing {{Ar}} content in the gas mixture and applied voltage. {n}{{e}} reveals that the higher densities of {{OH}} and {{O}} radicals are produced in the discharge due to more effective electron impact dissociation of {{{H}}}2{{O}} and {{{O}}}2 molecules caused by higher kinetic energies as gained by electrons from the enhanced electric field as well as by enhanced {n}{{e}}. The productions of {{OH}} and {{O}} are decreasing with increasing air flow rate due to removal of Joule heat from the discharge region but enhanced air flow rate significantly modifies discharge maintenance properties. Besides, {T}{{g}} significantly reduces with the enhanced air flow rate. This investigation reveals that {{Ar}} plays a significant role in the production of {{OH}} and {{O}} radicals.

The denitrification paradox: The role of O2 in sediment N2O production

NASA Astrophysics Data System (ADS)

Barnes, Jonathan; Upstill-Goddard, Robert C.

2018-01-01

We designed a novel laboratory sediment flux chamber in which we maintained the headspace O2 partial pressure at preselected values, allowing us to experimentally regulate "in-situ" O2 to evaluate its role in net N2O production by an intertidal estuarine sediment (Tyne, UK). In short-term (30 h) incubations with 10 L of overlying estuarine water (∼3 cm depth) and headspace O2 regulation (headspace: sediment/water ratio ∼9:1), net N2O production was highest at 1.2% O2 (sub-oxic; 32.3 nmol N2O m-2 d-1), an order of magnitude higher than at either 0.0% (anoxic; 2.5 N2O nmol m-2 d-1) or 20.85% (ambient; 2.3 nmol N2O m-2 d-1) O2. In a longer-term sealed incubation (∼490 h) without O2 control, time-dependent behaviour of N2O in the tank headspace was highly non-linear with time, showing distinct phases: (i) an initial period of no or little change in O2 or N2O up to ∼ 100 h; (ii) a quasi-linear, inverse correlation between O2 and N2O to ∼360 h, in which O2 declined to ∼2.1% and N2O rose to ∼7800 natm; (iii) over the following 50 h a slower O2 decline, to ∼1.1%, and a more rapid N2O increase, to ∼12000 natm; (iv) over the next 24 h a slowed O2 decline towards undetectable levels and a sharp fall in N2O to ∼4600 natm; (iv) a continued N2O decrease at zero O2, to ∼3000 natm by ∼ 490 h. These results show clearly that rapid N2O consumption (∼115 nmol m-2 d-1), presumably via heterotrophic denitrification (HD), occurs under fully anoxic conditions and therefore that N2O production, which was optimal for sub-oxic O2, results from other nitrogen transformation processes. In experiments in which we amended sediment overlying water to either 1 mM NH4+ or 1 mM NO3-, N2O production rates were 2-134 nmol N2O m-2 d-1 (NH4+ addition) and 0.4-2.2 nmol N2O m-2 d-1 (NO3- addition). We conclude that processes involving NH4+ oxidation (nitrifier nitrification; nitrifier denitrification; nitrification-coupled denitrification) are principally responsible for N2O

Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

NASA Astrophysics Data System (ADS)

Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

1994-05-01

Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

Preparation and enhanced visible-light photocatalytic H2-production activity of CdS-sensitized Pt/TiO2 nanosheets with exposed (001) facets.

PubMed

Qi, Lifang; Yu, Jiaguo; Jaroniec, Mietek

2011-05-21

CdS-sensitized Pt/TiO(2) nanosheets with exposed (001) facets were prepared by hydrothermal treatment of a Ti(OC(4)H(9))(4)-HF-H(2)O mixed solution followed by photochemical reduction deposition of Pt nanoparticles (NPs) on TiO(2) nanosheets (TiO(2) NSs) and chemical bath deposition of CdS NPs on Pt/TiO(2) NSs, successively. The UV and visible-light driven photocatalytic activity of the as-prepared samples was evaluated by photocatalytic H(2) production from lactic acid aqueous solution under UV and visible-light (λ ≥ 420 nm) irradiation. It was shown that no photocatalytic H(2)-production activity was observed on the pure TiO(2) NSs under UV and/or visible-light irradiation. Deposition of CdS NPs on Pt/TiO(2) NSs caused significant enhancement of the UV and visible-light photocatalytic H(2)-production rates. The morphology of TiO(2) particles had also significant influence on the visible-light H(2)-production activity. Among TiO(2) NSs, P25 and the NPs studied, the CdS-sensitized Pt/TiO(2) NSs show the highest photocatalytic activity (13.9% apparent quantum efficiency obtained at 420 nm), exceeding that of CdS-sensitized Pt/P25 by 10.3% and that of Pt/NPs by 1.21%, which can be attributed to the combined effect of several factors including the presence of exposed (001) facets, surface fluorination and high specific surface area. After many replication experiments of the photocatalytic hydrogen production in the presence of lactic acid, the CdS-sensitized Pt/TiO(2) NSs did not show great loss in the photocatalytic activity, confirming that the CdS/Pt/TiO(2) NSs system is stable and not photocorroded. © The Owner Societies 2011

Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

PubMed

Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

2016-04-05

UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

VUV photoionization cross sections of HO2, H2O2, and H2CO.

PubMed

Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

2015-02-26

The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

Enhanced photocatalytic H2-production activity of graphene-modified titania nanosheets

NASA Astrophysics Data System (ADS)

Xiang, Quanjun; Yu, Jiaguo; Jaroniec, Mietek

2011-09-01

Graphene-modified TiO2 nanosheets with exposed (001) facets (graphene/TiO2) were prepared by microwave-hydrothermal treatment of graphene oxide (GO) and hydrothermally synthesized TiO2 nanosheets with exposed (001) facets in an ethanol-water solvent. These nanocomposite samples showed high photocatalytic H2-production activity in aqueous solutions containing methanol, as sacrificial reagent, even without Pt co-catalyst. The optimal graphene content was found to be ~1.0 wt%, giving a H2-production rate of 736 μmol h-1 g-1 with a quantum efficiency (QE) of 3.1%, which exceeded the rate observed on pure TiO2 nanosheets by more than 41 times. This high photocatalytic H2-production activity is due to the deposition of TiO2 nanosheets on graphene sheets, which act as an electron acceptor to efficiently separate the photogenerated charge carriers. The observed enhancement in the photocatalytic activity is due to the lower absolute potential of graphene/graphene z.rad- (-0.08 V vs. SHE, pH = 0) in comparison to the conduction band (-0.24 V) of anatase TiO2, meanwhile the aforementioned absolute value is higher than the reduction potential of H+ (0 V), which favors the electron transfer from the conduction band (CB) of TiO2 to graphene sheets and the reduction of H+, thus enhancing photocatalytic H2-production activity. The proposed mechanism for the observed photocatalytic performance of TiO2 nanosheets, modified with a small amount of graphene, was further confirmed by photoluminescence spectroscopy and transient photocurrent response. This work not only shows a possibility for the utilization of low cost graphene sheets as a substitute for noble metals (such as Pt) in the photocatalytic H2-production but also for the first time shows a significant enhancement in the H2-production activity by using metal-free carbon material as an effective co-catalyst.

Catalase-like activity of horseradish peroxidase: relationship to enzyme inactivation by H2O2.

PubMed Central

Hernández-Ruiz, J; Arnao, M B; Hiner, A N; García-Cánovas, F; Acosta, M

2001-01-01

H2O2 is the usual oxidizing substrate of horseradish peroxidase C (HRP-C). In the absence in the reaction medium of a one-electron donor substrate, H2O2 is able to act as both oxidizing and reducing substrate. However, under these conditions the enzyme also undergoes a progressive loss of activity. There are several pathways that maintain the activity of the enzyme by recovering the ferric form, one of which is the decomposition of H2O2 to molecular oxygen in a similar way to the action of catalase. This production of oxygen has been kinetically characterized with a Clark-type electrode coupled to an oxygraph. HRP-C exhibits a weak catalase-like activity, the initial reaction rate of which is hyperbolically dependent on the H2O2 concentration, with values for K(2) (affinity of the first intermediate, compound I, for H2O2) and k(3) (apparent rate constant controlling catalase activity) of 4.0 +/- 0.6 mM and 1.78 +/- 0.12 s(-1) respectively. Oxygen production by HRP-C is favoured at pH values greater than approx. 6.5; under similar conditions HRP-C is also much less sensitive to inactivation during incubations with H2O2. We therefore suggest that this pathway is a major protective mechanism of HRP-C against such inactivation. PMID:11171085

Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

PubMed

Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

2014-08-30

The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. Copyright © 2014 Elsevier B.V. All rights reserved.

X-ray irradiation activates K+ channels via H2O2 signaling.

PubMed

Gibhardt, Christine S; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

2015-09-09

Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels.

Rate constant for the H˙ + H2O → ˙OH + H2 reaction at elevated temperatures measured by pulse radiolysis.

PubMed

Muroya, Y; Yamashita, S; Lertnaisat, P; Sanguanmith, S; Meesungnoen, J; Jay-Gerin, J-P; Katsumura, Y

2017-11-22

Maintaining the structural integrity of materials in nuclear power plants is an essential issue associated with safe operation. Hydrogen (H 2 ) addition or injection to coolants is a powerful technique that has been widely applied such that the reducing conditions in the coolant water avoid corrosion and stress corrosion cracking (SCC). Because the radiation-induced reaction of ˙OH + H 2 → H˙ + H 2 O plays a crucial role in these systems, the rate constant has been measured at operation temperatures of the reactors (285-300 °C) by pulse radiolysis, generating sufficient data for analysis. The reverse reaction H˙ + H 2 O → ˙OH + H 2 is negligibly slow at ambient temperature; however, it accelerates considerably quickly at elevated temperatures. Although the reverse reaction reduces the effectiveness of H 2 addition, reliable rate constants have not yet been measured. In this study, the rate constants have been determined in a temperature range of 250-350 °C by pulse radiolysis in an aqueous I - solution.

Progesterone amplifies oxidative stress signal and promotes NO production via H2O2 in mouse kidney arterial endothelial cells.

PubMed

Yuan, Xiao-Hua; Fan, Yang-Yang; Yang, Chun-Rong; Gao, Xiao-Rui; Zhang, Li-Li; Hu, Ying; Wang, Ya-Qin; Jun, Hu

2016-01-01

The role of progesterone on the cardiovascular system is controversial. Our present research is to specify the effect of progesterone on arterial endothelial cells in response to oxidative stress. Our result showed that H2O2 (150 μM and 300 μM) induced cellular antioxidant response. Glutathione (GSH) production and the activity of Glutathione peroxidase (GPx) were increased in H2O2-treated group. The expression of glutamate cysteine ligase catalytic subunit (GCLC) and modifier subunit (GCLM) was induced in response to H2O2. However, progesterone absolutely abolished the antioxidant response through increasing ROS level, inhibiting the activity of Glutathione peroxidase (GPx), decreasing GSH level and reducing expression of GClC and GCLM. In our study, H2O2 induced nitrogen monoxide (NO) production and endothelial nitric oxide synthase (eNOS) expression, and progesterone promoted H2O2-induced NO production. Progesterone increased H2O2-induced expression of hypoxia inducible factor-α (HIFα) which in turn regulated eNOS expression and NO synthesis. Further study demonstrated that progesterone increased H2O2 concentration of culture medium which may contribute to NO synthesis. Exogenous GSH decreased the content of H2O2 of culture medium pretreated by progesterone combined with H2O2 or progesterone alone. GSH also inhibited expression of HIFα and eNOS, and abolished NO synthesis. Collectively, our study demonstrated for the first time that progesterone inhibited cellular antioxidant effect and increased oxidative stress, promoted NO production of arterial endothelial cells, which may be due to the increasing H2O2 concentration and amplified oxidative stress signal. Copyright © 2015. Published by Elsevier Ltd.

Water Ice Radiolytic O2, H2, and H2O2 Yields for Any Projectile Species, Energy, or Temperature: A Model for Icy Astrophysical Bodies

NASA Astrophysics Data System (ADS)

Teolis, B. D.; Plainaki, C.; Cassidy, T. A.; Raut, U.

2017-10-01

O2, H2, and H2O2 radiolysis from water ice is pervasive on icy astrophysical bodies, but the lack of a self-consistent, quantitative model of the yields of these water products versus irradiation projectile species and energy has been an obstacle to estimating the radiolytic oxidant sources to the surfaces and exospheres of these objects. A major challenge is the wide variation of O2 radiolysis yields between laboratory experiments, ranging over 4 orders of magnitude from 5 × 10-7 to 5 × 10-3 molecules/eV for different particles and energies. We revisit decades of laboratory data to solve this long-standing puzzle, finding an inverse projectile range dependence in the O2 yields, due to preferential O2 formation from an 30 Å thick oxygenated surface layer. Highly penetrating projectile ions and electrons with ranges ≳30 Å are therefore less efficient at producing O2 than slow/heavy ions and low-energy electrons (≲ 400 eV) which deposit most energy near the surface. Unlike O2, the H2O2 yields from penetrating projectiles fall within a comparatively narrow range of (0.1-6) × 10-3 molecules/eV and do not depend on range, suggesting that H2O2 forms deep in the ice uniformly along the projectile track, e.g., by reactions of OH radicals. We develop an analytical model for O2, H2, and H2O2 yields from pure water ice for electrons and singly charged ions of any mass and energy and apply the model to estimate possible O2 source rates on several icy satellites. The yields are upper limits for icy bodies on which surface impurities may be present.

Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

NASA Astrophysics Data System (ADS)

Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

1996-11-01

The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

Photodegradation of the antineoplastic cyclophosphamide: a comparative study of the efficiencies of UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2 processes.

PubMed

Lutterbeck, Carlos Alexandre; Machado, Ênio Leandro; Kümmerer, Klaus

2015-02-01

Anticancer drugs are harmful substances that can have carcinogenic, mutagenic, teratogenic, genotoxic, and cytotoxic effects even at low concentrations. More than 50 years after its introduction, the alkylating agent cyclophosphamide (CP) is still one of the most consumed anticancer drug worldwide. CP has been detected in water bodies in several studies and is known as being persistent in the aquatic environment. As the traditional water and wastewater treatment technologies are not able to remove CP from the water, different treatment options such as advanced oxidation processes (AOPs) are under discussion to eliminate these compounds. The present study investigated the degradation of CP by three different AOPs: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. The light source was a Hg medium-pressure lamp. Prescreening tests were carried out and afterwards experiments based on the optimized conditions were performed. The primary elimination of the parent compounds and the detection of transformation products (TPs) were monitored with LC-UV-MS/MS analysis, whereas the degree of mineralization was monitored by measuring the dissolved organic carbon (DOC). Ecotoxicological assays were carried out with the luminescent bacteria Vibrio fischeri. CP was completely degraded in all treatments and UV/Fe(2+)/H2O2 was the fastest process, followed by UV/H2O2 and UV/TiO2. All the reactions obeyed pseudo-first order kinetics. Considering the mineralization UV/Fe(2+)/H2O2 and UV/TiO2 were the most efficient process with mineralization degrees higher than 85%, whereas UV/H2O2 achieved 72.5% of DOC removal. Five transformation products were formed during the reactions and identified. None of them showed significant toxicity against V. fischeri. Copyright © 2014 Elsevier Ltd. All rights reserved.

The reaction of H2O2 with NO2 and NO

NASA Technical Reports Server (NTRS)

Gray, D.; Lissi, E.; Heicklen, J.

1972-01-01

The reactions of NO and NO2 with H2O2 have been examined at 25 C. Reaction mixtures were monitored by continuously bleeding through a pinhole into a monopole mass spectrometer. NO2 was also monitored by its optical absorption in the visible part of the spectrum. Reaction mixtures containing initially 1.5 - 2.5 torr of NO2 and 0.8 - 1.4 torr of H2O2 or 1 - 12 torr of NO and 0.5 - 1.5 torr of H2O2 were studied. The H2O2 - NO reaction was complex. There was an induction period followed by a marked acceleration in reactant removal. The final products of the reaction, NO2, probably H2O, and possibly HONO2 were produced mainly after all the H2O2 was removed. The HONO intermediate was shown to disproportionate to NO2 + NO + H2O in a relatively slow first order reaction. The acceleration in H2O2 removal after the NO - H2O2 reaction is started is caused by NO2 catalysis.

Co-modification of amorphous-Ti(IV) hole cocatalyst and Ni(OH)2 electron cocatalyst for enhanced photocatalytic H2-production performance of TiO2

NASA Astrophysics Data System (ADS)

Wang, Ping; Lu, Yanggang; Wang, Xuefei; Yu, Huogen

2017-01-01

Highly efficient TiO2 photocatalysts co-modified by amorphous-Ti(IV) hole cocatalyst and Ni(OH)2 electron cocatalyst (referred to as Ni(OH)2-Ti(IV)/TiO2) were prepared by facile two-step process which was the initial formation of amorphous Ti(IV) on the TiO2 surface via hydrolysis method and the following formation of Ni(OH)2 via precipitation reaction. It was found that the Ni(OH)2-Ti(IV)/TiO2 showed obviously high hydrogen-production performance. When the amount of Ni(OH)2 and Ti(IV) was 1 wt% and 0.1 wt%, respectively, the hydrogen-production rate of the resultant Ni(OH)2-Ti(IV)/TiO2 reached 7280.04 μmol h-1 g-1, which was significantly higher than that of TiO2, Ti(IV)/TiO2 and Ni(OH)2/TiO2 by a factor of 215, 63 and 1.8, respectively. Moreover, it was found that Ni(OH)2-Ti(IV)/TiO2 photocatalyst preserved a steady and highly efficient H2-production performance during repeated tests and also exhibited a high transient photocurrent density. The enhanced hydrogen-production performance of Ni(OH)2-Ti(IV)/TiO2 can be attributed to the synergistic effect of Ti(IV) hole cocatalyst and Ni(OH)2 electron cocatalyst to simultaneously accelerate the interfacial transfer of photogenerated holes and electrons. The present surface modification of dual cocatalysts can be regarded as one of the ideal strategies for the preparation of highly efficient hydrogen-production materials in view of their abundance, low cost and facile method.

H2O2 production rate in Lactobacillus johnsonii is modulated via the interplay of a heterodimeric flavin oxidoreductase with a soluble 28 Kd PAS domain containing protein

PubMed Central

Valladares, Ricardo B.; Graves, Christina; Wright, Kaitlyn; Gardner, Christopher L.; Lorca, Graciela L.; Gonzalez, Claudio F.

2015-01-01

Host and commensals crosstalk, mediated by reactive oxygen species (ROS), has triggered a growing scientific interest to understand the mechanisms governing such interaction. However, the majority of the scientific studies published do not evaluate the ROS production by commensals bacteria. In this context we recently showed that Lactobacillus johnsonii N6.2, a strain of probiotic value, modulates the activity of the critical enzymes 2,3-indoleamine dioxygenase via H2O2 production. L. johnsonii N6.2 by decreasing IDO activity, is able to modify the tryptophan/kynurenine ratio in the host blood with further systemic consequences. Understanding the mechanisms of H2O2 production is critical to predict the probiotic value of these strains and to optimize bacterial biomass production in industrial processes. We performed a transcriptome analysis to identify genes differentially expressed in L. johnsonii N6.2 cells collected from cultures grown under different aeration conditions. Herein we described the biochemical characteristics of a heterodimeric FMN reductase (FRedA/B) whose in vitro activity is controlled by LjPAS protein with a typical Per-Arnst-Sim (PAS) sensor domain. Interestingly, LjPAS is fused to the FMN reductase domains in other lactobacillaceae. In L. johnsonii, LjPAS is encoded by an independent gene which expression is repressed under anaerobic conditions (>3 fold). Purified LjPAS was able to slow down the FRedA/B initial activity rate when the holoenzyme precursors (FredA, FredB, and FMN) were mixed in vitro. Altogether the results obtained suggest that LjPAS module regulates the H2O2 production helping the cells to minimize oxidative stress in response to environmental conditions. PMID:26236298

H2O2 production rate in Lactobacillus johnsonii is modulated via the interplay of a heterodimeric flavin oxidoreductase with a soluble 28 Kd PAS domain containing protein.

PubMed

Valladares, Ricardo B; Graves, Christina; Wright, Kaitlyn; Gardner, Christopher L; Lorca, Graciela L; Gonzalez, Claudio F

2015-01-01

Host and commensals crosstalk, mediated by reactive oxygen species (ROS), has triggered a growing scientific interest to understand the mechanisms governing such interaction. However, the majority of the scientific studies published do not evaluate the ROS production by commensals bacteria. In this context we recently showed that Lactobacillus johnsonii N6.2, a strain of probiotic value, modulates the activity of the critical enzymes 2,3-indoleamine dioxygenase via H2O2 production. L. johnsonii N6.2 by decreasing IDO activity, is able to modify the tryptophan/kynurenine ratio in the host blood with further systemic consequences. Understanding the mechanisms of H2O2 production is critical to predict the probiotic value of these strains and to optimize bacterial biomass production in industrial processes. We performed a transcriptome analysis to identify genes differentially expressed in L. johnsonii N6.2 cells collected from cultures grown under different aeration conditions. Herein we described the biochemical characteristics of a heterodimeric FMN reductase (FRedA/B) whose in vitro activity is controlled by LjPAS protein with a typical Per-Arnst-Sim (PAS) sensor domain. Interestingly, LjPAS is fused to the FMN reductase domains in other lactobacillaceae. In L. johnsonii, LjPAS is encoded by an independent gene which expression is repressed under anaerobic conditions (>3 fold). Purified LjPAS was able to slow down the FRedA/B initial activity rate when the holoenzyme precursors (FredA, FredB, and FMN) were mixed in vitro. Altogether the results obtained suggest that LjPAS module regulates the H2O2 production helping the cells to minimize oxidative stress in response to environmental conditions.

OH-LIF measurement of H2/O2/N2 flames in a micro flow reactor with a controlled temperature profile

NASA Astrophysics Data System (ADS)

Shimizu, T.; Nakamura, H.; Tezuka, T.; Hasegawa, S.; Maruta, K.

2014-11-01

This paper presents combustion and ignition characteristic of H2/O2/N2 flames in a micro flow reactor with a controlled temperature profile. OH-LIF measurement was conducted to capture flame images. Flame responses were investigated for variable inlet flow velocity, U, and equivalence ratio, phi. Three kinds of flame responses were experimentally observed for the inlet flow velocities: stable flat flames (normal flames) in the high inlet flow velocity regime; unstable flames called Flames with Repetitive Extinction and Ignition (FREI) in the intermediate flow velocity regime; and stable weak flames in the low flow velocity regime, at phi = 0.6, 1.0 and 1.2. On the other hand, weak flame was not observed at phi = 3.0 by OH-LIF measurement. Computational OH mole fractions showed lower level at the rich conditions than those at stoichiometric and lean conditions. To examine this response of OH signal to equivalence ratio, rate of production analysis was conducted and four kinds of major contributed reaction for OH production: R3(O + H2 <=> H + OH); R38(H + O2 <=> O + OH); R46(H + HO2 <=> 2OH); and R86(2OH <=> O + H2O), were found. Three reactions among them, R3, R38 and R46, did not showed significant difference in rate of OH production for different equivalence ratios. On the other hand, rate of OH production from R86 at phi = 3.0 was extremely lower than those at phi = 0.6 and 1.0. Therefore, R86 was considered to be a key reaction for the reduction of the OH production at phi = 3.0.

LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

NASA Astrophysics Data System (ADS)

Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

2016-01-01

Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

Quantum chemical study of the mechanism of reaction between NH (X 3sigma-) and H2, H2O, and CO2 under combustion conditions.

PubMed

Mackie, John C; Bacskay, George B

2005-12-29

Reactions of ground-state NH (3sigma-) radicals with H2, H2O, and CO2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction potential energy surfaces, that is, reactants, products, intermediates, and transition states, have been identified at the G3//B3LYP level of theory. Reaction between NH and H2 takes place via a simple abstraction transition state, and the rate coefficient for this reaction as derived from the quantum chemical calculations, k(NH + H2) = (1.1 x 10(14)) exp(-20.9 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K, is found to be in good agreement with experiment. For reaction between triplet NH and H2O, no stable intermediates were located on the triplet reaction surface although several stable species were found on the singlet surface. No intersystem crossing seam between triplet NH + H2O and singlet HNO + H2 (the products of lowest energy) was found; hence there is no evidence to support the existence of a low-energy pathway to these products. A rate coefficient of k(NH + H2O) = (6.1 x 10(13)) exp(-32.8 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K for the reaction NH (3sigma-) + H2O --> NH2 (2B) + OH (2pi) was derived from the quantum chemical results. The reverse rate coefficient, calculated via the equilibrium constant, is in agreement with values used in modeling the thermal de-NO(x) process. For the reaction between triplet NH and CO2, several stable intermediates on both triplet and singlet reaction surfaces were located. Although a pathway from triplet NH + CO2 to singlet HNO + CO involving intersystem crossing in an HN-CO2 adduct was discovered, no pathway of sufficiently low activation energy was discovered to compare with that found in an earlier experiment [Rohrig, M.; Wagner, H. G. Proc. Combust. Inst. 1994, 25, 993.].

Photodegradation of 4-tert-butylphenol in aqueous solution by UV-C, UV/H2O2 and UV/S2O8(2-) system.

PubMed

Wu, Yanlin; Zhu, Xiufen; Chen, Hongche; Dong, Wenbo; Zhao, Jianfu

2016-01-01

The photolytic degradation of 4-tert-butylphenol (4-t-BP) in aqueous solution was investigated using three kinds of systems: UV-C directly photodegradation system, UV/H2O2 and UV/S2O8(2-) system. Under experimental conditions, the degradation rate of 4-t-BP was in the order: UV/S2O8(2-) > UV/H2O2 > UV-C. The reaction kinetics of UV/S2O8(2-) system were thoroughly investigated. The increase of S2O8(2-) concentration enhanced the 4-t-BP degradation rate, which was inhibited when the concentration of S2O8(2-) exceeded 4.0 mM. The highest efficacy in 4-t-BP degradation was obtained at pH 6.5. The oxidation rate of 4-t-BP could be accelerated by increasing the reaction temperature and irradiation intensity. The highest rate constant (kobs = 8.4 × 10(-2) min(-1)) was acquired when the reaction temperature was 45 °C. The irradiation intensity was measured by irradiation distance, and the optimum irradiation distance was 10 cm. Moreover, the preliminary mechanism of 4-t-BP degradation was studied. The bond scission of the 4-t-BP molecule occurred by the oxidation of SO4(•-), which dimerized and formed two main primary products. Under the conditions of room temperature (25 °C ± 1 °C) and low concentration of K2S2O8 (0.5 mM), 35.4% of total organic carbon (TOC) was removed after 8.5-h irradiation. The results showed that UV/S2O8(2-) system was effective for the degradation of 4-t-BP.

Reaction of H2 with O2 in Excited Electronic States: Reaction Pathways and Rate Constants.

PubMed

Pelevkin, Alexey V; Loukhovitski, Boris I; Sharipov, Alexander S

2017-12-21

Comprehensive quantum chemical analysis with the use of the multireference state-averaged complete active space self-consistent field approach was carried out to study the reactions of H 2 with O 2 in a 1 Δ g , b 1 Σ g + , c 1 Σ u - , and A' 3 Δ u electronically excited states. The energetically favorable reaction pathways and possible intersystem crossings have been revealed. The energy barriers were refined employing the extended multiconfiguration quasi-degenerate second-order perturbation theory. It has been shown that the interaction of O 2 (a 1 Δ g ) and O 2 (A' 3 Δ u ) with H 2 occurs through the H-abstraction process with relatively low activation barriers that resulted in the formation of the HO 2 molecule in A″ and A' electronic states, respectively. Meanwhile, molecular oxygen in singlet sigma states (b 1 Σ g + and c 1 Σ u - ) was proved to be nonreactive with respect to the molecular hydrogen. Appropriate rate constants for revealed reaction and quenching channels have been estimated using variational transition-state theory including corrections for the tunneling effect, possible nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. It was demonstrated that the calculated reaction rate constant for the H 2 + O 2 (a 1 Δ g ) process is in reasonable agreement with known experimental data. The Arrhenius approximations for these processes have been proposed for the temperature range T = 300-3000 K.

Ab initio and transition state theory study of the OH + HO2 → H2O + O2(3Σg-)/O2(1Δg) reactions: yield and role of O2(1Δg) in H2O2 decomposition and in combustion of H2.

PubMed

Monge-Palacios, M; Sarathy, S Mani

2018-02-07

Reactions of hydroxyl (OH) and hydroperoxyl (HO 2 ) are important for governing the reactivity of combustion systems. We performed post-CCSD(T) ab initio calculations at the W3X-L//CCSD = FC/cc-pVTZ level to explore the triplet ground-state and singlet excited-state potential energy surfaces of the OH + HO 2 → H 2 O + O 2 ( 3 Σ g - )/O 2 ( 1 Δ g ) reactions. Using microcanonical and multistructural canonical transition state theories, we calculated the rate constant for the triplet and singlet channels over the temperature range 200-2500 K, represented by k(T) = 3.08 × 10 12 T 0.07  exp(1151/RT) + 8.00 × 10 12 T 0.32  exp(-6896/RT) and k(T) = 2.14 × 10 6 T 1.65  exp(-2180/RT) in cm 3 mol -1 s -1 , respectively. The branching ratios show that the yield of singlet excited oxygen is small (<0.5% below 1000 K). To ascertain the importance of singlet oxygen channel, our new kinetic information was implemented into the kinetic model for hydrogen combustion recently updated by Konnov (Combust. Flame, 2015, 162, 3755-3772). The updated kinetic model was used to perform H 2 O 2 thermal decomposition simulations for comparison against shock tube experiments performed by Hong et al. (Proc. Combust. Inst., 2013, 34, 565-571), and to estimate flame speeds and ignition delay times in H 2 mixtures. The simulation predicted a larger amount of O 2 ( 1 Δ g ) in H 2 O 2 decomposition than that predicted by Konnov's original model. These differences in the O 2 ( 1 Δ g ) yield are due to the use of a higher ab initio level and a more sophisticated methodology to compute the rate constant than those used in previous studies, thereby predicting a significantly larger rate constant. No effect was observed on the rate of the H 2 O 2 decomposition and on the flame speeds and ignition delay times of different H 2 -oxidizer mixtures. However, if the oxidizer is seeded with O 3 , small differences appear in the flame speed. Given that O 2 ( 1 Δ g ) is much more reactive than O

X-ray irradiation activates K+ channels via H2O2 signaling

PubMed Central

Gibhardt, Christine S.; Roth, Bastian; Schroeder, Indra; Fuck, Sebastian; Becker, Patrick; Jakob, Burkhard; Fournier, Claudia; Moroni, Anna; Thiel, Gerhard

2015-01-01

Ionizing radiation is a universal tool in tumor therapy but may also cause secondary cancers or cell invasiveness. These negative side effects could be causally related to the human-intermediate-conductance Ca2+-activated-K+-channel (hIK), which is activated by X-ray irradiation and affects cell proliferation and migration. To analyze the signaling cascade downstream of ionizing radiation we use genetically encoded reporters for H2O2 (HyPer) and for the dominant redox-buffer glutathione (Grx1-roGFP2) to monitor with high spatial and temporal resolution, radiation-triggered excursions of H2O2 in A549 and HEK293 cells. The data show that challenging cells with ≥1 Gy X-rays or with UV-A laser micro-irradiation causes a rapid rise of H2O2 in the nucleus and in the cytosol. This rise, which is determined by the rate of H2O2 production and glutathione-buffering, is sufficient for triggering a signaling cascade that involves an elevation of cytosolic Ca2+ and eventually an activation of hIK channels. PMID:26350345

[Mechanism and performance of styrene oxidation by O3/H2O2].

PubMed

He, Jue-Cong; Huang, Qian-Ru; Ye, Qi-Hong; Luo, Yu-Wei; Zhang, Zai-Li; Fan, Qing-Juan; Wei, Zai-Shan

2013-10-01

It can produce a large number of free radicals in O3/H2O2, system, ozone and free radical coupling oxidation can improve the styrene removal efficiency. Styrene oxidation by O3/H2O2 was investigated. Ozone dosage, residence time, H2o2 volume fraction, spray density and molar ratio of O3/C8H8 on styrene removal were evaluated. The experimental results showed that styrene removal efficiency achieved 85.7%. The optimal residence time, H2O2, volume fraction, spray density and O3/C8H8 molar ratio were 20. 6 s, 10% , 1.72 m3.(m2.h)-1 and 0.46, respectively. The gas-phase degradation intermediate products were benzaldehyde(C6H5CHO) and benzoic acid (C6H5 COOH) , which were identified by means of gas chromatography-mass spectrometry(GC-MS). The degradation mechanism of styrene is presented.

Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

NASA Astrophysics Data System (ADS)

Cole, David R.

2000-03-01

Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order

The reaction of O(1 D) with H2O and the reaction of OH with C3H6

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Heicklen, J.

1972-01-01

The N2O was photolyzed at 2139 A to produce O(1 D) atoms in the presence of H2O and CO. The O(1 D) atoms react with H2O to produce HO radicals, as measured by CO2 production from the reaction of OH with CO. The relative rate constant for O(1 D) removal by H2O compared to that by N2O is 2.1. In the presence of C3H6, the OH can be removed by reaction with either CO or C3H6.

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

Age-related differences in cigarette smoke extract-induced H2O2 production by lung endothelial cells.

PubMed

Downs, Charles A; Montgomery, David W; Merkle, Carrie J

2011-11-01

Cigarette smoke causes oxidative stress in the lung resulting in injury and disease. The purpose of this study was to determine if there were age-related differences in cigarette smoke extract (CSE)-induced production of reactive species in single and co-cultures of alveolar epithelial type I (AT I) cells and microvascular endothelial cells harvested from the lungs (MVECLs) of neonatal, young and old male Fischer 344 rats. Cultures of AT I cells and MVECLs grown separately (single culture) and together (co-culture) were exposed to CSE (1, 10, 50, 100%). Cultures were assayed for the production of intracellular reactive oxygen species (ROS), hydroxyl radical (OH), peroxynitrite (ONOO(-)), nitric oxide (NO) and extracellular hydrogen peroxide (H(2)O(2)). Single and co-cultures of AT I cells and MVECLs from all three ages produced minimal intracellular ROS in response to CSE. All ages of MVECLs produced H(2)O(2) in response to CSE, but young MVECLs produced significantly less H(2)O(2) compared to neonatal and old MVECLs. Interestingly, when grown as a co-culture with age-matched AT I cells, neonatal and old MVECLs demonstrated ~50% reduction in H(2)O(2) production in response to CSE. However, H(2)O(2) production in young MVECLs grown as a co-culture with young AT I cells did not change with CSE exposure. To begin investigating for a potential mechanism to explain the reduction in H(2)O(2) production in the co-cultures, we evaluated single and co-cultures for extracellular total antioxidant capacity. We also performed gene expression profiling specific to oxidant and anti-oxidant pathways. The total antioxidant capacity of the AT I cell supernatant was ~5 times greater than that of the MVECLs, and when grown as a co-culture and exposed to CSE (≥ 10%), the total antioxidant capacity of the supernatant was reduced by ~50%. There were no age-related differences in total antioxidant capacity of the cell supernatants. Gene expression profiling found eight genes to be

Direct Z-scheme TiO2/CdS hierarchical photocatalyst for enhanced photocatalytic H2-production activity

NASA Astrophysics Data System (ADS)

Meng, Aiyun; Zhu, Bicheng; Zhong, Bo; Zhang, Liuyang; Cheng, Bei

2017-11-01

Photocatalytic H2 evolution, which utilizes solar energy via water splitting, is a promising route to deal with concerns about energy and environment. Herein, a direct Z-scheme TiO2/CdS binary hierarchical photocatalyst was fabricated via a successive ionic layer adsorption and reaction (SILAR) technique, and photocatalytic H2 production was measured afterwards. The as-prepared TiO2/CdS hybrid photocatalyst exhibited noticeably promoted photocatalytic H2-production activity of 51.4 μmol h-1. The enhancement of photocatalytic activity was ascribed to the hierarchical structure, as well as the efficient charge separation and migration from TiO2 nanosheets to CdS nanoparticles (NPs) at their tight contact interfaces. Moreover, the direct Z-scheme photocatalytic reaction mechanism was demonstrated to elucidate the improved photocatalytic performance of TiO2/CdS composite photocatalyst. The photoluminescence (PL) analysis of hydroxyl radicals were conducted to provide clues for the direct Z-scheme mechanism. This work provides a facile route for the construction of redox mediator-free Z-scheme photocatalytic system for photocatalytic water splitting.

Reaction of N2O5 with H2O on carbonaceous surfaces

NASA Technical Reports Server (NTRS)

Brouwer, L.; Rossi, M. J.; Golden, D. M.

1986-01-01

The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

Low levels of iron enhance UV/H2O2 efficiency at neutral pH.

PubMed

Ulliman, Sydney L; McKay, Garrett; Rosario-Ortiz, Fernando L; Linden, Karl G

2018-03-01

While the presence of iron is generally not seen as favorable for UV-based treatment systems due to lamp fouling and decreased UV transmittance, we show that low levels of iron can lead to improvements in the abatement of chemicals in the UV-hydrogen peroxide advanced oxidation process. The oxidation potential of an iron-assisted UV/H 2 O 2 (UV 254  + H 2 O 2  + iron) process was evaluated at neutral pH using iron levels below USEPA secondary drinking water standards (<0.3 mg/L). Para-chlorobenzoic acid (pCBA) was used as a hydroxyl radical (HO) probe to quantify HO steady state concentrations. Compounds degraded by different mechanisms including, carbamazepine (CBZ, HO oxidation) and N-nitrosodimethylamine (NDMA, direct photolysis), were used to investigate the effect of iron on compound degradation for UV/H 2 O 2 systems. The effects of iron species (Fe 2+ and Fe 3+ ), iron concentration (0-0.3 mg/L), H 2 O 2 concentration (0-10 mg/L) and background water matrix (low-carbon tap (LCT) and well water) on HO production and compound removal were examined. Iron-assisted UV/H 2 O 2 efficiency was most influenced by the target chemical and the water matrix. Added iron to UV/H 2 O 2 was shown to increase the steady-state HO concentration by approximately 25% in all well water scenarios. While CBZ removal was unchanged by iron addition, 0.3 mg/L iron improved NDMA removal rates in both LCT and well water matrices by 15.1% and 4.6% respectively. Furthermore, the combination of UV/Fe without H 2 O 2 was also shown to enhance NDMA removal when compared to UV photolysis alone indicating the presence of degradation pathways other than HO oxidation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Herschel Survey of Galactic OH+, H2O+, and H3O+: Probing the Molecular Hydrogen Fraction and Cosmic-Ray Ionization Rate

NASA Astrophysics Data System (ADS)

Indriolo, Nick; Neufeld, D. A.; Gerin, M.; Schilke, P.; Benz, A. O.; Winkel, B.; Menten, K. M.; Chambers, E. T.; Black, John H.; Bruderer, S.; Falgarone, E.; Godard, B.; Goicoechea, J. R.; Gupta, H.; Lis, D. C.; Ossenkopf, V.; Persson, C. M.; Sonnentrucker, P.; van der Tak, F. F. S.; van Dishoeck, E. F.; Wolfire, Mark G.; Wyrowski, F.

2015-02-01

In diffuse interstellar clouds the chemistry that leads to the formation of the oxygen-bearing ions OH+, H2O+, and H3O+ begins with the ionization of atomic hydrogen by cosmic rays, and continues through subsequent hydrogen abstraction reactions involving H2. Given these reaction pathways, the observed abundances of these molecules are useful in constraining both the total cosmic-ray ionization rate of atomic hydrogen (ζH) and molecular hydrogen fraction (f_H_2). We present observations targeting transitions of OH+, H2O+, and H3O+ made with the Herschel Space Observatory along 20 Galactic sight lines toward bright submillimeter continuum sources. Both OH+ and H2O+ are detected in absorption in multiple velocity components along every sight line, but H3O+ is only detected along 7 sight lines. From the molecular abundances we compute f_H_2 in multiple distinct components along each line of sight, and find a Gaussian distribution with mean and standard deviation 0.042 ± 0.018. This confirms previous findings that OH+ and H2O+ primarily reside in gas with low H2 fractions. We also infer ζH throughout our sample, and find a lognormal distribution with mean log (ζH) = -15.75 (ζH = 1.78 × 10-16 s-1) and standard deviation 0.29 for gas within the Galactic disk, but outside of the Galactic center. This is in good agreement with the mean and distribution of cosmic-ray ionization rates previously inferred from H_3^+ observations. Ionization rates in the Galactic center tend to be 10-100 times larger than found in the Galactic disk, also in accord with prior studies. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

Investigation into the disparate origin of CO 2 and H 2O outgassing for comet 67P

NASA Astrophysics Data System (ADS)

Fink, Uwe; Doose, Lyn; Rinaldi, Giovanna; Capaccioni, Fabrizio; Bockelee-Morvan, Dominique; VIRTIS Team

2016-10-01

We present an investigation of the emission intensity of CO2 and H2O and their distribution in the coma of 67P/ Churyumov-Gerasimenko obtained by the VIRTIS-M imaging spectrometer on the Rosetta mission. We analyze 4 data cubes from Feb. 28, and 7 data cubes from April 27, 2015. For both data sets the spacecraft was at a sufficiently large distance from the comet to allow images of the whole nucleus and the surrounding coma.We find that unlike water which has a reasonably predictable behavior and correlates well with the solar illumination, CO2 outgasses mostly in local regions or spots. Furthermore for the data on April 27, the CO2 evolves almost exclusively from the southern hemisphere, a region of the comet that has not received solar illumination since the comet's last perihelion passage. Because CO2 and H2O have such disparate origins, deriving mixing ratios from local column density measurements cannot provide a meaningful measurement of the CO2/H2O ratio in the coma of the comet. We obtain total production rates of H2O and CO2 by integrating the band intensity in an annulus surrounding the nucleus and obtain pro-forma production rate CO2/H2O mixing ratios of ~5.0% and ~2.5% for Feb. 28 and April 27 respectively. Because of the highly variable nature of the CO2 evolution we do not believe that these numbers are diagnostic of the comets bulk CO2/H2O composition. We believe that our investigation provides an explanation for the large observed variations reported in the literature for the CO2/H2O production rate ratios. Our mixing ratio maps indicate that, besides the difference in vapor pressure of the two gases, this ratio depends on the comet's geometric shape, illumination and past orbital history.Our annulus measurement for the total water production for Feb. 28 at 2.21AU from the sun is 2.5x1026 molecules/s while for April 27 at 1.76 AU it is 4.65x1026. We find that about 83% of the H2O resides in the illuminated portion of our annulus and about 17% on the

Chlorogenic acid analogues from Gynura nepalensis protect H9c2 cardiomyoblasts against H2O2-induced apoptosis

PubMed Central

Yu, Bang-wei; Li, Jin-long; Guo, Bin-bin; Fan, Hui-min; Zhao, Wei-min; Wang, He-yao

2016-01-01

Aim: Chlorogenic acid has shown protective effect on cardiomyocytes against oxidative stress-induced damage. Herein, we evaluated nine caffeoylquinic acid analogues (1–9) isolated from the leaves of Gynura nepalensis for their protective effect against H2O2-induced H9c2 cardiomyoblast damage and explored the underlying mechanisms. Methods: H9c2 cardiomyoblasts were exposed to H2O2 (0.3 mmol/L) for 3 h, and cell viability was detected with MTT assay. Hoechst 33342 staining was performed to evaluate cell apoptosis. MMPs (mitochondrial membrane potentials) were measured using a JC-1 assay kit, and ROS (reactive oxygen species) generation was measured using CM-H2 DCFDA. The expression levels of relevant proteins were detected using Western blot analysis. Results: Exposure to H2O2 markedly decreased the viability of H9c2 cells and catalase activity, and increased LDH release and intracellular ROS production; accompanied by a loss of MMP and increased apoptotic rate. Among the 9 chlorogenic acid analogues as well as the positive control drug epigallocatechin gallate (EGCG) tested, compound 6 (3,5-dicaffeoylquinic acid ethyl ester) was the most effective in protecting H9c2 cells from H2O2-induced cell death. Pretreatment with compound 6 (1.56–100 μmol/L) dose-dependently alleviated all the H2O2-induced detrimental effects. Moreover, exposure to H2O2 significantly increased the levels of Bax, p53, cleaved caspase-8, and cleaved caspase-9, and decreased the level of Bcl-2, resulting in cell apoptosis. Exposure to H2O2 also significantly increased the phosphorylation of p38, JNK and ERK in the H9c2 cells. Pretreatment with compound 6 (12.5 and 25 μmol/L) dose-dependently inhibited the H2O2-induced increase in the level of cleaved caspase-9 but not of cleaved caspase-8. It also dose-dependently suppressed the H2O2-induced phosphorylation of JNK and ERK but not that of p38. Conclusion: Compound 6 isolated from the leaves of Gynura nepalensis potently protects H9c2

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2015-07-14

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2015-07-01

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

Gas Production at Comet 67P/Churyumov-Gerasimenko as Measured by the ROSINA Instrument: Long Term Trends and Correlations with H2O and CO2

NASA Astrophysics Data System (ADS)

Hansen, K. C.; Altwegg, K.; Berthelier, J. J.; Combi, M. R.; De Keyser, J.; Fiethe, B.; Fougere, N.; Fuselier, S. A.; Gombosi, T. I.; Huang, Z.; Rubin, M.; Tenishev, V.; Toth, G.; Tzou, C. Y.

2017-12-01

The Rosetta Orbiter Spectrometer for Ion and Neutral Analysis (ROSINA) instrument onboard the Rosetta spacecraft measured the in situ gas density of comet 67P/Churyumov-Gerasimenko during the full perihelion passage of the comet within 3.5au. During this time, ROSINA sampled the neutral coma, measuring the broad range of cometary species including both the major constituents such as H2O, CO2, CO as well as many other species that are interesting to the general astrophysical community, such as O2, Xe, Si and even amino acids. Many of these species are hard to detect and therefore measurements are limited to when the spacecraft was close to the comet or the production rate was high. In contrast, in this work we will consider species that are most easily measured due to either their higher production rates or the ease with which their mass peaks are located (H2O, CO2, CO, O2, 18OH, HDO, OCS, SO2, H2S, CN, HCN, NH3, CH4, C2H2, C2H3, CH3OH and F). The advantage of examining these species is that we are able to present measurements over the entire perihelion passage at reasonably high time resolution. In this work we will present two important results. First, we will examine the long-term trend and heliocentric distance dependence of the production of these species over the entire perihelion passage of 67P. Second we will consider the correlation of the production of each species with the production of H2O and CO2. The study will consider both the long term correspondence between production of different species as well as the shorter term correlation.

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

PubMed

Zhao, Hai-Qian; Wang, Zhong-Hua; Gao, Xing-Cun; Liu, Cheng-Hao; Qi, Han-Bing

2018-01-01

H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures

PubMed Central

Wang, Zhong-hua; Gao, Xing-cun; Liu, Cheng-hao; Qi, Han-bing

2018-01-01

H2O2 was adopted to oxidize NO in simulated flue gas at 100–500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300–500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption. PMID:29668672

Succinate modulation of H2O2 release at NADH:ubiquinone oxidoreductase (Complex I) in brain mitochondria

PubMed Central

Zoccarato, Franco; Cavallini, Lucia; Bortolami, Silvia; Alexandre, Adolfo

2007-01-01

Complex I (NADH:ubiquinone oxidoreductase) is responsible for most of the mitochondrial H2O2 release, both during the oxidation of NAD-linked substrates and during succinate oxidation. The much faster succinate-dependent H2O2 production is ascribed to Complex I, being rotenone-sensitive. In the present paper, we report high-affinity succinate-supported H2O2 generation in the absence as well as in the presence of GM (glutamate/malate) (1 or 2 mM of each). In brain mitochondria, their only effect was to increase from 0.35 to 0.5 or to 0.65 mM the succinate concentration evoking the semi-maximal H2O2 release. GM are still oxidized in the presence of succinate, as indicated by the oxygen-consumption rates, which are intermediate between those of GM and of succinate alone when all substrates are present together. This effect is removed by rotenone, showing that it is not due to inhibition of succinate influx. Moreover, α-oxoglutarate production from GM, a measure of the activity of Complex I, is decreased, but not stopped, by succinate. It is concluded that succinate-induced H2O2 production occurs under conditions of regular downward electron flow in Complex I. Succinate concentration appears to modulate the rate of H2O2 release, probably by controlling the hydroquinone/quinone ratio. PMID:17477844

[Degradation of Organic Sunscreens 2-hydroxy-4-methoxybenzophenone by UV/ H2O2 Process: Kinetics and Factors].

PubMed

Feng, Xin-xin; Du, Er-deng; Guo, Ying-qing; Li, Hua-jie; Liu, Xiang; Zhou, Fang

2015-06-01

Organic sunscreens continue to enter the environment through people's daily consumption, and become a kind of emerging contaminants. The photochemical degradation of benzophenone-3 (BP-3) in water by UV/H2O2 process was investigated. Several factors, including the initial BP-3 concentration, H2O2 concentration, UV light intensity, coexisting cations and anions, humic acid and tert-butyl alcohol, were also discussed. The results showed that BP-3 degradation rate constant decreased with increasing initial BP-3 concentration, while increased with increasing H2O2 dosage and UV intensity. Coexisting anions could reduce the degradation rate, while coexisting ferric ions could stimulate the production of OH through Fenton-like reaction, further significantly accelerated BP-3 degradation process. The BP-3 degradation would be inhibited by humic acid or tert-butyl alcohol. The electrical energy per order (E(Eo)) values were also calculated to evaluate the cost of BP-3 degradation by UV/H2O2 process. The addition of ferric ions significantly reduced the value of E(Eo). The investigation of processing parameter could provide a reference for the practical engineering applications of benzophenone compounds removal by UV/H2O2 process.

O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

PubMed

Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

2017-10-05

Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

High temperature kinetic study of the reactions H + O2 = OH + O and O + H2 = OH + H in H2/O2 system by shock tube-laser absorption spectroscopy

NASA Technical Reports Server (NTRS)

Ryu, Si-Ok; Hwang, Soon Muk; Dewitt, Kenneth J.

1995-01-01

The reactions: (1) H + O2 = OH + O; and (2) O + H2 = OH + H are the most important elementary reactions in gas phase combustion. They are the main chain-branching reaction in the oxidation of H2 and hydrocarbon fuels. In this study, rate coefficients of the reactions and have been measured over a wide range of composition, pressure, density and temperature behind the reflected shock waves. The experiments were performed using the shock tube - laser absorption spectroscopic technique to monitor OH radicals formed in the shock-heated H2/O2/Ar mixtures. The OH radicals were detected using the P(1)(5) line of (0,0) band of the A(exp 2) Sigma(+) from X(exp 2) Pi transition of OH at 310.023 nm (air). The data were analyzed with the aid of computer modeling. In the experiments great care was exercised to obtain high time resolution, linearity and signal-to-noise. The results are well represented by the Arrhenius expressions. The rate coefficient expression for reaction (1) obtained in this study is k(1) = (7.13 +/- 0.31) x 10(exp 13) exp(-6957+/- 30 K/T) cu cm/mol/s (1050 K less than or equal to T less than or equal to 2500 K) and a consensus expression for k(1) from a critical review of the most recent evaluations of k(1) (including our own) is k(1) = 7.82 x 10(exp 13) exp(-7105 K/T) cu cm/mol/s (960 K less than or equal to T less than or equal to 5300 K). The rate coefficient expression of k(2) is given by k(2) = (1.88 +/- 0.07) x 10(exp 14) exp(-6897 +/- 53 K/T) cu cm/mol/s (1424 K less than or equal to T less than or equal to 2427 K). For k(1), the temperature dependent A-factor and the correlation between the values of k(1) and the inverse reactant densities were not found. In the temperature range of this study, non-Arrhenius expression of k(2) which shows the upward curvature was not supported.

Manganese ions enhance mitochondrial H2O2 emission from Krebs cycle oxidoreductases by inducing permeability transition.

PubMed

Bonke, Erik; Siebels, Ilka; Zwicker, Klaus; Dröse, Stefan

2016-10-01

Manganese-induced toxicity has been linked to mitochondrial dysfunction and an increased generation of reactive oxygen species (ROS). We could recently show in mechanistic studies that Mn 2+ ions induce hydrogen peroxide (H 2 O 2 ) production from the ubiquinone binding site of mitochondrial complex II (II Q ) and generally enhance H 2 O 2 formation by accelerating the rate of superoxide dismutation. The present study with intact mitochondria reveals that manganese additionally enhances H 2 O 2 emission by inducing mitochondrial permeability transition (mPT). In mitochondria fed by NADH-generating substrates, the combination of Mn 2+ and different respiratory chain inhibitors led to a dynamically increasing H 2 O 2 emission which was sensitive to the mPT inhibitor cyclosporine A (CsA) as well as Ru-360, an inhibitor of the mitochondrial calcium uniporter (MCU). Under these conditions, flavin-containing enzymes of the mitochondrial matrix, e.g. the mitochondrial 2-oxoglutaratedehydrogenase (OGDH), were major sources of ROS. With succinate as substrate, Mn 2+ stimulated ROS production mainly at complex II, whereby the applied succinate concentration had a marked effect on the tendency for mPT. Also Ca 2+ increased the rate of H 2 O 2 emission by mPT, while no direct effect on ROS-production of complex II was observed. The present study reveals a complex scenario through which manganese affects mitochondrial H 2 O 2 emission: stimulating its production from distinct sites (e.g. site II Q ), accelerating superoxide dismutation and enhancing the emission via mPT which also leads to the loss of soluble components of the mitochondrial antioxidant systems and favors the ROS production from flavin-containing oxidoreductases of the Krebs cycle. Copyright © 2016 Elsevier Inc. All rights reserved.

Tracking the energy flow in the hydrogen exchange reaction OH + H2O → H2O + OH.

PubMed

Zhu, Yongfa; Ping, Leilei; Bai, Mengna; Liu, Yang; Song, Hongwei; Li, Jun; Yang, Minghui

2018-05-09

The prototypical hydrogen exchange reaction OH + H2O → H2O + OH has attracted considerable interest due to its importance in a wide range of chemically active environments. In this work, an accurate global potential energy surface (PES) for the ground electronic state was developed based on ∼44 000 ab initio points at the level of UCCSD(T)-F12a/aug-cc-pVTZ. The PES was fitted using the fundamental invariant-neural network method with a root mean squared error of 4.37 meV. The mode specific dynamics was then studied by the quasi-classical trajectory method on the PES. Furthermore, the normal mode analysis approach was employed to calculate the final vibrational state distribution of the product H2O, in which a new scheme to acquire the Cartesian coordinates and momenta of each atom in the product molecule from the trajectories was proposed. It was found that, on one hand, excitation of either the symmetric stretching mode or the asymmetric stretching mode of the reactant H2O promotes the reaction more than the translational energy, which can be rationalized by the sudden vector projection model. On the other hand, the relatively higher efficacy of exciting the symmetric stretching mode than that of the asymmetric stretching mode is caused by the prevalence of the indirect mechanism at low collision energies and the stripping mechanism at high collision energies. In addition, the initial collision energy turns ineffectively into the vibrational energy of the products H2O and OH while a fraction of the energy transforms into the rotational energy of the product H2O. Fundamental excitation of the stretching modes of H2O results in the product H2O having the highest population in the fundamental state of the asymmetric stretching mode, followed by the ground state and the fundamental state of the symmetric stretching mode.

Theoretical kinetics of O + C 2H 4

DOE PAGES

Li, Xiaohu; Jasper, Ahren W.; Zádor, Judit; ...

2016-06-01

The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3O+C 2H 4 and for this class of reactions generally, decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The two surfaces share some bimolecular products but feature different intermediates, pathways, and transition states. In addition, the overall product branching is therefore a sensitive function of the ISC rate. The 3O+C 2Hmore » 4 reaction has been extensively studied, but previous experimental work has not provided detailed branching information at elevated temperatures, while previous theoretical studies have employed empirical treatments of ISC. Here we predict the kinetics of 3O+C 2H 4 using an ab initio transition state theory based master equation (AITSTME) approach that includes an a priori description of ISC. Specifically, the ISC rate is calculated using Landau–Zener statistical theory, consideration of the four lowest-energy electronic states, and a direct classical trajectory study of the product branching immediately after ISC. The present theoretical results are largely in good agreement with existing low-temperature experimental kinetics and molecular beam studies. Good agreement is also found with past theoretical work, with the notable exception of the predicted product branching at elevated temperatures. Above ~1000 K, we predict CH 2CHO+H and CH 2+CH 2O as the major products, which differs from the room temperature preference for CH 3+HCO (which is assumed to remain at higher temperatures in some models) and from the prediction of a previous detailed master equation study.« less

Characterization and optimization of cathodic conditions for H2O2 synthesis in microbial electrochemical cells.

PubMed

Sim, Junyoung; An, Junyeong; Elbeshbishy, Elsayed; Ryu, Hodon; Lee, Hyung-Sool

2015-11-01

Cathode potential and O2 supply methods were investigated to improve H2O2 synthesis in an electrochemical cell, and optimal cathode conditions were applied for microbial electrochemical cells (MECs). Using aqueous O2 for the cathode significantly improved current density, but H2O2 conversion efficiency was negligible at 0.3-12%. Current density decreased for passive O2 diffusion to the cathode, but H2O2 conversion efficiency increased by 65%. An MEC equipped with a gas diffusion cathode was operated with acetate medium and domestic wastewater, which presented relatively high H2O2 conversion efficiency from 36% to 47%, although cathode overpotential was fluctuated. Due to different current densities, the maximum H2O2 production rate was 141 mg H2O2/L-h in the MEC fed with acetate medium, but it became low at 6 mg H2O2/L-h in the MEC fed with the wastewater. Our study clearly indicates that improving anodic current density and mitigating membrane fouling would be key parameters for large-scale H2O2-MECs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of Background H2O on the Collision-Induced Dissociation Products Generated from [UO2NO3]+

NASA Astrophysics Data System (ADS)

Van Stipdonk, Michael J.; Iacovino, Anna; Tatosian, Irena

2018-04-01

Developing a comprehensive understanding of the reactivity of uranium-containing species remains an important goal in areas ranging from the development of nuclear fuel processing methods to studies of the migration and fate of the element in the environment. Electrospray ionization (ESI) is an effective way to generate gas-phase complexes containing uranium for subsequent studies of intrinsic structure and reactivity. Recent experiments by our group have demonstrated that the relatively low levels of residual H2O in a 2-D, linear ion trap (LIT) make it possible to examine fragmentation pathways and reactions not observed in earlier studies conducted with 3-D ion traps (Van Stipdonk et al. J. Am. Soc. Mass Spectrom. 14, 1205-1214, 2003). In the present study, we revisited the dissociation of complexes composed of uranyl nitrate cation [UVIO2(NO3)]+ coordinated by alcohol ligands (methanol and ethanol) using the 2-D LIT. With relatively low levels of background H2O, collision-induced dissociation (CID) of [UVIO2(NO3)]+ primarily creates [UO2(O2)]+ by the ejection of NO. However, CID (using He as collision gas) of [UVIO2(NO3)]+ creates [UO2(H2O)]+ and UO2 + when the 2-D LIT is used with higher levels of background H2O. Based on the results presented here, we propose that product ion spectrum in the previous experiments was the result of a two-step process: initial formation of [UVIO2(O2)]+ followed by rapid exchange of O2 for H2O by ion-molecule reaction. Our experiments illustrate the impact of residual H2O in ion trap instruments on the product ions generated by CID and provide a more accurate description of the intrinsic dissociation pathway for [UVIO2(NO3)]+. [Figure not available: see fulltext.

Influence of experimental parameters on sonochemistry dosimetries: KI oxidation, Fricke reaction and H2O2 production.

PubMed

Merouani, Slimane; Hamdaoui, Oualid; Saoudi, Fethi; Chiha, Mahdi

2010-06-15

Central events of the ultrasonic action are the cavitation bubbles that can be considered as microreactors. Adiabatic collapse of cavitation bubbles leads to the formation of reactive species such as hydroxyl radicals (*OH), hydrogen peroxide (H(2)O(2)) and hydroperoxyl radicals (HOO*). Several chemical methods were used to detect the production of these reactive moieties in sonochemistry. In this work, the influence of several operational parameters on the sonochemistry dosimetries namely KI oxidation, Fricke reaction and H(2)O(2) production using 300 kHz ultrasound was investigated. The main experimental parameters showing significant effect in KI oxidation dosimetry were initial KI concentration, acoustic power and pH. The solution temperature showed restricted influence on KI oxidation. The acoustic power and liquid temperature highly affected Fricke reaction dosimetry. Operational conditions having important influence on H(2)O(2) formation were acoustic power, solution temperature and pH. For the three tested dosimetries, the sonochemical efficiency was independent of liquid volume. Copyright 2010 Elsevier B.V. All rights reserved.

Synthesis of zinc sulfide nanoparticles during zinc oxidization by H2S and H2S/H2O supercritical fluids

NASA Astrophysics Data System (ADS)

Vostrikov, A. A.; Fedyaeva, O. N.; Sokol, M. Ya.; Shatrova, A. V.

2014-12-01

Formation of zinc sulfide nanoparticles was detected during interaction of bulk samples with hydrogen sulfide at supercritical parameters. Synthesis proceeds with liberation of H2 by the reaction nZn + nH2S = (ZnS) n + nH2. It has been found by the X-ray diffraction method, scanning electron microscopy, and mass spectrometry that the addition of water stimulates coupled reactions of nanoparticle synthesis nZn + nH2O = (ZnO) n + nH2 and (ZnO) n + nH2S = (ZnS) n + nH2O and brings about an increase in the synthesis rate and morphological changes of (ZnS) n nanoparticles.

Stibiconite (Sb3O6OH), senarmontite (Sb2O3) and valentinite (Sb2O3): Dissolution rates at pH 2-11 and isoelectric points

NASA Astrophysics Data System (ADS)

Biver, M.; Shotyk, W.

2013-05-01

Batch reactor experiments were carried out in order to derive rate laws for the proton promoted dissolution of the main natural antimony oxide phases, namely stibiconite (idealized composition SbSb2O6OH), senarmontite (cubic Sb2O3) and (metastable) valentinite (orthorhombic Sb2O3) over the range 2 ⩽ pH ⩽ 11, under standard conditions and ionic strength I = 0.01 mol l-1. The rates of antimony release by stibiconite were r = (2.2 ± 0.2) × 10-9 a(H+)0.11±0.01 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 4.74 and r = (4.3 ± 0.2) × 10-10 a(H+)-0.030±0.003 mol m-2 s-1 for 4.74 ⩽ pH ⩽ 10.54. The rates of dissolution of senarmontite were r = (5.3 ± 2.2) × 10-7 a(H+)0.54±0.05 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 6.93 and r = (1.4 ± 0.3) × 10-14 a(H+)-0.53±0.07 mol m-2 s-1 for 6.93 ⩽ pH ⩽ 10.83. The rates of dissolution of valentinite were r = (6.3 ± 0.2) × 10-8 a(H+)0.052±0.003 mol m-2 s-1 for 1.97 ⩽ pH ⩽ 6.85. Above pH = 6.85, valentinite was found to dissolve at a constant rate of r = (2.79 ± 0.05) × 10-8 mol m-2 s-1. Activation energies were determined at selected pH values in the acidic and basic domain, over the temperature range 25-50 °C. The values for stibiconite are -10.6 ± 1.9 kJ mol-1 (pH = 2.00) and 53 ± 14 kJ mol-1 (pH = 8.7). For senarmontite, we found 46.6 ± 4.7 kJ mol-1 (pH = 3.0) and 68.1 ± 6.1 kJ mol-1 (pH = 9.9) and for valentinite 41.9 ± 1.1 kJ mol-1 (pH = 3.0) and 39.0 ± 4.6 kJ mol-1 (pH = 9.9). These activation energies are interpreted in the text. The solubility of stibiconite at 25 °C in the pH domain from 2 to 10 was determined; solubilities decrease from 452.0 μg l-1 (as Sb) at pH = 2.00 to 153.2 μg l-1 at pH = 7.55 and increase again in the basic region, up to 176.6 μg l-1 at pH = 9.92. A graphical synopsis of all the kinetic results, including those of stibnite (Sb2S3) from earlier work, is presented. This allows an easy comparison between the dissolution rates of stibnite and the minerals examined in the present work

Effect of Soil pH Increase by Biochar on NO, N2O and N2 Production during Denitrification in Acid Soils

PubMed Central

Obia, Alfred; Cornelissen, Gerard; Mulder, Jan; Dörsch, Peter

2015-01-01

Biochar (BC) application to soil suppresses emission of nitrous- (N2O) and nitric oxide (NO), but the mechanisms are unclear. One of the most prominent features of BC is its alkalizing effect in soils, which may affect denitrification and its product stoichiometry directly or indirectly. We conducted laboratory experiments with anoxic slurries of acid Acrisols from Indonesia and Zambia and two contrasting BCs produced locally from rice husk and cacao shell. Dose-dependent responses of denitrification and gaseous products (NO, N2O and N2) were assessed by high-resolution gas kinetics and related to the alkalizing effect of the BCs. To delineate the pH effect from other BC effects, we removed part of the alkalinity by leaching the BCs with water and acid prior to incubation. Uncharred cacao shell and sodium hydroxide (NaOH) were also included in the study. The untreated BCs suppressed N2O and NO and increased N2 production during denitrification, irrespective of the effect on denitrification rate. The extent of N2O and NO suppression was dose-dependent and increased with the alkalizing effect of the two BC types, which was strongest for cacao shell BC. Acid leaching of BC, which decreased its alkalizing effect, reduced or eliminated the ability of BC to suppress N2O and NO net production. Just like untreated BCs, NaOH reduced net production of N2O and NO while increasing that of N2. This confirms the importance of altered soil pH for denitrification product stoichiometry. Addition of uncharred cacao shell stimulated denitrification strongly due to availability of labile carbon but only minor effects on the product stoichiometry of denitrification were found, in accordance with its modest effect on soil pH. Our study indicates that stimulation of denitrification was mainly due to increases in labile carbon whereas change in product stoichiometry was mainly due to a change in soil pH. PMID:26397367

Effect of Soil pH Increase by Biochar on NO, N2O and N2 Production during Denitrification in Acid Soils.

PubMed

Obia, Alfred; Cornelissen, Gerard; Mulder, Jan; Dörsch, Peter

2015-01-01

Biochar (BC) application to soil suppresses emission of nitrous- (N2O) and nitric oxide (NO), but the mechanisms are unclear. One of the most prominent features of BC is its alkalizing effect in soils, which may affect denitrification and its product stoichiometry directly or indirectly. We conducted laboratory experiments with anoxic slurries of acid Acrisols from Indonesia and Zambia and two contrasting BCs produced locally from rice husk and cacao shell. Dose-dependent responses of denitrification and gaseous products (NO, N2O and N2) were assessed by high-resolution gas kinetics and related to the alkalizing effect of the BCs. To delineate the pH effect from other BC effects, we removed part of the alkalinity by leaching the BCs with water and acid prior to incubation. Uncharred cacao shell and sodium hydroxide (NaOH) were also included in the study. The untreated BCs suppressed N2O and NO and increased N2 production during denitrification, irrespective of the effect on denitrification rate. The extent of N2O and NO suppression was dose-dependent and increased with the alkalizing effect of the two BC types, which was strongest for cacao shell BC. Acid leaching of BC, which decreased its alkalizing effect, reduced or eliminated the ability of BC to suppress N2O and NO net production. Just like untreated BCs, NaOH reduced net production of N2O and NO while increasing that of N2. This confirms the importance of altered soil pH for denitrification product stoichiometry. Addition of uncharred cacao shell stimulated denitrification strongly due to availability of labile carbon but only minor effects on the product stoichiometry of denitrification were found, in accordance with its modest effect on soil pH. Our study indicates that stimulation of denitrification was mainly due to increases in labile carbon whereas change in product stoichiometry was mainly due to a change in soil pH.

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

NASA Astrophysics Data System (ADS)

Weng, Sheng-Feng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-04-01

Two novel materials, [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La(1a), Ce(1b)) and [Ce2(C2O4)(C6H6O7)2] . 4H2O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1¯ (No. 2); compound 2 crystallized in monoclinic space group P21/c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of CuII ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d1 excited state and two levels of the 4f1 ground state (2F5/2 and 2F7/2). Compounds 1b and 2 containing CeIII ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers.

A kinetic study of Ca-containing ions reacting with O, O2, CO2 and H2O: implications for calcium ion chemistry in the upper atmosphere.

PubMed

Broadley, Sarah; Vondrak, Tomas; Wright, Timothy G; Plane, John M C

2008-09-14

A series of gas-phase reactions involving molecular Ca-containing ions was studied by the pulsed laser ablation of a calcite target to produce Ca+ in a fast flow of He, followed by the addition of reagents downstream and detection of ions by quadrupole mass spectrometry. Most of the reactions that were studied are important for describing the chemistry of meteor-ablated calcium in the earth's upper atmosphere. The following rate coefficients were measured: k(CaO+ + O --> Ca+ + O2) = (4.2 +/- 2.8) x 10(-11) at 197 K and (6.3 +/- 3.0) x 10(-11) at 294 K; k(CaO+ + CO --> Ca+ + CO2, 294 K) = (2.8 +/- 1.5) x 10(-10); k(Ca+.CO2 + O2 --> CaO2+ + CO2, 294 K) = (1.2 +/- 0.5) x10(-10); k(Ca+.CO2 + H2O --> Ca+.H2O + CO2) = (13.0 +/- 4.0) x 10(-10); and k(Ca+.H2O + O2 --> CaO2+ + H2O, 294 K) = (4.0 +/- 2.5) x 10(-10) cm3 molecule(-1) s(-1). The quoted uncertainties are a combination of the 1 sigma standard errors in the kinetic data and the systematic errors in the models used to extract the rate coefficients. Rate coefficients were also obtained for the following recombination (also termed association) reactions in He bath gas: k(Ca+.CO2 + CO2 --> Ca+.(CO2)2, 294 K) = (2.6 +/- 1.0) x 10(-29); k(Ca+.H2O + H2O --> Ca+.(H2O)2) = (1.6 +/- 1.1) x 10(-27); and k(CaO2+ + O2 --> CaO2+.O2) < 1 x 10(-31) cm6 molecule(-2) s(-1). These recombination rate coefficients, as well as those for the ligand-switching reactions listed above, were then interpreted using a combination of high level quantum chemistry calculations and RRKM theory using an inverse Laplace transform solution of the master equation. The surprisingly slow reaction between CaO+ and O was explained using quantum chemistry calculations on the lowest 2A', 2A'' and 4A'' potential energy surfaces. These calculations indicate that reaction mostly occurs on the 2A' surface, leading to production of Ca+ (2S) + O2(1 Delta g). The importance of this reaction for controlling the lifetime of Ca+ in the upper mesosphere and lower

Photogeneration of H2O2 in Water-Swollen SPEEK/PVA Polymer Films.

PubMed

Lockhart, PaviElle; Little, Brian K; Slaten, B L; Mills, G

2016-06-09

Efficient reduction of O2 took place via illumination with 350 nm photons of cross-linked films containing a blend of sulfonated poly(ether etherketone) and poly(vinyl alcohol) in contact with air-saturated aqueous solutions. Swelling of the solid macromolecular matrices in H2O enabled O2 diffusion into the films and also continuous extraction of the photogenerated H2O2, which was the basis for a method that allowed quantification of the product. Peroxide formed with similar efficiencies in films containing sulfonated polyketones prepared from different precursors and the initial photochemical process was found to be the rate-determining step. Generation of H2O2 was most proficient in the range of 4.9 ≤ pH ≤ 8 with a quantum yield of 0.2, which was 10 times higher than the efficiencies determined for solutions of the polymer blend. Increases in temperature as well as [O2] in solution were factors that enhanced the H2O2 generation. H2O2 quantum yields as high as 0.6 were achieved in H2O/CH3CN mixtures with low water concentrations, but peroxide no longer formed when film swelling was suppressed. A mechanism involving reduction of O2 by photogenerated α-hydroxy radicals from the polyketone in competition with second-order radical decay processes explains the kinetic features. Higher yields result from the films because cross-links present in them hinder diffusion of the radicals, limiting their decay and enhancing the oxygen reduction pathway.

Investigation into the disparate origin of CO2 and H2O outgassing for Comet 67/P

NASA Astrophysics Data System (ADS)

Fink, Uwe; Doose, Lyn; Rinaldi, Giovanna; Bieler, André; Capaccioni, Fabrizio; Bockelée-Morvan, Dominique; Filacchione, Gianrico; Erard, Stephane; Leyrat, Cedric; Blecka, Maria; Capria, Maria Teresa; Combi, Michael; Crovisier, Jacques; De Sanctis, Maria Cristina; Fougere, Nicolas; Taylor, Fred; Migliorini, Alessandra; Piccioni, Giuseppe

2016-10-01

We present an investigation of the emission intensity of CO2 and H2O and their distribution in the coma of 67P/ Churyumov-Gerasimenko obtained by the VIRTIS-M imaging spectrometer on the Rosetta mission. We analyze 4 data cubes from Feb. 28, and 7 data cubes from April 27, 2015. For both data sets the spacecraft was at a sufficiently large distance from the comet to allow images of the whole nucleus and the surrounding coma. We find that unlike water which has a reasonably predictable behavior and correlates well with the solar illumination, CO2 outgasses mostly in local regions or spots. Furthermore for the data on April 27, the CO2 evolves almost exclusively from the southern hemisphere, a region of the comet that has not received solar illumination since the comet's last perihelion passage. Because CO2 and H2O have such disparate origins, deriving mixing ratios from local column density measurements cannot provide a meaningful measurement of the CO2/H2O ratio in the coma of the comet. We obtain total production rates of H2O and CO2 by integrating the band intensity in an annulus surrounding the nucleus and obtain pro-forma production rate CO2/H2O mixing ratios of ∼5.0% and ∼2.5% for Feb. 28 and April 27, respectively. Because of the highly variable nature of the CO2 evolution from the surface we do not believe that these numbers are diagnostic of the comet's bulk CO2/H2O composition. We believe that our investigation provides an explanation for the large observed variations reported in the literature for the CO2/H2O production rate ratios. Our mixing ratio maps indicate that, besides the difference in vapor pressure of the two gases, this ratio depends on the comet's rotational orientation combined with its complex geometric shape which can result in quite variable rates of erosion for different surface areas such as the northern and southern hemisphere. Our annulus measurement for the total water production for Feb. 28 at 2.21AU from the Sun is 2.5 × 1026

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

NASA Technical Reports Server (NTRS)

Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

2004-01-01

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

NASA Astrophysics Data System (ADS)

Roggensack, K.; Allison, C. M.; Clarke, A. B.

2017-12-01

A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that

Mesospheric H2O Concentrations Retrieved from SABER/TIMED Measurements

NASA Technical Reports Server (NTRS)

Feofilov, A. G.; Marshall, B. T.; Garcia-Comas, M.; Kutepov, A. A.; Lopez-Puertas, M.; Manuilova, R. O.; Yankovsky, V.A.; Goldberg, R. A.; Gordley, L. L.; Petelin, S.;

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

NASA Astrophysics Data System (ADS)

Song, Lei; Kästner, Johannes

2017-12-01

Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

Nuclear factor erythroid 2-related factor 2 antioxidant response element pathways protect bovine mammary epithelial cells against H2O2-induced oxidative damage in vitro.

PubMed

Ma, Y F; Wu, Z H; Gao, M; Loor, J J

2018-06-01

The experiment was conducted to determine the role of nuclear factor (erythroid-derived 2)-like factor 2 (NFE2L2, formerly Nrf2) antioxidant response element (ARE) pathway in protecting bovine mammary epithelial cells (BMEC) against H 2 O 2 -induced oxidative stress injury. An NFE2L2 small interfering RNA (siRNA) interference or a pCMV6-XL5-NFE2L2 plasmid fragment was transfected to independently downregulate or upregulate expression of NFE2L2. Isolated BMEC in triplicate were exposed to H 2 O 2 (600 μM) for 6 h to induce oxidative stress before transient transfection with scrambled siRNA, NFE2L2-siRNA, pCMV6-XL5, and pCMV6-XL5-NFE2L2. Cell proliferation, apoptosis and necrosis rates, antioxidant enzyme activities, reactive oxygen species (ROS) and malondialdehyde (MDA) production, protein and mRNA expression of NFE2L2 and downstream target genes, and fluorescence activity of ARE were measured. The results revealed that compared with the control, BMEC transfected with NFE2L2-siRNA3 had proliferation rates that were 9 or 65% lower without or with H 2 O 2 , respectively. These cells also had apoptosis and necrosis rates that were 27 and 3.5 times greater with H 2 O 2 compared with the control group, respectively. In contrast, transfected pCMV6-XL5-NFE2L2 had proliferation rates that were 64.3% greater or 17% lower without or with H 2 O 2 compared with the control group, respectively. Apoptosis rates were 1.8 times lower with H 2 O 2 compared with the control. In addition, compared with the control, production of ROS and MDA and activities of superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), catalase (CAT), and glutathione-S-transferase (GST) increased markedly in cells transfected with pCMV6-XL5-NFE2L2 and without H 2 O 2 . However, compared with the control, production of ROS and MDA and activity of CAT and GSH-Px increased markedly, whereas activities of SOD and GST decreased in cells transfected with pCMV6-XL5-NFE2L2 and incubated with H 2 O 2

UV and VUV photolysis vs. UV/H2O2 and VUV/H2O2, treatment for removal of clofibric acid from aqueous solution.

PubMed

Li, Wenzhen; Lu, Shuguang; Qiu, Zhaofu; Lin, Kuangfei

2011-07-01

Clofibric acid (CA), a metabolite of lipid regulators, was investigated in ultra-pure water and sewage treatment plant (STP) effluent at 10 degrees C under UV, vacuum UV (VUV), UV/H2O2 and VUV/H2O2 processes. The influences of NO3-, HCO3- and humic acid (HA) on CA photolysis in all processes were examined. The results showed that all the experimental data well fitted the pseudo-first-order kinetic model, and the apparent rate constant (k(ap)) and half-life time (t(1/2)) were calculated accordingly. Direct photolysis of CA through UV irradiation was the main process, compared with the indirect oxidation of CA due to the slight generation of hydroxyl radicals dissociated from water molecules under UV irradiation below 200 nm monochromatic wavelength emission. In contrast, indirect oxidation was the main CA degradation mechanism in UV/H2O2 and VUV/H2O2, and VUV/H2O2 was the most effective process for CA degradation. The addition of 20 mg L(-1) HA could significantly inhibit CA degradation, whereas, except for UV irradiation, the inhibitive effects of NO3- and HCO3- (1.0 x 10(-3) and 0.1 mol L(-1), respectively) on CA degradation were observed in all processes, and their adverse effects were more significant in UV/H2O2 and VUV/H2O2 processes, particularly at the high NO3- and HCO3- concentrations. The degradation rate decreased 1.8-4.9-fold when these processes were applied to a real STP effluent owing to the presence of complex constituents. Of the four processes, VUV/H2O2 was the most effective, and the CA removal efficiency reached over 99% after 40 min in contrast to 80 min in both the UV/H2O2 and VUV processes and 240 min in the UV process.

The effect of ZnO addition on H2O activation over Co/ZrO2 catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davidson, Stephen D.; Sun, Junming; Wang, Yong

The effect of ZnO addition on the dissociation of H2O and subsequent effects on cobalt oxidation state and ethanol reaction pathway were investigated over Co/ZrO2 catalyst during ethanol steam reforming (ESR). Catalyst physical properties were characterized by BET, XRD, and TEM. To characterize the catalysts ability to dissociate H2O, Raman spectroscopy, H2O-TPO, and pulsed H2O oxidation coupled with H2-TPR were used. It was found that the addition of ZnO to cobalt supported on ZrO2 decreased the activity for H2O dissociation, leading to a lower degree of cobalt oxidation. The decreased H2O dissociation was also found to affect the reaction pathway,more » evidenced by a shift in liquid product selectivity away from acetone and towards acetaldehyde.« less

Solar kerosene from H2O and CO2

NASA Astrophysics Data System (ADS)

Furler, P.; Marxer, D.; Scheffe, J.; Reinalda, D.; Geerlings, H.; Falter, C.; Batteiger, V.; Sizmann, A.; Steinfeld, A.

2017-06-01

The entire production chain for renewable kerosene obtained directly from sunlight, H2O, and CO2 is experimentally demonstrated. The key component of the production process is a high-temperature solar reactor containing a reticulated porous ceramic (RPC) structure made of ceria, which enables the splitting of H2O and CO2 via a 2-step thermochemical redox cycle. In the 1st reduction step, ceria is endo-thermally reduced using concentrated solar radiation as the energy source of process heat. In the 2nd oxidation step, nonstoichiometric ceria reacts with H2O and CO2 to form H2 and CO - syngas - which is finally converted into kerosene by the Fischer-Tropsch process. The RPC featured dual-scale porosity for enhanced heat and mass transfer: mm-size pores for volumetric radiation absorption during the reduction step and μm-size pores within its struts for fast kinetics during the oxidation step. We report on the engineering design of the solar reactor and the experimental demonstration of over 290 consecutive redox cycles for producing high-quality syngas suitable for the processing of liquid hydrocarbon fuels.

Nanostructured N-doped TiO2 marigold flowers for an efficient solar hydrogen production from H2S

NASA Astrophysics Data System (ADS)

Chaudhari, Nilima S.; Warule, Sambhaji S.; Dhanmane, Sushil A.; Kulkarni, Milind V.; Valant, Matjaz; Kale, Bharat B.

2013-09-01

Nitrogen-doped TiO2 nanostructures in the form of marigold flowers have been synthesized for the first time using a facile solvothermal method. The structural analysis has shown that such an N-doped TiO2 system crystallizes in the anatase structure. The optical absorption spectra have clearly shown the shift in the absorption edge towards the visible-light range, which indicates successful nitrogen doping. The nitrogen doping has been further confirmed by photoluminescence and photoemission spectroscopy. Microscopy studies have shown the thin nanosheets (petals) of N-TiO2 with a thickness of ~2-3 nm, assembled in the form of the marigold flower with a high surface area (224 m2 g-1). The N-TiO2 nanostructure with marigold flowers is an efficient photocatalyst for the decomposition of H2S and production of hydrogen under solar light. The maximum hydrogen evolution obtained is higher than other known N-TiO2 systems. It is noteworthy that photohydrogen production using the unique marigold flowers of N-TiO2 from abundant H2S under solar light is hitherto unattempted. The proposed synthesis method can also be utilized to design other hierarchical nanostructured N-doped metal oxides.Nitrogen-doped TiO2 nanostructures in the form of marigold flowers have been synthesized for the first time using a facile solvothermal method. The structural analysis has shown that such an N-doped TiO2 system crystallizes in the anatase structure. The optical absorption spectra have clearly shown the shift in the absorption edge towards the visible-light range, which indicates successful nitrogen doping. The nitrogen doping has been further confirmed by photoluminescence and photoemission spectroscopy. Microscopy studies have shown the thin nanosheets (petals) of N-TiO2 with a thickness of ~2-3 nm, assembled in the form of the marigold flower with a high surface area (224 m2 g-1). The N-TiO2 nanostructure with marigold flowers is an efficient photocatalyst for the decomposition of H2S and

The Relationship of HCN, C2H6, & H2O in Comets: A Key Clue to Origins?

NASA Astrophysics Data System (ADS)

Mumma, Michael J.; Charnley, Steven B.; Cordiner, Martin; Paganini, Lucas; Villanueva, Geronimo Luis

2017-10-01

Background: HCN, C2H6, and H2O are three of the best characterized volatiles in comets. It is often assumed that all three are primary volatiles, native to the nucleus. Here, we compare their properties in 26 comets (9 JFC and 17 Oort-cloud), making 6 points:1. Both HCN and C2H6 are poor proxies for water production. The production rate ratio (Q-ratio) of each trace gas relative to water varies by a factor of six among these comets.2. All 26 comets have Q-ratios HCN/C2H6 > 0.1. In 18 comets the Q-ratios HCN/H2O and C2H6/H2O are correlated, with a mean ratio of 0.33. In 6 comets undergoing complete disruption, this Q-ratio exceeds 0.5.3. Q-ratios HCN/C2H6 are not correlated with Q(H2O), nor are they correlated with dynamical class (Oort cloud vs. JFC).4. The nucleus-centered rotational temperatures measured for H2O and other primary species (C2H6, CH3OH) usually agree within error, but those for HCN are often slightly cooler. Could this mean that HCN is not fully developed in the warm near-nucleus region, and instead is at least in part a product species?5. With its strong dipole moment and H-bonding character, HCN should be linked more strongly in the nuclear ice to other molecules with similar properties (H2O, CH3OH), but instead its spatial release in some comets seems strongly coupled to volatiles that lack a dipole moment and thus do not form H-bonds (methane, ethane). Is HCN produced in part from an apolar precursor?6. ALMA maps of HCN and the dust continuum show a slight displacement in their centroids. Is this the signature of extended production of HCN?HCN as a product species: Points 4-6 suggest that HCN may have a significant distributed source. The astrochemical species ammonium cyanide is a strong candidate for this HCN precursor; at moderately low temperatures (< 200K) NH4CN is a stable solid, but it dissociates into HCN and NH3 when warmed. Disruption could eject macroscopic solid NH4CN into the coma where subsequent warming and release could augment

Kinetic Studies of Iron Deposition Catalyzed by Recombinant Human Liver Heavy, and Light Ferritins and Azotobacter Vinelandii Bacterioferritin Using O2 and H2O2 as Oxidants

NASA Technical Reports Server (NTRS)

Bunker, Jared; Lowry, Thomas; Davis, Garrett; Zhang, Bo; Brosnahan, David; Lindsay, Stuart; Costen, Robert; Choi, Sang; Arosio, Paolo; Watt, Gerald D.

2005-01-01

The discrepancy between predicted and measured H2O2 formation during iron deposition with recombinant heavy human liver ferritin (rHF) was attributed to reaction with the iron protein complex [Biochemistry 40 (2001) 10832-10838]. This proposal was examined by stopped-flow kinetic studies and analysis for H2O2 production using (1) rHF, and Azotobacter vinelandii bacterial ferritin (AvBF), each containing 24 identical subunits with ferroxidase centers; (2) site-altered rHF mutants with functional and dysfunctional ferroxidase centers; and (3) rccombinant human liver light ferritin (rLF), containing 110 ferroxidase center. For rHF, nearly identical pseudo-first-order rate constants of 0.18 per second at pH 7.5 were measured for Fe(2+) oxidation by both O2 and H2O2, but for rLF, the rate with O2 was 200-fold slower than that for H2O2 (k-0.22 per second). A Fe(2+)/O2 stoichiometry near 2.4 was measured for rHF and its site altered forms, suggesting formation of H2O2. Direct measurements revealed no H2O2 free in solution 0.5-10 min after all Fe(2+) was oxidized at pH 6.5 or 7.5. These results are consistent with initial H2O2 formation, which rapidly reacts in a secondary reaction with unidentified solution components. Using measured rate constants for rHF, simulations showed that steady-state H2O2 concentrations peaked at 14 pM at approx. 600 ms and decreased to zero at 10-30 s. rLF did not produce measurable H2O2 but apparently conducted the secondary reaction with H2O2. Fe(2+)/O2 values of 4.0 were measured for AvBF. Stopped-flow measurements with AvBF showed that both H2O2 and O2 react at the same rate (k=0.34 per second), that is faster than the reactions with rHF. Simulations suggest that AvBF reduces O2 directly to H2O without intermediate H2O2 formation.

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

NASA Technical Reports Server (NTRS)

Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

1981-01-01

Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

H2O-EG-assisted synthesis of uniform urchinlike rutile TiO2 with superior lithium storage properties.

PubMed

Chen, Jun Song; Liang, Yen Nan; Li, Yongmei; Yan, Qingyu; Hu, Xiao

2013-10-23

A facile green method to synthesize uniform nanostructured urchinlike rutile TiO2 is demonstrated. Titanium trichloride was selected as the TiO2 precursor, and a mixed solvent containing H2O and ethylene glycol was used. By using this binary medium, the nucleation and crystal growth of rutile TiO2 can be regulated, giving rise to very uniform urchinlike structures with tailorable sizes. As confirmed by the SEM and TEM analysis, large particles with dense aggregation of needle-like building blocks or small ones with loosely packed subunits could be obtained at different reaction conditions. The as-prepared samples were applied as the anode material for lithium-ion batteries, and they were shown to have superior properties with a high reversible capacity of 140 mA h g(-1) at a high current rate of 10 C for up to 300 cycles, which is almost unmatched by other rutile TiO2-based electrodes. A stable capacity of 88 mA h g(-1) can also be delivered at an extremely high rate of 50 C, suggesting the great potential of the as-prepared product for high-rate lithium-ion batteries.

Comparative investigation of X-ray contrast medium degradation by UV/chlorine and UV/H2O2.

PubMed

Kong, Xiujuan; Jiang, Jin; Ma, Jun; Yang, Yi; Pang, Suyan

2018-02-01

The degradation of iopamidol and diatrizoate sodium (DTZ) by UV/chlorine was carried out according to efficiency, mechanism, and oxidation products, and compared to that by UV/H 2 O 2 . The pseudo-first order rate (k') of iopamidol and DTZ was accelerated by UV/chlorine compared to that by UV and chlorine alone. k' of iopamidol and DTZ by UV/chlorine increased with increasing chlorine dosage. Both of iopamidol and DTZ could not be effectively removed by UV/H 2 O 2 compared to that by UV/chlorine. Secondary radicals (Cl 2 - and ClO) rather than primary radicals (HO and Cl) were demonstrated to be mainly responsible for the enhanced removal of iopamidol and DTZ by UV/chlorine. The oxidation products of iopamidol and DTZ resulting from UV/chlorine and UV/H 2 O 2 process were identified, and differences existed in the two systems. IO 3 - (the desired sink of I - ) was the major inorganic product in the UV/chlorine process whereas I - was the predominant inorganic product in the UV/H 2 O 2 process. The formation of chlorine-containing products during the degradation of iopamidol and DTZ by UV/chlorine was also observed. H-abstraction, additions, de-iodination were shared during the degradation of iopamidol by UV/chlorine and UV/H 2 O 2 . Neutral pH condition was preferred for the removal of iopamidol and DTZ by UV/chlorine. UV/chlorine could also be applied in real waters for the removal of iopamidol and DTZ. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

NASA Astrophysics Data System (ADS)

Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

2012-02-01

We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

PubMed

Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

2012-02-20

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

N2O production by nitrifier denitrification in the Benguela Upwelling System

NASA Astrophysics Data System (ADS)

Frame, C. H.; Hou, L.; Lehmann, M. F.

2014-12-01

The Benguela upwelling system off the coast of southwestern Africa is an important zone of marine N2O production whose upwelling rates vary seasonally. Here we present N2O stable isotopic and isotopomeric data collected during a period of high upwelling (September 2013) and low upwelling (January 2014). During both periods, 15N-nitrite and 15N-ammonium tracer inucbation experiments were used to investigate N2O production by ammonia oxidizing microorganisms in the top 150m of the water column. N2O production from 15N-ammonium was not measurable during these incubations. However, we detected N2O production from 15N-nitrite, suggesting that nitrifier denitrification is a source of shallow N2O in this region. Furthermore, decreasing the pH of the incubation water enhanced the amount of N2O produced, suggesting that upwelling of CO2-rich/low-pH deep water may enhance N2O production in this region. Finally, we present our incubation data in the larger context of the N2O and nitrite isotopic and concentration profiles, with an eye toward comparing incubation-based N2O production rates with profile-based estimates.

Reflected shock tube studies of high-temperature rate constants for OH + NO2 --> HO2 + NO and OH + HO2 --> H2O + O2.

PubMed

Srinivasan, Nanda K; Su, Meng-Chih; Sutherland, James W; Michael, Joe V; Ruscic, Branko

2006-06-01

The motivation for the present study comes from the preceding paper where it is suggested that accepted rate constants for OH + NO2 --> NO + HO2 are high by approximately 2. This conclusion was based on a reevaluation of heats of formation for HO2, OH, NO, and NO2 using the Active Thermochemical Table (ATcT) approach. The present experiments were performed in C2H5I/NO2 mixtures, using the reflected shock tube technique and OH-radical electronic absorption detection (at 308 nm) and using a multipass optical system. Time-dependent profile decays were fitted with a 23-step mechanism, but only OH + NO2, OH + HO2, both HO2 and NO2 dissociations, and the atom molecule reactions, O + NO2 and O + C2H4, contributed to the decay profile. Since all of the reactions except the first two are known with good accuracy, the profiles were fitted by varying only OH + NO2 and OH + HO2. The new ATcT approach was used to evaluate equilibrium constants so that back reactions were accurately taken into account. The combined rate constant from the present work and earlier work by Glaenzer and Troe (GT) is k(OH+NO2) = 2.25 x 10(-11) exp(-3831 K/T) cm3 molecule(-1) s(-1), which is a factor of 2 lower than the extrapolated direct value from Howard but agrees well with NO + HO2 --> OH + NO2 transformed with the updated equilibrium constants. Also, the rate constant for OH + HO2 suitable for combustion modeling applications over the T range (1200-1700 K) is (5 +/- 3) x 10(-11) cm3 molecule(-1) s(-1). Finally, simulating previous experimental results of GT using our updated mechanism, we suggest a constant rate for k(HO2+NO2) = (2.2 +/- 0.7) x 10(-11) cm3 molecule(-1) s(-1) over the T range 1350-1760 K.

CO2 splitting by H2O to CO and O2 under UV light in TiMCM-41silicate sieve

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Wenyong; Han, Hongxian; Frei, Heinz

2004-04-06

The 266 nm light-induced reaction of CO{sub 2} and H{sub 2}O gas mixtures (including isotopic modifications {sup 13}CO{sub 2}, C{sup 18}O{sub 2}, and D{sub 2}O) in framework TiMCM-41 silicate sieve was monitored by in-situ FT-IR spectroscopy at room temperature. Carbon monoxide gas was observed as the sole product by infrared, and the growth was found to depend linearly on the photolysis laser power. H{sub 2}O was confirmed as stoichiometric electron donor. The work establishes CO as the single photon, 2-electron transfer product of CO{sub 2} photoreduction by H{sub 2}O at framework Ti centers for the first time. O{sub 2} wasmore » detected as co-product by mass spectrometric analysis of the photolysis gas mixture. These results are explained by single UV photon-induced splitting of CO{sub 2} by H{sub 2}O to CO and surface OH radical.« less

Stimulation of H(2)O(2) generation by calcium in brain mitochondria respiring on alpha-glycerophosphate.

PubMed

Tretter, Laszlo; Takacs, Katalin; Kövér, Kinga; Adam-Vizi, Vera

2007-11-15

It has been reported recently (Tretter et al., 2007b) that in isolated guinea pig brain mitochondria supported by alpha-glycerophosphate (alpha-GP) reactive oxygen species (ROS) are produced through the reverse electron transport (RET) in the respiratory chain and by alpha-glycerophosphate dehydrogenase (alpha-GPDH). We studied the effect of calcium on the generation of H(2)O(2) as measured by the Amplex Red fluorescent assay in this model. H(2)O(2) production in alpha-GP-supported mitochondria was increased significantly in the presence of 100, 250, and 500 nM Ca(2+), respectively. In addition, Ca(2+) enhanced the membrane potential, the rate of oxygen consumption, and the NAD(P)H autofluorescence in these mitochondria. Direct measurement of alpha-GPDH activity showed that Ca(2+) stimulated the enzyme by decreasing the Km for alpha-GP. In those mitochondria where RET was eliminated by the Complex I inhibitor rotenone (2 microM) or due to depolarization by ADP (1 mM), the rate of H(2)O(2) formation was smaller and the stimulation of H(2)O(2) generation by Ca(2+) was prevented partly, but the stimulatory effect of Ca(2+) was still significant. These data indicate that in alpha-GP-supported mitochondria activation of alpha-GPDH by Ca(2+) leads to an accelerated RET-mediated ROS generation as well as to a stimulated ROS production by alpha-GPDH.

Heterogeneous Ag-TiO2-SiO2 composite materials as novel catalytic systems for selective epoxidation of cyclohexene by H2O2

PubMed Central

Wang, Xin; Xue, Jianyue; Wang, Xinyun; Liu, Xiaoheng

2017-01-01

TiO2-SiO2 composites were synthesized using cetyl trimethyl ammonium bromide (CTAB) as the structure directing template. Self-assembly hexadecyltrimethyl- ammonium bromide TiO2-SiO2/(CTAB) were soaked into silver nitrate (AgNO3) aqueous solution. The Ag-TiO2-SiO2(Ag-TS) composite were prepared via a precipitation of AgBr in soaking process and its decomposition at calcination stage. Structural characterization of the materials was carried out by various techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption and ultraviolet visible spectroscopy (UV-Vis). Characterization results revealed that Ag particles were incorporated into hierarchical TiO2-SiO2 without significantly affecting the structures of the supports. Further heating-treatment at 723 K was more favorable for enhancing the stability of the Ag-TS composite. The cyclohexene oxide was the major product in the epoxidation using H2O2 as the oxidant over the Ag-TS catalysts. Besides, the optimum catalytic activity and stability of Ag-TS catalysts were obtained under operational conditions of calcined at 723 K for 2 h, reaction time of 120 min, reaction temperature of 353 K, catalyst amount of 80 mg, aqueous H2O2 (30 wt.%) as oxidant and chloroform as solvent. High catalytic activity with conversion rate up to 99.2% of cyclohexene oxide could be obtainable in water-bathing. The catalyst was found to be stable and could be reused three times without significant loss of catalytic activity under the optimized reaction conditions. PMID:28493879

Degradation of 40 selected pharmaceuticals by UV/H2O2.

PubMed

Wols, B A; Hofman-Caris, C H M; Harmsen, D J H; Beerendonk, E F

2013-10-01

The occurrence of pharmaceuticals in source waters is increasing. Although UV advanced oxidation is known to be an effective barrier against micropollutants, degradation rates are only available for limited amounts of pharmaceuticals. Therefore, the degradation of a large group of pharmaceuticals has been studied in this research for the UV/H2O2 process under different conditions, including pharmaceuticals of which the degradation by UV/H2O2 was never reported before (e.g., metformin, paroxetine, pindolol, sotalol, venlafaxine, etc.). Monochromatic low pressure (LP) and polychromatic medium pressure (MP) lamps were used for three different water matrices. In order to have well defined hydraulic conditions, all experiments were conducted in a collimated beam apparatus. Degradation rates for the pharmaceuticals were determined. For those compounds used in this research that are also reported in literature, measured degradation results are in good agreement with literature data. Pharmaceutical degradation for only photolysis with LP lamps is small, which is increased by using a MP lamp. Most of the pharmaceuticals are well removed when applying both UV (either LP or MP) and H2O2. However, differences in degradation rates between pharmaceuticals can be large. For example, ketoprofen, prednisolone, pindolol are very well removed by UV/H2O2, whereas metformin, cyclophosphamide, ifosfamide are very little removed by UV/H2O2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Are H and O Being Lost From the Mars Atmosphere in the H2O Stoichiometric Ratio of 2:1?

NASA Astrophysics Data System (ADS)

Jakosky, B. M.; Chaffin, M.; Deighan, J.; Brain, D.; Halekas, J. S.

2017-12-01

Loss of gas from the Mars upper atmosphere to space has been a significant process in the evolution of the Mars atmosphere through time. H is derived from photodissociation of H2O, and is lost by Jeans (thermal) escape. O comes from photodissociation of either H2O or CO2, and is lost by non-thermal processes including dissociative recombination, ion pickup, or sputtering by pick-up ions impacting the atmosphere (in order of importance today). McElroy (1972) proposed that H and O are lost in the ratio of 2:1 that comes from photodissociation of H2O; any imbalance would result in build-up of the lesser-escaping atom that increases its loss rate until the rates were in balance. For the Mars year observed by MAVEN, the large seasonal variation in H loss rate makes this hypothesis difficult to evaluate; however, current best estimates of loss rates suggest that they could be in balance, given the observational uncertainties and seasonal variations (both of which are significant). Even if they are in balance over longer timescales, they still might not be during the "MAVEN" year due to: (i) complications resulting from the interplay between multiple loss processes for O beyond only photochemical loss as considered by McElroy, (ii) interannual and longer-term variations in the lower-atmosphere dust and water cycles that can change the escape rate, (iii) the variation in loss rate expected throughout the 11-year solar cycle, (iv) changes in lower-atmosphere forcing due to the changing orbital elements, or (v) loss of C, H, or O to the crust via reaction with surface minerals. The higher (and unequal) loss rates for all species early in history are likely to have kept H and O from being in balance over the 4-billion-year timescale.

Fluoresence cross section of the H2O(+) A 2A1(0,7,0) produced through photoionization of H2O

NASA Technical Reports Server (NTRS)

Wu, C. Y. Robert; Hwang, M. Y.

1988-01-01

The cross section for the production of the H2O(+) A 2A1(0,7,0) - X 2B1(0,0,0) fluorescence through photoionization of H2O was measured in the 14.5-20.5 eV region. The maximum quantum yield is 1.4 x 10 to the -3rd at 16.5 eV.

Surface modification of layered perovskite Sr2TiO4 for improved CO2 photoreduction with H2O to CH4.

PubMed

Kwak, Byeong Sub; Do, Jeong Yeon; Park, No-Kuk; Kang, Misook

2017-11-27

Layered perovskite Sr 2 TiO 4 photocatalyst was synthesized by using sol-gel method with citric acid. In order to increase the surface area of layered perovskite Sr 2 TiO 4 , and thus to improve its photocatalytic activity for CO 2 reduction, its surface was modified via hydrogen treatment or exfoliation. The physical and chemical properties of the prepared catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, elemental mapping analysis, energy-dispersive X-ray spectroscopy, N 2 adsorption-desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electrophoretic light scattering. CO 2 photoreduction was performed in a closed reactor under 6 W/cm 2 UV irradiation. The gaseous products were analyzed using a gas chromatograph equipped with flame ionization and thermal conductivity detectors. The exfoliated Sr 2 TiO 4 catalyst (E-Sr 2 TiO 4 ) exhibited a narrow band gap, a large surface area, and high dispersion. Owing to these advantageous properties, E-Sr 2 TiO 4 photocatalyst showed an excellent catalytic performance for CO 2 photoreduction reaction. The rate of CH 4 production from the photoreduction of CO 2 with H 2 O using E-Sr 2 TiO 4 was about 3431.77 μmol/g cat after 8 h.

Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

H2O Paradox and its Implications on H2O in Moon

NASA Astrophysics Data System (ADS)

Zhang, Youxue

2017-04-01

The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The

Generation of H2, O2, and H2O2 from water by the use of intense femtosecond laser pulses and the possibility of laser sterilization

NASA Astrophysics Data System (ADS)

Chin, S. L.; Lagacé, S.

1996-02-01

An intense femtosecond Ti-sapphire laser pulse was focused into water, leading to self-focusing. Apart from generating a white light (supercontinuum), the intense laser field in the self-focusing regions of the laser pulse dissociated the water molecules, giving rise to hydrogen and oxygen gas as well as hydrogen peroxide. Our analysis shows that the formation of free radicals O, H, and OH preceded the formation of the stable products of H2, O2, and H2O2. Because O radicals and H2O2 are strong oxydizing agents, one can take advantage of this phenomenon to design a laser scheme for sterilization in medical and biological applications.

Crystal and molecular structure of Sr{sub 2}(Edta) . 5H{sub 2}O, Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O, and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O strontium ethylenediaminetetraacetates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Poznyak, A. L.; Sergienko, V. S.

2009-03-15

Three Sr{sup 2+} compounds with the Edta{sup 4-} and H{sub 2}Edta{sup 2-} ligands-Sr{sub 2}(Edta) . 5H{sub 2}O (I), Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O (II), and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O (III)-are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta{sup 4-} ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with threemore » O atoms of the Edta{sup 4-} ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)-2.656(3) and 2.527(3)-2.683(2) A, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) A long. In II and III, the H{sub 2}Edta{sup 2-} anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H{sub 2}Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H{sub 2}Edta{sup 2-} ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)-2.732(2) and 2.482(2)-2.746(3) A, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) A, respectively. In II, all the structural elements are linked into wavy layers. The O-H-O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr{sup 2+} cations and H{sub 2}Edta{sup -} anions form a three-dimensional [Sr{sub 2}(H{sub 2}Edta)(H{sub 2}O){sub 3}]{sub n}{sup 2n+} framework. The Cl{sup -} anions are fixed in channels of the framework by hydrogen bonds with four water

Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

NASA Technical Reports Server (NTRS)

Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

1988-01-01

A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

2-Oxoglutarate dehydrogenase is a more significant source of O2(·-)/H2O2 than pyruvate dehydrogenase in cardiac and liver tissue.

PubMed

Mailloux, Ryan J; Gardiner, Danielle; O'Brien, Marisa

2016-08-01

Pyruvate dehydrogenase (Pdh) and 2-oxoglutarate dehydrogenase (Ogdh) are vital for Krebs cycle metabolism and sources of reactive oxygen species (ROS). O2(·-)/H2O2 formation by Pdh and Ogdh from porcine heart were compared when operating under forward or reverse electron transfer conditions. Comparisons were also conducted with liver and cardiac mitochondria. During reverse electron transfer (RET) from NADH, purified Ogdh generated ~3-3.5× more O2(·-)/H2O2 in comparison to Pdh when metabolizing 0.5-10µM NADH. Under forward electron transfer (FET) conditions Ogdh generated ~2-4× more O2(·-)/H2O2 than Pdh. In both liver and cardiac mitochondria, Ogdh displayed significantly higher rates of ROS formation when compared to Pdh. Ogdh was also a significant source of ROS in liver mitochondria metabolizing 50µM and 500µM pyruvate or succinate. Finally, we also observed that DTT directly stimulated O2(·-)/H2O2 formation by purified Pdh and Ogdh and in cardiac or liver mitochondria in the absence of substrates and cofactors. Taken together, Ogdh is a more potent source of ROS than Pdh in liver and cardiac tissue. Ogdh is also an important ROS generator regardless of whether pyruvate or succinate serve as the sole source of carbon. Our observations provide insight into the ROS generating capacity of either complex in cardiac and liver tissue. The evidence presented herein also indicates DTT, a reductant that is routinely added to biological samples, should be avoided when assessing mitochondrial O2(·-)/H2O2 production. Copyright © 2016 Elsevier B.V. All rights reserved.

Characteristics of alpha-glycerophosphate-evoked H2O2 generation in brain mitochondria.

PubMed

Tretter, Laszlo; Takacs, Katalin; Hegedus, Vera; Adam-Vizi, Vera

2007-02-01

Characteristics of reactive oxygen species (ROS) production in isolated guinea-pig brain mitochondria respiring on alpha-glycerophosphate (alpha-GP) were investigated and compared with those supported by succinate. Mitochondria established a membrane potential (DeltaPsi(m)) and released H(2)O(2) in parallel with an increase in NAD(P)H fluorescence in the presence of alpha-GP (5-40 mm). H(2)O(2) formation and the increase in NAD(P)H level were inhibited by rotenone, ADP or FCCP, respectively, being consistent with a reverse electron transfer (RET). The residual H(2)O(2) formation in the presence of FCCP was stimulated by myxothiazol in mitochondria supported by alpha-GP, but not by succinate. ROS under these conditions are most likely to be derived from alpha-GP-dehydrogenase. In addition, huge ROS formation could be provoked by antimycin in alpha-GP-supported mitochondria, which was prevented by myxothiazol, pointing to the generation of ROS at the quinol-oxidizing center (Q(o)) site of complex III. FCCP further stimulated the production of ROS to the highest rate that we observed in this study. We suggest that the metabolism of alpha-GP leads to ROS generation primarily by complex I in RET, and in addition a significant ROS formation could be ascribed to alpha-GP-dehydrogenase in mammalian brain mitochondria. ROS generation by alpha-GP at complex III is evident only when this complex is inhibited by antimycin.

OH+ and H2O+: Probes of the Molecular Hydrogen Fraction and Cosmic-Ray Ionization Rate

NASA Astrophysics Data System (ADS)

Indriolo, Nick; Neufeld, D. A.; Gerin, M.; PRISMAS; WISH

2014-01-01

The fast ion-molecule chemistry that occurs in the interstellar medium (ISM) is initiated by cosmic-ray ionization of both atomic and molecular hydrogen. Species that are near the beginning of the network of interstellar chemistry such as the oxygen-bearing ions OH+ and H2O+ can be useful probes of the cosmic-ray ionization rate. This parameter is of particular interest as, to some extent, it controls the abundances of several molecules. Using observations of OH+ and H2O+ made with HIFI on board Herschel, we have inferred the cosmic-ray ionization rate of atomic hydrogen in multiple distinct clouds along 12 Galactic sight lines. These two molecules also allow us to determine the molecular hydrogen fraction (amount of hydrogen nuclei in H2 versus H) as OH+ and H2O+ abundances are dependent on the competition between dissociative recombination with electrons and hydrogen abstraction reactions involving H2. Our observations of OH+ and H2O+ indicate environments where H2 accounts for less than 10% of the available hydrogen nuclei, suggesting that these species primarily reside in the diffuse, atomic ISM. Average ionization rates in this gas are on the order of a few times 10-16 s-1, with most values in specific clouds above or below this average by a factor of 3 or so. This result is in good agreement with the most up-to-date determination of the distribution of cosmic-ray ionization rates in diffuse molecular clouds as inferred from observations of H3+.

Degradation of sulfamethoxazole by UV, UV/H2O2 and UV/persulfate (PDS): Formation of oxidation products and effect of bicarbonate.

PubMed

Yang, Yi; Lu, Xinglin; Jiang, Jin; Ma, Jun; Liu, Guanqi; Cao, Ying; Liu, Weili; Li, Juan; Pang, Suyan; Kong, Xiujuan; Luo, Congwei

2017-07-01

The frequent detection of sulfamethoxazole (SMX) in wastewater and surface waters gives rise of concerns about their ecotoxicological effects and potential risks to induce antibacterial resistant genes. UV/hydrogen peroxide (UV/H 2 O 2 ) and UV/persulfate (UV/PDS) advanced oxidation processes have been demonstrated to be effective for the elimination of SMX, but there is still a need for a deeper understanding of product formations. In this study, we identified and compared the transformation products of SMX in UV, UV/H 2 O 2 and UV/PDS processes. Because of the electrophilic nature of SO 4 - , the second-order rate constant for the reaction of sulfate radical (SO 4 - ) with the anionic form of SMX was higher than that with the neutral form, while hydroxyl radical (OH) exhibited comparable reactivity to both forms. The direct photolysis of SMX predominately occurred through cleavage of the NS bond, rearrangement of the isoxazole ring, and hydroxylation mechanisms. Hydroxylation was the dominant pathway for the reaction of OH with SMX. SO 4 - favored attack on NH 2 group of SMX to generate a nitro derivative and dimeric products. The presence of bicarbonate in UV/H 2 O 2 inhibited the formation of hydroxylated products, but promoted the formation of the nitro derivative and the dimeric products. In UV/PDS, bicarbonate increased the formation of the nitro derivative and the dimeric products, but decreased the formation of the hydroxylated dimeric products. The different effect of bicarbonate on transformation products in UV/H 2 O 2 vs. UV/PDS suggested that carbonate radical (CO 3 - ) oxidized SMX through the electron transfer mechanism similar to SO 4 - but with less oxidation capacity. Additionally, SO 4 - and CO 3 - exhibited higher reactivity to the oxazole ring than the isoxazole ring of SMX. Ecotoxicity of transformation products was estimated by ECOSAR program based on the quantitative structure-activity relationship analysis as well as by experiments using

On the role of the termolecular reactions 2O2 + H2 → 2HO2 and 2O2 + H2 → H + HO2 + O2 in formation of the first radicals in hydrogen combustion: ab initio predictions of energy barriers.

PubMed

Monge-Palacios, M; Rafatijo, Homayoon

2017-01-18

We have investigated the role of termolecular reactions in the early chemistry of hydrogen combustion. We performed molecular chemical dynamics simulations using ReaxFF in LAMMPS to identify potential initial reactions for a 1 : 4 mixture of H 2  : O 2 in the NVT ensemble at density 276.3 kg m -3 and ∼3000 K (∼4000 atm) and ∼4000 K (∼5000 atm), and then characterized the saddle points for those reactions using ab initio methods: CCSD(T) = FC/cc-pVTZ//MP2/6-31G, CCSD(T) = FULL/aug-cc-pVTZ//CCSD = FC/cc-pVTZ and CASSCF MP2/6-31G//MP2/6-31G. The main initial reaction is H 2 + O 2 → H + HO 2 , frequently occurring in the presence of a second O 2 as a third body; that is, 2O 2 + H 2 → H + HO 2 + O 2 . The second most frequent reaction is 2O 2 + H 2 → 2HO 2 . We found three saddle points on the triplet PES of these termolecular reactions: one for 2O 2 + H 2 → H + HO 2 + O 2 and two for 2O 2 + H 2 → 2HO 2 . In the latter case, one has a symmetric structure consistent with simultaneous formation of two HO 2 and the other corresponds to a bimolecular reaction between O 2 and H 2 that is "interrupted" by a second O 2 before going to completion. The classical barrier height of the symmetric saddle point for 2O 2 + H 2 → 2HO 2 is 49.8 kcal mol -1 . The barrier to H 2 + O 2 → H + HO 2 is 58.9 kcal mol -1 . The termolecular reaction will be competitive with H 2 + O 2 → H + HO 2 only at sufficiently high pressures.

H2O2 modulates the energetic metabolism of the cloud microbiome

NASA Astrophysics Data System (ADS)

Wirgot, Nolwenn; Vinatier, Virginie; Deguillaume, Laurent; Sancelme, Martine; Delort, Anne-Marie

2017-12-01

Chemical reactions in clouds lead to oxidation processes driven by radicals (mainly HO⚫, NO3⚫, or HO2⚫) or strong oxidants such as H2O2, O3, nitrate, and nitrite. Among those species, hydrogen peroxide plays a central role in the cloud chemistry by driving its oxidant capacity. In cloud droplets, H2O2 is transformed by microorganisms which are metabolically active. Biological activity can therefore impact the cloud oxidant capacity. The present article aims at highlighting the interactions between H2O2 and microorganisms within the cloud system. First, experiments were performed with selected strains studied as a reference isolated from clouds in microcosms designed to mimic the cloud chemical composition, including the presence of light and iron. Biotic and abiotic degradation rates of H2O2 were measured and results showed that biodegradation was the most efficient process together with the photo-Fenton process. H2O2 strongly impacted the microbial energetic state as shown by adenosine triphosphate (ATP) measurements in the presence and absence of H2O2. This ATP depletion was not due to the loss of cell viability. Secondly, correlation studies were performed based on real cloud measurements from 37 cloud samples collected at the PUY station (1465 m a.s.l., France). The results support a strong correlation between ATP and H2O2 concentrations and confirm that H2O2 modulates the energetic metabolism of the cloud microbiome. The modulation of microbial metabolism by H2O2 concentration could thus impact cloud chemistry, in particular the biotransformation rates of carbon compounds, and consequently can perturb the way the cloud system is modifying the global atmospheric chemistry.

Oxygen vacancy rich Cu2O based composite material with nitrogen doped carbon as matrix for photocatalytic H2 production and organic pollutant removal.

PubMed

Lu, Lele; Xu, Xinxin; Yan, Jiaming; Shi, Fa-Nian; Huo, Yuqiu

2018-02-06

A nitrogen doped carbon matrix supported Cu 2 O composite material (Cu/Cu2O@NC) was fabricated successfully with a coordination polymer as precursor through calcination. In this composite material, Cu 2 O particles with a size of about 6-10 nm were dispersed evenly in the nitrogen doped carbon matrix. After calcination, some coordinated nitrogen atoms were doped in the lattice of Cu 2 O and replace oxygen atoms, thus generating a large number of oxygen vacancies. In Cu/Cu2O@NC, the existence of oxygen vacancies has been confirmed by electron spin resonance (ESR) and X-ray photoelectron spectroscopy (XPS). Under visible light irradiation, Cu/Cu2O@NC exhibits excellent H 2 production with the rate of 379.6 μmol h -1 g -1 . Its photocatalytic activity affects organic dyes, such as Rhodamine B (RhB) and methyl orange (MO). In addition to photocatalysis, Cu/Cu2O@NC also exhibits striking catalytic activity in reductive conversion of 4-nitrophenol to 4-aminophenol with in presence of sodium borohydride (NaBH 4 ). The conversion efficiency reaches almost 100% in 250 s with the quantity of Cu/Cu2O@NC as low as 5 mg. The outstanding H 2 production and organic pollutants removal are attributed to the oxygen vacancy. We expect that Cu/Cu2O@NC will find its way as a new resource for hydrogen energy as well as a promising material in water purification.

Synthesis, DFT calculations of structure, vibrational and thermal decomposition studies of the metal complex Pb[Mn(C3H2O4)2(H2O)2].

PubMed

Gil, Diego M; Carbonio, Raúl E; Gómez, María Inés

2015-04-15

The metallo-organic complex Pb[Mn(C3H2O4)2(H2O)2] was synthesized and characterized by IR and Raman spectroscopy and powder X-ray diffraction methods. The cell parameters for the complex were determined from powder X-ray diffraction using the autoindexing program TREOR, and refined by the Le Bail method with the Fullprof program. A hexagonal unit cell was determined with a=b=13.8366(7)Å, c=9.1454(1)Å, γ=120°. The DFT calculated geometry of the complex anion [Mn(C3H2O4)2(H2O)2](2-) is very close to the experimental data reported for similar systems. The IR and Raman spectra and the thermal analysis of the complex indicate that only one type of water molecules is present in the structure. The thermal decomposition of Pb[Mn(C3H2O4)2(H2O)2] at 700 °C in air produces PbO and Pb2MnO4 as final products. The crystal structure of the mixed oxide is very similar to that reported for Pb3O4. Copyright © 2015 Elsevier B.V. All rights reserved.

Removal of pharmaceutically active compounds from synthetic and real aqueous mixtures and simultaneous disinfection by supported TiO2/UV-A, H2O2/UV-A, and TiO2/H2O2/UV-A processes.

PubMed

Bosio, Morgana; Satyro, Suéllen; Bassin, João Paulo; Saggioro, Enrico; Dezotti, Márcia

2018-05-01

Pharmaceutically active compounds are carried into aquatic bodies along with domestic sewage, industrial and agricultural wastewater discharges. Psychotropic drugs, which can be toxic to the biota, have been detected in natural waters in different parts of the world. Conventional water treatments, such as activated sludge, do not properly remove these recalcitrant substances, so the development of processes able to eliminate these compounds becomes very important. Advanced oxidation processes are considered clean technologies, capable of achieving high rates of organic compounds degradation, and can be an efficient alternative to conventional treatments. In this study, the degradation of alprazolam, clonazepam, diazepam, lorazepam, and carbamazepine was evaluated through TiO 2 /UV-A, H 2 O 2 /UV-A, and TiO 2 /H 2 O 2 /UV-A, using sunlight and artificial irradiation. While using TiO 2 in suspension, best results were found at [TiO 2 ] = 0.1 g L -1 . H 2 O 2 /UV-A displayed better results under acidic conditions, achieving from 60 to 80% of removal. When WWTP was used, degradation decreased around 50% for both processes, TiO 2 /UV-A and H 2 O 2 /UV-A, indicating a strong matrix effect. The combination of both processes was shown to be an adequate approach, since removal increased up to 90%. H 2 O 2 /UV-A was used for disinfecting the aqueous matrices, while mineralization was obtained by TiO 2 -photocatalysis.

H2O2 Production in Species of the Lactobacillus acidophilus Group: a Central Role for a Novel NADH-Dependent Flavin Reductase

PubMed Central

Hertzberger, Rosanne; Arents, Jos; Dekker, Henk L.; Pridmore, R. David; Gysler, Christof; Kleerebezem, Michiel

2014-01-01

Hydrogen peroxide production is a well-known trait of many bacterial species associated with the human body. In the presence of oxygen, the probiotic lactic acid bacterium Lactobacillus johnsonii NCC 533 excretes up to 1 mM H2O2, inducing growth stagnation and cell death. Disruption of genes commonly assumed to be involved in H2O2 production (e.g., pyruvate oxidase, NADH oxidase, and lactate oxidase) did not affect this. Here we describe the purification of a novel NADH-dependent flavin reductase encoded by two highly similar genes (LJ_0548 and LJ_0549) that are conserved in lactobacilli belonging to the Lactobacillus acidophilus group. The genes are predicted to encode two 20-kDa proteins containing flavin mononucleotide (FMN) reductase conserved domains. Reductase activity requires FMN, flavin adenine dinucleotide (FAD), or riboflavin and is specific for NADH and not NADPH. The Km for FMN is 30 ± 8 μM, in accordance with its proposed in vivo role in H2O2 production. Deletion of the encoding genes in L. johnsonii led to a 40-fold reduction of hydrogen peroxide formation. H2O2 production in this mutant could only be restored by in trans complementation of both genes. Our work identifies a novel, conserved NADH-dependent flavin reductase that is prominently involved in H2O2 production in L. johnsonii. PMID:24487531

Ground and excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters: Insight into the electronic structure of the [Fe(H2O)6]2+ – [Fe(H2O)6]3+ complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miliordos, Evangelos; Xantheas, Sotiris S.

We report the ground and low lying electronically excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters using multi-configuration electronic structure theory. In particular, we have constructed the Potential Energy Curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations as theymore » contain at least one H2O+ fragment and a positive metal center. The most stable equilibrium structures emanate – via intersections and/or avoided crossings – from the channels consisting of the lowest electronic states of Fe2+(5D; 3d6) or Fe3+(6S; 3d5) and six neutral water molecules. Upon hydration, the ground state of Fe2+(H2O)6 is a triply (5Tg) degenerate one with the doubly (5Eg) degenerate state lying slightly higher in energy. Similarly, Fe3+(H2O)6 has a ground state of 6Ag symmetry under Th symmetry. We furthermore examine a multitude of electronically excited states of many possible spin multiplicities, and report the optimized geometries for several selected states. The PECs for those cases are characterized by a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6]2+ and [Fe(H2O)6]3+ clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe2+(H2O)6 – Fe3+(H2O)6 gas phase complex for different Fe–Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We examined a total of ten electronic states for this complex, including those corresponding to the

Upper limits for the rate constant for the reaction Br + H2O2 yields HB2 + HO2

NASA Technical Reports Server (NTRS)

Leu, M.-T.

1980-01-01

Upper limits for the rate constant for the reaction Br + H2O2 yields HBr + HO2 have been measured over the temperature range 298 to 417 K in a discharge flow system using a mass spectrometer as a detector. Results are k sub 1 less than 1.5 x 10 to the -15th power cu cm/s at 298 K and k sub 1 less than 3.0 x 10 to the -15th power cu cm/s at 417 K, respectively. The implication to stratospheric chemistry is discussed.

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Novel Process of Simultaneous Removal of Nitric Oxide and Sulfur Dioxide Using a Vacuum Ultraviolet (VUV)-Activated O2/H2O/H2O2 System in A Wet VUV-Spraying Reactor.

PubMed

Liu, Yangxian; Wang, Qian; Pan, Jianfeng

2016-12-06

A novel process for NO and SO 2 simultaneous removal using a vacuum ultraviolet (VUV, with 185 nm wavelength)-activated O 2 /H 2 O/H 2 O 2 system in a wet VUV-spraying reactor was developed. The influence of different process variables on NO and SO 2 removal was evaluated. Active species (O 3 and ·OH) and liquid products (SO 3 2- , NO 2 - , SO 4 2- , and NO 3 - ) were analyzed. The chemistry and routes of NO and SO 2 removal were investigated. The oxidation removal system exhibits excellent simultaneous removal capacity for NO and SO 2 , and a maximum removal of 96.8% for NO and complete SO 2 removal were obtained under optimized conditions. SO 2 reaches 100% removal efficiency under most of test conditions. NO removal is obviously affected by several process variables. Increasing VUV power, H 2 O 2 concentration, solution pH, liquid-to-gas ratio, and O 2 concentration greatly enhances NO removal. Increasing NO and SO 2 concentration obviously reduces NO removal. Temperature has a dual impact on NO removal, which has an optimal temperature of 318 K. Sulfuric acid and nitric acid are the main removal products of NO and SO 2 . NO removals by oxidation of O 3 , O·, and ·OH are the primary routes. NO removals by H 2 O 2 oxidation and VUV photolysis are the complementary routes. A potential scaled-up removal process was also proposed initially.

The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

DOE PAGES

Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

2016-04-16

Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

New Optical Constants for Amorphous and Crystalline H2O-ice and H2O-mixtures.

NASA Technical Reports Server (NTRS)

Mastrapa, Rachel; Bernstein, Max; Sandford, Scott

2006-01-01

We will present the products of new laboratory measurements of ices relevant to Trans-Neptunian Objects. We have calculated the real and imaginary indices of refraction for amorphous and crystalline H2O-ice and also H2O-rich ices containing other molecular species. We create ice samples by condensing gases onto a cold substrate. We measure the thickness of the sample by reflecting a He-Ne laser off of the sample and counting interference fringes as it grows. We then collect transmission spectra of the samples in the wavelength range from 0.7-22 micrometers. Using the thickness and the transmission spectra of the ice we calculate the imaginary part of the index of refraction. We then use a Kramers-Kronig calculation to calculate the real part of the index of refraction (Berland et al. 1994; Hudgins et al. 1993). These optical constants can then be used to create model spectra for comparison to spectra from Solar System objects, including TNOs. We will summarize the difference between the amorphous and crystalline H2O-ice spectra. These changes include weakening of features and shifting of features to shorter wavelength. One important result is that the 2 pm feature is stronger in amorphous H2O ice than it is in crystalline H2O-ice. We will also discuss the changes seen when H2O is mixed with other components, including CO2, CH4, HCN, and NH3 (Bernstein et al. 2005; Bernstein et al. 2006).

N2O production in the Fe(II)(EDTA)-NO reduction process: the effects of carbon source and pH.

PubMed

Chen, Jun; Wang, Lei; Zheng, Ji; Chen, Jianmeng

2015-07-01

Chemical absorption-biological reduction (BioDeNOx), which uses Fe(II)(EDTA) as a complexing agent for promoting the mass transfer efficiency of NO from gas to water, is a promising technology for removing nitric oxide (NO) from flue gases. The carbon source and pH are important parameters for Fe(II)(EDTA)-NO (the production of absorption) reduction and N2O emissions from BioDeNOx systems. Batch tests were performed to evaluate the effects of four different carbon sources (i.e., methanol, ethanol, sodium acetate, and glucose) on Fe(II)(EDTA)-NO reduction and N2O emissions at an initial pH of 7.2 ± 0.2. The removal efficiency of Fe(II)(EDTA)-NO was 93.9%, with a theoretical rate of 0.77 mmol L(-1) h(-1) after 24 h of operation. The highest N2O production was 0.025 mmol L(-1) after 3 h when glucose was used as the carbon source. The capacities of the carbon sources to enhance the activity of the Fe(II)(EDTA)-NO reductase enzyme decreased in the following order based on the C/N ratio: glucose > ethanol > sodium acetate > methanol. Over the investigated pH range of 5.5-8.5, the Fe(II)(EDTA)-NO removal efficiency was highest at a pH of 7.5, with a theoretical rate of 0.88 mmol L(-1) h(-1). However, the N2O production was lowest at a pH of 8.5. The primary effect of pH on denitrification resulted from the inhibition of nosZ in acidic conditions.

Abatement of Polychoro-1,3-butadienes in Aqueous Solution by Ozone, UV Photolysis, and Advanced Oxidation Processes (O3/H2O2 and UV/H2O2).

PubMed

Lee, Minju; Merle, Tony; Rentsch, Daniel; Canonica, Silvio; von Gunten, Urs

2017-01-03

The abatement of 9 polychloro-1,3-butadienes (CBDs) in aqueous solution by ozone, UV-C(254 nm) photolysis, and the corresponding advanced oxidation processes (AOPs) (i.e., O 3 /H 2 O 2 and UV/H 2 O 2 ) was investigated. The following parameters were determined for 9 CBDs: second-order rate constants for the reactions of CBDs with ozone (k O 3 ) (<0.1-7.9 × 10 3 M -1 s -1 ) or with hydroxyl radicals (k • OH ) (0.9 × 10 9 - 6.5 × 10 9 M -1 s -1 ), photon fluence-based rate constants (k') (210-2730 m 2 einstein -1 ), and quantum yields (Φ) (0.03-0.95 mol einstein -1 ). During ozonation of CBDs in a natural groundwater, appreciable abatements (>50% at specific ozone doses of 0.5 gO 3 /gDOC to ∼100% at ≥1.0 gO 3 /gDOC) were achieved for tetra-CBDs followed by (Z)-1,1,2,3,4-penta-CBD and hexa-CBD. This is consistent with the magnitude of the determined k O 3 and k • OH . The formation of bromate, a potentially carcinogenic ozonation byproduct, could be significantly reduced by addition of H 2 O 2 . For a typical UV disinfection dose (400 J/m 2 ), various extents of phototransformations (10-90%) could be achieved. However, the efficient formation of photoisomers from CBDs with E/Z configuration must be taken into account because of their potential residual toxicity. Under UV-C(254 nm) photolysis conditions, no significant effect of H 2 O 2 addition on CBDs abatement was observed due to an efficient direct phototransformation of CBDs.

Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

Decoloration Kinetics of Waste Cooking Oil by 60Co γ-ray/H2O2

NASA Astrophysics Data System (ADS)

Xiang, Yulin; Xiang, Yuxiu; Wang, Lipeng

2016-03-01

In order to decolorize, waste cooking oil, a dark red close to black solution from homes and restaurants, was subjected to 60Co γ-ray/H2O2 treatment. By virtue of UV/Vis spectrophotometric method, the influence of Gamma irradiation to decoloration kinetics and rate constants of the waste cooking oil in the presence of H2O2 was researched. In addition, the influence of different factors such as H2O2 concentration and irradiation dose on the decoloration rate of waste cooking oil was investigated. Results indicated that the decoloration kinetics of waste cooking oil conformed to the first-order reaction. The decoloration rate increased with the increase of irradiation dose and H2O2 concentration. Saponification analysis and sensory evaluation showed that the sample by 60Co γ-ray/H2O2 treatment presented better saponification performance and sensory score. Furthermore, according to cost estimate, the cost of the 60Co γ-ray/H2O2 was lower and more feasible than the H2O2 alone for decoloration of waste cooking oil.

Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

PubMed

Srithep, Sirinthip; Phattarapattamawong, Songkeart

2017-06-01

The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Bi2O3 cocatalyst improving photocatalytic hydrogen evolution performance of TiO2

NASA Astrophysics Data System (ADS)

Xu, Difa; Hai, Yang; Zhang, Xiangchao; Zhang, Shiying; He, Rongan

2017-04-01

Photocatalytic hydrogen production using water splitting is of potential importance from the viewpoint of renewable energy development. Herein, Bi2O3-TiO2 composite photocatalysts presented as Bi-Bi2O3-anatase-rutile TiO2 multijunction were first fabricated by a simple impregnation-calcination method using Bi2O3 as H2-production cocatalysts. The obtained multijunction samples exhibit an obvious enhancement in photocatalytic H2 evolution activity in the presence of glycerol. The effect of Bi2O3 amount on H2-evolution activity of TiO2 was investigated and the optimal Bi2O3 content was found to be 0.89 mol%, achieving a H2-production rate of 920 μmol h-1, exceeding that of pure TiO2 by more than 73 times. The enhanced mechanism of photocatalytic H2-evolution activity is proposed. This study will provide new insight into the design and fabrication of TiO2-based hydrogen-production photocatalysts using low-cost Bi2O3 as cocatalyst.

Degradation mechanism of cyanide in water using a UV-LED/H2O2/Cu2+ system.

PubMed

Kim, Tae-Kyoung; Kim, Taeyeon; Jo, Areum; Park, Suhyun; Choi, Kyungho; Zoh, Kyung-Duk

2018-06-01

In this study, we developed a UV-LED/H 2 O 2 /Cu 2+ system to remove cyanide, which is typically present in metal electroplating wastewater. The results showed the synergistic effects of UV-LED, H 2 O 2 , and Cu 2+ ions on cyanide removal in comparison with UV-LED photolysis, H 2 O 2 oxidation, UV-LED/H 2 O 2 , and H 2 O 2 /Cu 2+ systems. Cyanide was removed completely in 30 min in the UV-LED/H 2 O 2 /Cu 2+ system, and its loss followed pseudo-first order kinetics. Statistically, both H 2 O 2 and Cu 2+ ions showed positive effects on cyanide removal, but Cu 2+ ions exhibited a greater effect. The highest cyanide removal rate constant (k = 0.179 min -1 ) was achieved at pH 11, but the lowest was achieved at pH 12.5 (k = 0.064 min -1 ) due to the hydrolysis of H 2 O 2 (pK a of H 2 O 2  = 11.75). The presence of dissolved organic matter (DOM) inhibited cyanide removal, and the removal rate constant exhibited a negative linear correlation with DOM (R 2  = 0.987). The removal rate of cyanide was enhanced by the addition of Zn 2+ ions (from 0.179 to 0.457 min -1 ), while the co-existence of Ni 2+ or Cr +6 ion with Cu 2+ ion reduced cyanide removal. The formation of OH radicals in the UV-LED/H 2 O 2 /Cu 2+ system was verified using an aminophenyl fluorescence (APF) probe. Cyanate ions and ammonia were detected as the byproducts of cyanide decomposition. Finally, an acute toxicity reduction of 64.6% was achieved in the system within 1 h, despite a high initial cyanide concentration (100 mg/L). In terms of removal efficiency and toxicity reduction, the UV-LED/H 2 O 2 /Cu 2+ system may be an alternative method of cyanide removal from wastewaters. Copyright © 2018 Elsevier Ltd. All rights reserved.

Active sites and mechanisms for H2O2 decomposition over Pd catalysts

PubMed Central

Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

2016-01-01

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

Lactobacillus Species Identification, H2O2 Production, and Antibiotic Resistance and Correlation with Human Clinical Status

PubMed Central

Felten, Annie; Barreau, Claude; Bizet, Chantal; Lagrange, Philippe Henri; Philippon, Alain

1999-01-01

Lactobacilli recovered from the blood, cerebrospinal fluid, respiratory tract, and gut of 20 hospitalized immunocompromised septic patients were analyzed. Biochemical carbohydrate fermentation and total soluble cell protein profiles were used to identify the species. Hydrogen peroxide production was measured. Susceptibility to 19 antibiotics was tested by a diffusion method, and the MICs of benzylpenicillin, amoxicillin, imipenem, erythromycin, vancomycin, gentamicin, and levofloxacin were determined. A small number of species produced H2O2, and antibiotic susceptibilities were species related. Eighteen (90%) of the isolates were L. rhamnosus, one was L. paracasei subsp. paracasei, and one was L. crispatus. L. rhamnosus, L. paracasei subsp. paracasei isolates, and the type strains were neither H2O2 producers nor vancomycin susceptible (MICs, ≥256 μg/ml). L. crispatus, as well as most of the type strains of lactobacilli which belong to the L. acidophilus group, was an H2O2 producer and vancomycin susceptible (MICs, <4 μg/ml). PMID:9986841

Enhanced photocatalytic H2-production activity of C-dots modified g-C3N4/TiO2 nanosheets composites.

PubMed

Li, Yang; Feng, Xionghan; Lu, Zhexue; Yin, Hui; Liu, Fan; Xiang, Quanjun

2018-03-01

As a new carbon-based material, carbon dots (C-dots) have got widely preference because of its excellent electronic transfer capability. In this work, a novel ternary layered C-dots/g-C 3 N 4 /TiO 2 nanosheets (CGT) composite photocatalysts were prepared by impregnation precipitation methods. The optimal ternary CGT composite samples revealed high photocatalytic hydrogen evolution rate in triethanolamine aqueous solutions, which exceeded the rate of the optimal g-C 3 N 4 /TiO 2 composite sample by a factor of 5 times. The improved photocatalytic activity is owed to the positive effects of C-dots and layered heterojunction structure of TiO 2 nanosheets and g-C 3 N 4 sheets. C-dots in the CGT composites can serve as electron reservoirs to capture the photo-induced electrons. The well-defined layered heterojunction structure of CGT provides the intimate contact and the strong interaction of anatase TiO 2 nanosheets and g-C 3 N 4 sheets via face-to-face orientation, which restrains the recombination of photogenerated charge carriers, and thus enhances the photocatalytic H 2 -production activity. Electron paramagnetic resonance and transient photocurrent response proved the strong interaction and improved interfacial charge transfer of TiO 2 nanosheets and g-C 3 N 4 sheets, respectively. The mechanism of improving the photocatalytic H 2 -evolution activity was further confirmed by time-resolved fluorescence, electron paramagnetic resonance, transient photocurrent response and electrochemical impedance spectroscopy. Copyright © 2017 Elsevier Inc. All rights reserved.

Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

USGS Publications Warehouse

Wang, Bronwen; Burau, Richard G.

1995-01-01

Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

H2O2 Synthesis Induced by Irradiation of H2O with Energetic H(+) and Ar(+) Ions at Various Temperatures

NASA Technical Reports Server (NTRS)

Baragiola, R. A.; Loeffler, M. J.; Raut, U.; Vidal, R. A.; Carlson, R. W.

2004-01-01

The detection of H2O2 on Jupiter's icy satellite Europa by the Galileo NIMS instrument presented a strong evidence for the importance of radiation effects on icy surfaces. A few experiments have investigated whether solar flux of protons incident on Europa ice could cause a significant if any H2O2 production. These published results differ as to whether H2O2 can be formed by ions impacting water at temperatures near 80 K, which are appropriate to Europa. This discrepancy may be a result of the use of different incident ion energies, different vacuum conditions, or different ways of processing the data. The latter possibility comes about from the difficulty of identifying the 3.5 m peroxide OH band on the long wavelength wing of the much stronger water 3.1 m band. The problem is aggravated by using straight line baselines to represent the water OH band with a curvature, in the region of the peroxide band, that increases with temperature. To overcome this problem, we use polynomial baselines that provide good fits to the water band and its derivative.

The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.