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Sample records for singlet oxygen mechanism

  1. Mechanism of singlet oxygen deactivation in an electric discharge oxygen - iodine laser

    Science.gov (United States)

    Azyazov, V. N.; Mikheyev, P. A.; Pershin, A. A.; Torbin, A. P.; Heaven, M. C.

    2014-12-01

    We have determined the influence of the reaction of molecular singlet oxygen with a vibrationally excited ozone molecule O2(a 1Δ) + O3(ν) → 2O2 + O on the removal rate of O2(a 1Δ) in an electric-discharge-driven oxygen - iodine laser. This reaction has been shown to be a major channel of O2(a 1Δ) loss at the output of an electric-discharge singlet oxygen generator. In addition, it can also contribute significantly to the loss of O2(a 1Δ) in the discharge region of the generator.

  2. Endogenous Generation of Singlet Oxygen and Ozone in Human and Animal Tissues: Mechanisms, Biological Significance, and Influence of Dietary Components

    Directory of Open Access Journals (Sweden)

    Arnold N. Onyango

    2016-01-01

    Full Text Available Recent studies have shown that exposing antibodies or amino acids to singlet oxygen results in the formation of ozone (or an ozone-like oxidant and hydrogen peroxide and that human neutrophils produce both singlet oxygen and ozone during bacterial killing. There is also mounting evidence that endogenous singlet oxygen production may be a common occurrence in cells through various mechanisms. Thus, the ozone-producing combination of singlet oxygen and amino acids might be a common cellular occurrence. This paper reviews the potential pathways of formation of singlet oxygen and ozone in vivo and also proposes some new pathways for singlet oxygen formation. Physiological consequences of the endogenous formation of these oxidants in human tissues are discussed, as well as examples of how dietary factors may promote or inhibit their generation and activity.

  3. Glow discharge in singlet oxygen

    International Nuclear Information System (INIS)

    Vagin, N.P.; Ionin, A.A.; Klimachev, Yu.M.; Sinitsyn, D.V.; Yuryshev, N.N.; Kochetov, I.V.; Napartovich, A.P.

    2003-01-01

    Currently, there is no experimental data on the plasma balance in gas mixtures with a high content of singlet delta oxygen O 2 ( 1 Δ g ). These data can be obtained by studying the parameters of an electric discharge in singlet oxygen produced by a chemical generator. The O 2 ( 1 Δ g ) molecules significantly change the kinetics of electrons and negative ions in plasma. Hence, the discharge conditions at low and high O 2 ( 1 Δ g ) concentrations are very different. Here, the parameters of the positive column of a glow discharge in a gas flow from a chemical singlet-oxygen generator are studied. It is experimentally shown that, at an O 2 ( 1 Δ g ) concentration of 50% and at pressures of 1.5 and 2 torr, the electric field required to sustain the discharge is considerably lower than in the case when all of the oxygen molecules are in the ground state. A theoretical model of the glow discharge is proposed whose predictions are in good agreement with the experimental data

  4. Singlet oxygen quenching by oxygen in tetraphenyl-porphyrin solutions

    International Nuclear Information System (INIS)

    Dedic, Roman; Korinek, Miloslav; Molnar, Alexander; Svoboda, Antonin; Hala, Jan

    2006-01-01

    Time-resolved measurement of singlet oxygen infrared phosphorescence is a powerful tool for determination of quantum yields and kinetics of its photosensitization. This technique was employed to investigate in detail the previously observed effect of singlet oxygen quenching by oxygen. The question whether the singlet oxygen is quenched by oxygen in ground or in excited state was addressed by study of two complementary dependencies of singlet oxygen lifetimes: on dissolved oxygen concentration and on excitation intensity. Oxygen concentration dependence study of meso-tetra(4-sulphonato)phenylporphyrin (TPPS 4 ) phosphorescence kinetics showed linearity of the dependence of TPPS 4 triplet state rate-constant. Corresponding bimolecular quenching constant of (1.5±0.1)x10 9 l/mol s was obtained. On the other hand, rate constants of singlet oxygen depopulation exhibit nonlinear dependence on oxygen concentration. Comparison of zero oxygen concentration-extrapolated value of singlet oxygen lifetime of (6.5±0.4) μs to (3.7±0.1) μs observed under air-saturated conditions indicates importance of the effect of quenching of singlet oxygen by oxygen. Upward-sloping dependencies of singlet oxygen depopulation rate-constant on excitation intensity evidence that singlet oxygen is predominantly quenched by oxygen in excited singlet state

  5. Holographic monitoring of spatial distributions of singlet oxygen in water

    Science.gov (United States)

    Belashov, A. V.; Bel'tyukova, D. M.; Vasyutinskii, O. S.; Petrov, N. V.; Semenova, I. V.; Chupov, A. S.

    2014-12-01

    A method for monitoring spatial distributions of singlet oxygen in biological media has been developed. Singlet oxygen was generated using Radachlorin® photosensitizer, while thermal disturbances caused by nonradiative deactivation of singlet oxygen were detected by the holographic interferometry technique. Processing of interferograms yields temperature maps that characterize the deactivation process and show the distribution of singlet oxygen species.

  6. Photochemical Oxidation of Thioketones by Singlet Molecular Oxygen Revisited: Insights into Photoproducts, Kinetics, and Reaction Mechanism.

    Science.gov (United States)

    Sánchez-Arroyo, Antonio J; Pardo, Zulay D; Moreno-Jiménez, Florencio; Herrera, Antonio; Martín, Nazario; García-Fresnadillo, David

    2015-11-06

    Photosensitized oxidation of trimethyl[2.2.1]bicycloheptane thioketones by (1)O2 can yield more photoproducts than exclusively ketones and sulfines. Moreover, the ketone/sulfine ratio can be reversed when protic conditions and high thioketone concentrations are used, conversely to earlier results reporting ketones as the main photoproducts. A new mechanistic proposal for sulfine formation is suggested following intermolecular oxygen transfer from a peroxythiocarbonyl intermediate to a second thioketone molecule. Reaction quantum yields (10(-5)-10(-2)) depend on the reaction conditions and time. Sulfine production reaches a maximum at short irradiation times, whereas decomposition to the corresponding ketone is observed at long reaction times. When the thioketone substrate has a hydrogen atom at the α position a peroxyvinylsulfenic acid intermediate can be formed by proton transfer. Reaction of this intermediate with another thioketone molecule can yield more sulfine and its tautomeric vinylsulfenic acid, which dimerizes in situ to the thiosulfinate. The hydroperoxyl group of the peroxyvinylsulfenic acid can also rearrange to the α position, and by reaction with the starting thioketone, α-hydroxy thioketone and additional sulfine can be formed, while dehydration yields the α-oxo thioketone. In situ [2 + 2] and [4 + 2] self-cycloaddition of the α-oxo thioketone yields significant amounts of the corresponding adducts at prolonged irradiation times.

  7. Singlet oxygen-mediated protein oxidation

    DEFF Research Database (Denmark)

    Wright, Adam; Bubb, William A; Hawkins, Clare Louise

    2002-01-01

    Singlet oxygen (1O2) is generated by a number of enzymes as well as by UV or visible light in the presence of a sensitizer and has been proposed as a damaging agent in a number of pathologies including cataract, sunburn, and skin cancers. Proteins, and Cys, Met, Trp, Tyr and His side chains in pa...

  8. In situ H(+)-mediated formation of singlet oxygen from NaBiO3 for oxidative degradation of bisphenol A without light irradiation: Efficiency, kinetics, and mechanism.

    Science.gov (United States)

    Ding, Yaobin; Xia, Xiangli; Ruan, Yufeng; Tang, Heqing

    2015-12-01

    Bisphenol A (BPA) is a ubiquitous environmental contaminant with endocrine disruption potential. This study explored the efficiency, kinetics, and mechanism of BPA removal from weakly acidic solutions by using NaBiO3 as a source of singlet oxygen. It was observed that the use of NaBiO3 (1gL(-1)) could eliminate almost all (more than 97%) of the added BPA (0.1mmolL(-1)) in solutions at pH 5.0 in 60min. The degradation of BPA followed pseudo-first-order kinetics over the pH range from 3 to 9, and the pseudo-first-order rate constant (k) was dependent on pH, NaBiO3 concentration and the coexisting compounds. As solution pH was decreased from 9 to 3 or NaBiO3 concentration was increased from 0.5 to 2gL(-1), the k value was increased logarithmically. Humic acid and Fe(3+) showed little effect on the BPA removal, but Mn(2+) exhibited exceptionally enhancing effect on the degradation of BPA. The involved reactive species were identified as singlet oxygen by using radical scavenger probes and ESR measurement, and the generated singlet oxygen was confirmed to be generated from the decomposition of NaBiO3 mediated by H(+) ions. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling.

    Science.gov (United States)

    Riethmüller, Michaela; Burger, Nils; Bauer, Georg

    2015-12-01

    Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2(.)) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  10. Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling☆

    Science.gov (United States)

    Riethmüller, Michaela; Burger, Nils; Bauer, Georg

    2015-01-01

    Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2.) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. PMID:26225731

  11. Singlet - oxygen therapy. 'MIT-S' apparatus

    International Nuclear Information System (INIS)

    Samosyuk, I.Z.; Chukhraev, N.V.; Pisanko, O.I.

    2003-01-01

    The described method is based on using singlet-oxygen mixture with antioxiding properties. This mixture is produced by photochemical sensibilization of air or water vapour in MIT-S apparatus. Technical parameters of MIT-S are presented. The method is used for therapy of different organs, for prophylactics, treatment and rehabilitation of a series of diseases (bronchial asthma, cardio-vascular, neurologic, sugar diabet, immune diseases)

  12. High-power generator of singlet oxygen

    Czech Academy of Sciences Publication Activity Database

    Jirásek, Vít; Čenský, Miroslav; Špalek, Otomar; Kodymová, Jarmila

    2013-01-01

    Roč. 36, č. 10 (2013), s. 1755-1763 ISSN 0930-7516 Grant - others:Laser Science and Technology Centre(IN) LASTEC/FE/RKT/54/10-11 Institutional research plan: CEZ:AV0Z10100523 Keywords : high-pressure singlet oxygen generator * spray generator * centrifugal separation Subject RIV: BH - Optics, Masers, Lasers Impact factor: 2.175, year: 2013

  13. The Contribution of Singlet Oxygen to Insulin Resistance

    Directory of Open Access Journals (Sweden)

    Arnold N. Onyango

    2017-01-01

    Full Text Available Insulin resistance contributes to the development of diabetes and cardiovascular dysfunctions. Recent studies showed that elevated singlet oxygen-mediated lipid peroxidation precedes and predicts diet-induced insulin resistance (IR, and neutrophils were suggested to be responsible for such singlet oxygen production. This review highlights literature suggesting that insulin-responsive cells such as endothelial cells, hepatocytes, adipocytes, and myocytes also produce singlet oxygen, which contributes to insulin resistance, for example, by generating bioactive aldehydes, inducing endoplasmic reticulum (ER stress, and modifying mitochondrial DNA. In these cells, nutrient overload leads to the activation of Toll-like receptor 4 and other receptors, leading to the production of both peroxynitrite and hydrogen peroxide, which react to produce singlet oxygen. Cytochrome P450 2E1 and cytochrome c also contribute to singlet oxygen formation in the ER and mitochondria, respectively. Endothelial cell-derived singlet oxygen is suggested to mediate the formation of oxidized low-density lipoprotein which perpetuates IR, partly through neutrophil recruitment to adipose tissue. New singlet oxygen-involving pathways for the formation of IR-inducing bioactive aldehydes such as 4-hydroperoxy-(or hydroxy or oxo-2-nonenal, malondialdehyde, and cholesterol secosterol A are proposed. Strategies against IR should target the singlet oxygen-producing pathways, singlet oxygen quenching, and singlet oxygen-induced cellular responses.

  14. Direct spectroscopic observation of singlet oxygen quenching and kinetic studies of physical and chemical singlet oxygen quenching rate constants of synthetic antioxidants (BHA, BHT, and TBHQ) in methanol.

    Science.gov (United States)

    Lee, Jun Hyun; Jung, Mun Yhung

    2010-08-01

    Singlet oxygen quenching by synthetic antioxidants (BHA, BHT, and TBHQ) was directly observed by spectroscopic monitoring of luminescence at 1268 nm. The luminescence data showed unambiguous evidence of singlet oxygen quenching by synthetic phenolic antioxidants with the highest activity for TBHQ, followed by BHA and BHT. The protective activities of these synthetic antioxidants on alpha-terpinene oxidation with chemically-induced singlet oxygen under dark further confirmed their singlet oxygen quenching abilities. Total singlet oxygen quenching rate constants (k(r) + k(q)) of BHA, BHT, and TBHQ were determined in a system containing alpha-terpinene (as a singlet oxygen trap) and methylene blue (as a sensitizer) during light irradiation, and the values were 5.14 x 10(7), 3.41 x 10(6), and 1.99 x 10(8) M(-1)s(-1), respectively. After the k(r) value of alpha-terpinene was first determined, the k(r) values of the synthetic antioxidants were calculated by measuring their relative reaction rates with singlet oxygen to that of alpha-terpinene under the identical conditions. The k(r) values of the BHA, BHT, and TBHQ were 3.90 x 10(5), 1.23 x 10(5), and 2.93 x 10(6), M(-1)s(-1). The percent partition of chemical quenching over total singlet oxygen quenching (k(r) x 100)/(k(r) + k(q)) for BHA, BHT, and TBHQ were 0.76%, 3.61%, and 1.47%, respectively. The results showed that the synthetic antioxidants quench singlet oxygen almost exclusively through the mechanism of physical quenching. This represents the first report on the singlet oxygen quenching mechanism of these synthetic antioxidants. Practical Application: The synthetic antioxidants, especially TBHQ, have been found to have a strong singlet oxygen quenching ability. This article also clearly showed that singlet oxygen quenching by synthetic antioxidants was mainly by the physical quenching mechanism. The results suggested that these synthetic antioxidants, especially TBHQ, could be used practically for the protection

  15. The development of efficient two-photon singlet oxygen sensitizers

    DEFF Research Database (Denmark)

    Nielsen, Christian Benedikt

    the singlet oxygen yield and the two-photon absorption cross section, where it was revealed that a careful balancing of the amount of charge transfer present in theexcited state of the sensitizer is necessary to obtain both a high singlet oxygen quantum yield and a high two-photon cross section. An increasing...... amount of charge-transfer is beneficial for high two-photon absorption cross sections but iscounter-productive for singlet oxygen generation. The design principles obtained from the studies in lipophilic solvents were applied to synthesize water-soluble twophoton singlet oxygen sensitizers......The development of efficient two-photon singlet oxygen sensitizers is addressed focusing on organic synthesis. Photophysical measurements were carried out on new lipophilic molecules, where two-photon absorption cross sections and singlet oxygen quantumyields were measured. Design principles...

  16. Optical detection of singlet oxygen from single cells

    DEFF Research Database (Denmark)

    Snyder, John; Skovsen, Esben; Lambert, John D. C.

    2006-01-01

    The lowest excited electronic state of molecular oxygen, singlet molecular oxygen, O2(a 1g), is a reactive species involved in many chemical and biological processes. To better understand the roles played by singlet oxygen in biological systems, particularly at the sub-cellular level, optical tools...

  17. Singlet oxygen-mediated damage to proteins and its consequences

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan

    2003-01-01

    as radical termination reactions. This paper reviews the data available on singlet oxygen-mediated protein oxidation and concentrates primarily on the mechanisms by which this excited state species brings about changes to both the side-chains and backbone of amino acids, peptides, and proteins. Recent work...... to other biological targets, and may play a significant role in bystander damage, or dark reactions, in systems where proteins are subjected to oxidation....

  18. Singlet oxygen-mediated protein oxidation

    DEFF Research Database (Denmark)

    Wright, Adam; Bubb, William A; Hawkins, Clare Louise

    2002-01-01

    Singlet oxygen (1O2) is generated by a number of enzymes as well as by UV or visible light in the presence of a sensitizer and has been proposed as a damaging agent in a number of pathologies including cataract, sunburn, and skin cancers. Proteins, and Cys, Met, Trp, Tyr and His side chains...... methods. The yield of these species is significantly enhanced in D2O and decreased by azide. Nuclear magnetic resonance and mass spectroscopic analysis of reaction mixtures, or materials separated by high-performance liquid chromatography, are consistent with the initial formation of an (undetected......-hydroxy-6-oxo-2,3,3a,6,7,7a-hexahydro-1H-indole-2-carboxylic acid. Hydroperoxides that lack a free alpha-amino group (e.g. those formed on 3-(4-hydroxyphenyl)propionic acid, N-Ac-Tyr and Tyr-containing peptides) are longer-lived, with half-lives of hours to days. These species undergo slow decay at low...

  19. Singlet oxygen: photosensitized generation, detection and reaction with organic molecules

    International Nuclear Information System (INIS)

    Barik, Atanu; Indira Priyadarsini, K.; Hari Mohan; Bajaj, P.N.; Sapre, A.V.; Mittal, J.P.; Mukherjee, T.

    2006-10-01

    Singlet molecular oxygen ( 1 O 2 ) is an excited state of molecular oxygen, having antiparallel spin in the same π antibonding orbital. The study of singlet oxygen production and reactivity has emerged as a rich and diverse area, with implication in diverse fields, such as synthetic chemistry, polymer chemistry, photodynamic therapy, etc. There are several known methods to produce singlet oxygen, and also various techniques employed to detect it. Out of these, photosensitization method is the most popular one. In this article, photosensitized production of singlet oxygen from triplet oxygen and photosensitizers in presence of light, and its detection by the infrared luminescence at 1270 nm have been presented. Further, some results using different types of photosensitizers, effect of solvent on singlet oxygen quantum yields and lifetime have been discussed. The quenching rate constants of singlet oxygen have been determined with different types of organic molecules such as derivatives of thiourea and its analogues, hydroxy indoles and antioxidants and the results have been presented. (author)

  20. Singlet-oxygen therapy. Scientific and methodological materials

    OpenAIRE

    Chukhraiev, N.; Chukhraieva, E.; Gun'ko, M.; Kurik, L.; Lomeiko, S.; Marushko, Y.; Samosyuk, N.; Tkalina, A.; Vladimirov, A.; Unichenko, A.; Zavorotnaya, R.; Zukow, W.

    2018-01-01

    Radomska Szkoła Wyższa w Radomiu MEDICAL INNOVATIVE TECHNOLOGIES SINGLET-OXYGEN THERAPY Scientific and methodological materials 2018 This edition had extended and translated from ukrainian Edited by Chukhraiev N., Vladimirov A., Zukow W. Radom, Kyiv Radomska Szkoła Wyższa w Radomiu MEDICAL INNOVATIVE TECHNOLOGIES SINGLET-OXYGEN THERAPY Scientific and methodological materials 2018 This edition had extended and translated from ukrainian Edited by ...

  1. Effect of oxygen concentration on singlet oxygen luminescence detection

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Longchao; Lin, Lisheng; Li, Yirong; Lin, Huiyun; Qiu, Zhihai [MOE Key Laboratory of OptoElectronic Science and Technology for Medicine, Fujian Provincial Key Laboratory for Photonics Technology, Fujian Normal University, Fuzhou 350007 (China); Gu, Ying [Department of Laser Medicine, Chinese PLA General Hospital, Beijing 100853 (China); Li, Buhong, E-mail: bhli@fjnu.edu.cn [MOE Key Laboratory of OptoElectronic Science and Technology for Medicine, Fujian Provincial Key Laboratory for Photonics Technology, Fujian Normal University, Fuzhou 350007 (China)

    2014-08-01

    Singlet oxygen ({sup 1}O{sub 2}) is a major phototoxic component in photodynamic therapy (PDT) and its generation is dependent on the availability of tissue oxygen. To examine the effect of oxygen concentration on {sup 1}O{sub 2} detection, two hydrophilic photosensitizer (PS), rose bengal (RB) and meso-metra (N-methyl-4-pyridyl) porphine tetra tosylate (TMPyP) were used as model PS. Irradiation was carried out using 523 nm under hypoxic (2%, 13%), normoxic (21%) and hyperoxic (65%) conditions. The spectral and spatial resolved {sup 1}O{sub 2} luminescence was measured by near-infrared (NIR) photomultiplier tube (PMT) and camera, respectively. Upon the irradiation, the emission signal mainly consisted of background scattering light, PS fluorescence and phosphorescence, and {sup 1}O{sub 2} luminescence. The PS phosphorescence was evidently dependent on the oxygen concentration and PS type, which resulted in the change of emission profile of {sup 1}O{sub 2} luminescence. This change was further demonstrated on {sup 1}O{sub 2} luminescence image. The present study suggests that the low oxygen concentration could affect {sup 1}O{sub 2} luminescence detection. - Highlights: • Both spectral and spatial resolved {sup 1}O{sub 2} luminescence measurements were performed. • Effect of oxygen concentration on {sup 1}O{sub 2} generation was quantitatively evaluated. • Low oxygen concentration could affect {sup 1}O{sub 2} luminescence detection.

  2. Exposure of vitamins to UVB and UVA radiation generates singlet oxygen.

    Science.gov (United States)

    Knak, Alena; Regensburger, Johannes; Maisch, Tim; Bäumler, Wolfgang

    2014-05-01

    Deleterious effects of UV radiation in tissue are usually attributed to different mechanisms. Absorption of UVB radiation in cell constituents like DNA causes photochemical reactions. Absorption of UVA radiation in endogenous photosensitizers like vitamins generates singlet oxygen via photosensitized reactions. We investigated two further mechanisms that might be involved in UV mediated cell tissue damage. Firstly, UVB radiation and vitamins also generate singlet oxygen. Secondly, UVB radiation may change the chemical structure of vitamins that may change the role of such endogenous photosensitizers in UVA mediated mechanisms. Vitamins were irradiated in solution using monochromatic UVB (308 nm) or UVA (330, 355, or 370 nm) radiation. Singlet oxygen was directly detected and quantified by its luminescence at 1270 nm. All investigated molecules generated singlet oxygen with a quantum yield ranging from 0.007 (vitamin D3) to 0.64 (nicotinamide) independent of the excitation wavelength. Moreover, pre-irradiation of vitamins with UVB changed their absorption in the UVB and UVA spectral range. Subsequently, molecules such as vitamin E and vitamin K1, which normally exhibit no singlet oxygen generation in the UVA, now produce singlet oxygen when exposed to UVA at 355 nm. This interplay of different UV sources is inevitable when applying serial or parallel irradiation with UVA and UVB in experiments in vitro. These results should be of particular importance for parallel irradiation with UVA and UVB in vivo, e.g. when exposing the skin to solar radiation.

  3. A Comparison of Singlet Oxygen Explicit Dosimetry (SOED and Singlet Oxygen Luminescence Dosimetry (SOLD for Photofrin-Mediated Photodynamic Therapy

    Directory of Open Access Journals (Sweden)

    Michele M. Kim

    2016-12-01

    Full Text Available Accurate photodynamic therapy (PDT dosimetry is critical for the use of PDT in the treatment of malignant and nonmalignant localized diseases. A singlet oxygen explicit dosimetry (SOED model has been developed for in vivo purposes. It involves the measurement of the key components in PDT—light fluence (rate, photosensitizer concentration, and ground-state oxygen concentration ([3O2]—to calculate the amount of reacted singlet oxygen ([1O2]rx, the main cytotoxic component in type II PDT. Experiments were performed in phantoms with the photosensitizer Photofrin and in solution using phosphorescence-based singlet oxygen luminescence dosimetry (SOLD to validate the SOED model. Oxygen concentration and photosensitizer photobleaching versus time were measured during PDT, along with direct SOLD measurements of singlet oxygen and triplet state lifetime (τΔ and τt, for various photosensitizer concentrations to determine necessary photophysical parameters. SOLD-determined cumulative [1O2]rx was compared to SOED-calculated [1O2]rx for various photosensitizer concentrations to show a clear correlation between the two methods. This illustrates that explicit dosimetry can be used when phosphorescence-based dosimetry is not feasible. Using SOED modeling, we have also shown evidence that SOLD-measured [1O2]rx using a 523 nm pulsed laser can be used to correlate to singlet oxygen generated by a 630 nm laser during a clinical malignant pleural mesothelioma (MPM PDT protocol by using a conversion formula.

  4. Singlet Oxygen Generation Mediated By Silicon Nanocrystal Assemblies

    Science.gov (United States)

    2011-01-01

    efficient red-orange emission under illumination by ultraviolet light appeared. Increase of the etching time results in significant increase of the...in the singlet oxygen-mediated oxidation of organic compounds K. Loponov, B. Goller, A. Moskalenko, D. Kovalev, A. Lapkin Journal of Photochemistry

  5. Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

    Directory of Open Access Journals (Sweden)

    Javier Morales

    Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

  6. Singlet oxygen reactions with flavonoids. A theoretical-experimental study.

    Science.gov (United States)

    Morales, Javier; Günther, Germán; Zanocco, Antonio L; Lemp, Else

    2012-01-01

    Detection of singlet oxygen emission, λ(max) = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T), and the reactive reaction rate constant, k(r), for the reaction between singlet oxygen and several flavonoids. Values of k(T) determined in deuterated water, ranging from 2.4×10(7) M(-1) s(-1) to 13.4×10(7) M(-1) s(-1), for rutin and morin, respectively, and the values measured for k(r), ranging from 2.8×10(5) M(-1) s(-1) to 65.7×10(5) M(-1) s(-1) for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.

  7. Label-free electrochemical detection of singlet oxygen protein damage

    Czech Academy of Sciences Publication Activity Database

    Vargová, Veronika; Gimenez, R.E.; Černocká, Hana; Trujillo, D.C.; Tulli, F.; Zanini, V.I.P.; Paleček, Emil; Borsarelli, C.D.; Ostatná, Veronika

    2016-01-01

    Roč. 187, JAN 2016 (2016), s. 662-669 ISSN 0013-4686 R&D Projects: GA ČR GA13-00956S Institutional support: RVO:68081707 Keywords : singlet oxygen protein damage * surface-attached protein stability * mercury and carbon electrodes Subject RIV: BO - Biophysics Impact factor: 4.798, year: 2016

  8. Reversible Photochemical Control of Singlet Oxygen Generation Using Diarylethene Photochromic Switches

    NARCIS (Netherlands)

    Hou, Lili; Zhang, Xiaoyan; Pijper, Thomas C.; Browne, Wesley R.; Feringa, Bernard

    2014-01-01

    Reversible noninvasive control over the generation of singlet oxygen is demonstrated in a bicomponent system comprising a diarylethene photochromic switch and a porphyrin photosensitizer by selective irradiation at distinct wavelengths. The efficient generation of singlet oxygen by the

  9. Photorelease of triplet and singlet oxygen from dioxygen complexes

    Czech Academy of Sciences Publication Activity Database

    Wagnerová, Dana Marie; Lang, Kamil

    2011-01-01

    Roč. 255, 23-24 (2011), s. 2904-2911 ISSN 0010-8545 R&D Projects: GA ČR GAP207/10/1447; GA ČR GAP208/10/1678 Institutional research plan: CEZ:AV0Z40320502 Keywords : singlet oxygen * triplet oxygen * photochemical elimination * photorelease * Dioxygen complex Subject RIV: CA - Inorganic Chemistry Impact factor: 12.110, year: 2011

  10. Spray generator of singlet oxygen for a chemical oxygen-iodine laser

    Czech Academy of Sciences Publication Activity Database

    Jirásek, Vít; Hrubý, Jan; Špalek, Otomar; Čenský, Miroslav; Kodymová, Jarmila

    2010-01-01

    Roč. 100, č. 4 (2010), s. 779-791 ISSN 0946-2171 Grant - others:European Office of Aerospace R&D(US) FA8655-09-1-3091 Institutional research plan: CEZ:AV0Z10100523; CEZ:AV0Z20760514 Keywords : spray generator of singlet oxygen * singlet oxygen * chemical oxygen-iodine laser Subject RIV: BH - Optics, Masers, Lasers Impact factor: 2.239, year: 2010

  11. Single Cell Responses to Spatially Controlled Photosensitized Production of Extracellular Singlet Oxygen

    DEFF Research Database (Denmark)

    Pedersen, Brian Wett; Sinks, Louise E.; Breitenbach, Thomas

    2011-01-01

    The response of individual HeLa cells to extracellularly produced singlet oxygen was examined. The spatial domain of singlet oxygen production was controlled using the combination of a membrane-impermeable Pd porphyrin-dendrimer, which served as a photosensitizer, and a focused laser, which served...... to localize the sensitized production of singlet oxygen. Cells in close proximity to the domain of singlet oxygen production showed morphological changes commonly associated with necrotic cell death. The elapsed post-irradiation “waiting period” before necrosis became apparent depended on (a) the distance...... between the cell membrane and the domain irradiated, (b) the incident laser fluence and, as such, the initial concentration of singlet oxygen produced, and (c) the lifetime of singlet oxygen. The data imply that singlet oxygen plays a key role in this process of light-induced cell death. The approach...

  12. Oxidação de proteínas por oxigênio singlete: mecanismos de dano, estratégias para detecção e implicações biológicas Singlet oxygen-mediated protein oxidation: damage mechanisms, detection techniques and biological implication

    Directory of Open Access Journals (Sweden)

    Graziella E. Ronsein

    2006-06-01

    Full Text Available Proteins are potential targets for singlet molecular oxygen (¹O2 oxidation. Damages occur only at tryptophan, tyrosine, histidine, methionine, and cysteine residues at physiological pH, generating oxidized compounds such as hydroperoxides. Therefore, it is important to understand the mechanisms by which ¹O2, hydroperoxides and other oxidized products can trigger further damage. The improvement and development of new tools, such as clean sources of ¹O2 and isotopic labeling approaches in association with HPLC/mass spectrometry detection will allow one to elucidate mechanistic features involving ¹O2-mediated protein oxidation.

  13. Graphene oxide functionalized with methylene blue and its performance in singlet oxygen generation

    Energy Technology Data Exchange (ETDEWEB)

    Wojtoniszak, M., E-mail: mwojtoniszak@zut.edu.pl [West Pomeranian University of Technology in Szczecin, Institute of Chemical and Environment Engineering, Pulaskiego 10, 70-322 Szczecin (Poland); Rogińska, D.; Machaliński, B. [Pomeranian Medical University, Department of General Pathology, Powstańców Wlkp. 72, 70-111 Szczecin (Poland); Drozdzik, M. [Pomeranian Medical University, Department of Pharmacology, Powstańców Wlkp. 72, 70-111 Szczecin (Poland); Mijowska, E. [West Pomeranian University of Technology in Szczecin, Institute of Chemical and Environment Engineering, Pulaskiego 10, 70-322 Szczecin (Poland)

    2013-07-15

    Graphical abstract: - Highlights: • Adsorption of methylene blue (MB) on graphene oxide (GO). • Characterization of graphene oxide–methylene blue nanocomposite (MB–GO). • Examination of MB–GO efficiency in singlet oxygen generation (SOG). • MB–GO performs higher SOG efficiency than pristine MB. - Abstract: Due to unique electronic, mechanical, optical and structural properties, graphene has shown promising applications in many fields, including biomedicine. One of them is noninvasive anticancer therapy – photodynamic therapy (PDT), where singlet oxygen (SO), generated under the irradiation of light with appropriate wavelengths, kills cancer cells. In this study, authors report graphene oxide (GO) noncovalent functionalization with methylene blue (MB). MB molecules underwent adsorption on the surface of GO. Detailed characterization of the obtained material was carried out with UV–vis spectroscopy, Raman spectroscopy, FT-IR spectroscopy, and confocal laser scanning microscopy. Furthermore, its performance in singlet oxygen generation (SOG) under irradiation of laser with excitation wavelengths of 785 nm was investigated. Interestingly, GO functionalized with MB (MB–GO) showed enhanced efficiency in singlet oxygen generation compared to pristine MB. The efficiency in SOG was detected by photobleaching of 9,10-anthracenediyl-bis(methylene)dimalonic acid (ABMDMA). These results indicate the material is promising in PDT anticancer therapy and further in vitro and in vivo studies are required.

  14. New strategies to produce and detect singlet oxygen in a cell

    DEFF Research Database (Denmark)

    Gollmer, Anita

    2012-01-01

    product of the reaction between SOSG and singlet oxygen is itself an efficient singlet oxygen sensitizer and, second, that despite published claims to the contrary, SOSG can, in fact, be incorporated into living mammalian cells. Further, a new fluorescent probe for singlet oxygen called “Aarhus Green...... to achieve a reproducible assessment of cell response to a controlled dose of singlet oxygen produced in a spatially-localized two-photon sensitized experiment. Different assays were used to visualize cell response. In this dissertation, various aspects of fluorescence imaging and two-photon excitation......Singlet oxygen, the first excited electronic state of molecular oxygen, plays a major role in oxygen-dependent photo-induced cell death. In such systems, singlet oxygen is generally produced in a photosensitized process wherein light is absorbed by a molecule (the so-called sensitizer) which...

  15. Singlet oxygen-mediated formation of protein peroxides within cells

    International Nuclear Information System (INIS)

    Wright, A.; Policarpio, V.

    2003-01-01

    Full text: Singlet oxygen is generated by a number of cellular, enzymatic and chemical reactions as well as by exposure to UV, or visible light in the presence of a sensitizer; as a consequence this oxidant has been proposed as a damaging agent in a number of pathologies including photo-aging and skin cancer. Proteins are major targets for singlet oxygen as a result of their abundance and high rate constants for reaction. In this study it is shown that illumination of viable, sensitizer-loaded, THP-1 (human monocyte-like) cells with visible light gives rise to intra-cellular protein-derived peroxides. The peroxide yield increases with illumination time, requires the presence of the sensitizer, is enhanced in D 2 O, and decreased by azide; these data are consistent with the mediation of singlet oxygen. The concentration of peroxides detected, which is not affected by glucose or ascorbate loading of the cells, corresponds to ca. 1.5 nmoles peroxide per 10 6 cells using rose bengal as sensitizer, or 10 nmoles per mg cell protein and account for up to ca. 15% of the O 2 consumed by the cells. Similar peroxides have been detected on isolated cellular proteins exposed to light in the presence of rose bengal and oxygen. After cessation of illumination, the cellular protein peroxide levels decreases with t 1/2 ca. 4 hrs at 37 deg C, and this is associated with increased cell lysis. Decomposition of protein peroxides formed within cells, or on isolated cellular proteins, by metal ions, gives rise to radicals as detected by EPR spin trapping. These protein peroxides, and radicals derived from them, can inactivate key cellular enzymes (including caspases, GAPDH and glutathione reductase) and induce DNA base oxidation, strand breaks and DNA-protein cross-links. These studies demonstrate that exposure of intact cells to visible light in the presence of a sensitizer gives rise to novel long-lived, but reactive, intra-cellular protein peroxides via singlet oxygen

  16. Singlet Oxygen Sensor Green: Photochemical Behavior in Solution and in a Mammalian Cell

    DEFF Research Database (Denmark)

    Gollmer, Anita; Arnbjerg, Jacob; Blaikie, Frances Helen

    2011-01-01

    The development of efficient and selective luminescent probes for reactive oxygen species, particularly for singlet molecular oxygen, is currently of great importance. In this study, the photochemical behavior of Singlet Oxygen Sensor Green® (SOSG), a commercially available fluorescent probe...... of the reaction between SOSG and singlet oxygen is, itself, an efficient singlet oxygen photosensitizer. Second, SOSG appears to efficiently bind to proteins which, in turn, can influence uptake by a cell as well as behavior in the cell. As such, incorrect use of SOSG can yield misleading data on yields...

  17. Ultraweak bioluminescence dynamics and singlet oxygen correlations during injury repair in sweet potato

    Science.gov (United States)

    Hossu, Marius; Ma, Lun; Chen, Wei

    2011-03-01

    Ultraweak bioluminescence at the level of hundreds of photons per second per square centimeter after cutting injury of sweet potato was investigated. A small emission peak immediate after cutting and a later and higher peak were observed. Selective singlet oxygen inhibitors and sensors have been use to study the contribution of singlet oxygen during the curing process, demonstrating increased presence of singlet oxygen during and after the late bioemission peak. It was confirmed that singlet oxygen has direct contribution to ultraweak bioluminescence but also induces the formation of other exited luminescent species that are responsible for the recorded bioluminescence.

  18. Singlet Oxygen Detection Using Red Wine Extracts as Photosensitizers.

    Science.gov (United States)

    Lagunes, Irene; Vázquez-Ortega, Fernanda; Trigos, Ángel

    2017-09-01

    Moderate consumption of red wine provides beneficial effects to health. This is attributed to polyphenol compounds present in wine such as resveratrol, quercetin, gallic acid, rutin, and vanillic acid. The amount of these antioxidants is variable; nevertheless, the main beneficial effects of red wine are attributed to resveratrol. However, it has been found that resveratrol and quercetin are able to photosensitize singlet oxygen generation and conversely, gallic acid acts as quencher. Therefore, and since resveratrol and quercetin are some of the most important antioxidants reported in red wines, the aim of this research was to evaluate the photosensitizing ability of 12 red wine extracts through photo-oxidation of ergosterol. The presence of 1 O 2 was detected by ergosterol conversion into peroxide of ergosterol through 1 H NMR analysis. Our results showed that 10 wine extracts were able to act as photosensitizers in the generation of singlet oxygen. The presence of 1 O 2 can damage other compounds of red wine and cause possible organoleptic alterations. Finally, although the reaction conditions employed in this research do not resemble the inherent conditions in wine making processing or storing, or even during its consumption, this knowledge could be useful to prevent possible pro-oxidant effects and avoid detrimental effects in red wines. © 2017 Institute of Food Technologists®.

  19. Non-self-sustained electric discharge in oxygen gas mixtures: singlet delta oxygen production

    CERN Document Server

    Ionin, A A; Kotkov, A A; Kochetov, I V; Napartovich, A P; Seleznev, L V; Sinitsyn, D V; Hager, G D

    2003-01-01

    The possibility of obtaining a high specific input energy in an electron-beam sustained discharge ignited in oxygen gas mixtures O sub 2 : Ar : CO (or H sub 2) at the total gas pressures of 10-100 Torr was experimentally demonstrated. The specific input energy per molecular component exceeded approx 6 kJ l sup - sup 1 atm sup - sup 1 (150 kJ mol sup - sup 1) as a small amount of carbon monoxide was added into a gas mixture of oxygen and argon. It was theoretically demonstrated that one might expect to obtain a singlet delta oxygen yield of 25% exceeding its threshold value needed for an oxygen-iodine laser operation at room temperature, when maintaining a non-self-sustained discharge in oxygen gas mixtures with molecular additives CO, H sub 2 or D sub 2. The efficiency of singlet delta oxygen production can be as high as 40%.

  20. Kinetics of oxygen species in an electrically driven singlet oxygen generator

    Science.gov (United States)

    Azyazov, V. N.; Torbin, A. P.; Pershin, A. A.; Mikheyev, P. A.; Heaven, M. C.

    2015-12-01

    The kinetics of oxygen species in the gaseous medium of a discharge singlet oxygen generator has been revisited. Vibrationally excited ozone O3(υ) formed in O + O2 recombination is thought to be a significant agent in the deactivation of singlet oxygen O2(a1Δ), oxygen atom removal and ozone formation. It is shown that the process O3(υ ⩾ 2) + O2(a1Δ) → 2O2 + O is the main O2(a1Δ) deactivation channel in the post-discharge zone. If no measures are taken to decrease the oxygen atom concentration, the contribution of this process to the overall O2(a1Δ) removal is significant, even in the discharge zone. A simplified model for the kinetics of vibrationally excited ozone is proposed. Calculations based on this model yield results that are in good agreement with the experimental data.

  1. In-vitro singlet oxygen threshold dose at PDT with Radachlorin photosensitizer

    Science.gov (United States)

    Klimenko, V. V.; Shmakov, S. V.; Kaydanov, N. E.; Knyazev, N. A.; Kazakov, N. V.; Rusanov, A. A.; Bogdanov, A. A.; Dubina, M. V.

    2017-07-01

    In this present study we investigate the Radachlorin photosensitizer accumulation in K562 cells and Hela cells and determined the cell viability after PDT. Using the macroscopic singlet oxygen modeling and cellular photosensitizer concentration the singlet oxygen threshold doses for K562 cells and Hela cells were calculated.

  2. Singlet oxygen-based electrosensing by molecular photosensitizers

    Science.gov (United States)

    Trashin, Stanislav; Rahemi, Vanoushe; Ramji, Karpagavalli; Neven, Liselotte; Gorun, Sergiu M.; de Wael, Karolien

    2017-07-01

    Enzyme-based electrochemical biosensors are an inspiration for the development of (bio)analytical techniques. However, the instability and reproducibility of the reactivity of enzymes, combined with the need for chemical reagents for sensing remain challenges for the construction of useful devices. Here we present a sensing strategy inspired by the advantages of enzymes and photoelectrochemical sensing, namely the integration of aerobic photocatalysis and electrochemical analysis. The photosensitizer, a bioinspired perfluorinated Zn phthalocyanine, generates singlet-oxygen from air under visible light illumination and oxidizes analytes, yielding electrochemically-detectable products while resisting the oxidizing species it produces. Compared with enzymatic detection methods, the proposed strategy uses air instead of internally added reactive reagents, features intrinsic baseline correction via on/off light switching and shows C-F bonds-type enhanced stability. It also affords selectivity imparted by the catalytic process and nano-level detection, such as 20 nM amoxicillin in μl sample volumes.

  3. Singlet oxygen in the low-temperature plasma of an electron-beam-sustained discharge

    International Nuclear Information System (INIS)

    Vagin, N. P.; Ionin, A. A.; Klimachev, Yu. M.; Kotkov, A. A.; Kochetov, I. V.; Napartovich, A. P.; Podmar'kov, Yu. P.; Rulev, O. A.; Seleznev, L. V.; Sinitsyn, D. V.; Frolov, M. P.; Yuryshev, N. N.

    2006-01-01

    Results are presented from experimental and theoretical studies of the production of singlet delta oxygen in a pulsed electron-beam-sustained discharge ignited in a large (∼18-1) volume at a total gas mixture pressure of up to 210 Torr. The measured yield of singlet oxygen reaches 10.5%. It is found that varying the reduced electric field from ∼2 to ∼11 kV/(cm atm) slightly affects singlet oxygen production. It is shown experimentally that an increase in the gas mixture pressure or the specific input energy reduces the duration of singlet oxygen luminescence. The calculated time evolution of the singlet oxygen concentration is compared with experimental results

  4. Centrifugal spray generator of singlet oxygen for a chemical oxygen-iodine laser

    Czech Academy of Sciences Publication Activity Database

    Špalek, Otomar; Hrubý, Jan; Čenský, Miroslav; Jirásek, Vít; Kodymová, Jarmila

    2010-01-01

    Roč. 100, č. 4 (2010), s. 793-802 ISSN 0946-2171 Grant - others:European Office of Aerospace R&D(US) FA8655-09-1-3091 Institutional research plan: CEZ:AV0Z10100523; CEZ:AV0Z20760514 Keywords : centrifugal generator of singlet oxygen * chemical oxygen-iodine laser Subject RIV: BH - Optics, Masers, Lasers Impact factor: 2.239, year: 2010

  5. Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production

    International Nuclear Information System (INIS)

    Yoshii, Hiroshi; Yoshii, Yukie; Asai, Tatsuya; Furukawa, Takako; Takaichi, Shinichi; Fujibayashi, Yasuhisa

    2012-01-01

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

  6. Singlet oxygen mediated DNA degradation by copper nanoparticles: potential towards cytotoxic effect on cancer cells

    OpenAIRE

    Sengupta Tapas K; Mandal Swadhin K; Santra Subhankar; Jose Gregor P

    2011-01-01

    Abstract The DNA degradation potential and anti-cancer activities of copper nanoparticles of 4-5 nm size are reported. A dose dependent degradation of isolated DNA molecules by copper nanoparticles through generation of singlet oxygen was observed. Singlet oxygen scavengers such as sodium azide and Tris [hydroxyl methyl] amino methane were able to prevent the DNA degradation action of copper nanoparticles confirming the involvement of activated oxygen species in the degradation process. Addit...

  7. Activation of transcription factor AP-2 mediates UVA radiation- and singlet oxygen-induced expression of the human intercellular adhesion molecule 1 gene

    International Nuclear Information System (INIS)

    Grether-Beck, S.; Olaizola-Horn, S.; Schmitt, H.; Grewe, M.

    1996-01-01

    UVA radiation is the major component of the UV solar spectrum that reaches the earth, and the therapeutic application of UVA radiation is increasing in medicine. Analysis of the cellular effects of UVA radiation has revealed that exposure of human cells to UVA radiation at physiological doses leads to increased gene expression and that this UVA response is primarily mediated through the generation of singlet oxygen. In this study, the mechanisms by which UVA radiation induces transcriptional activation of the human intercellular adhesion molecule 1 (ICAM-1) were examined. UVA radiation was capable of inducing activation of the human ICAM-1 promoter and increasing OCAM-1 mRNA and protein expression. These UVA radiation effects were inhibited by singlet oxygen quenchers, augmented by enhancement of singlet oxygen life-time, and mimicked in unirradiated cells by a singlet oxygen-generating system. UVA radiation as well as singlet oxygen-induced ICAM-1 promoter activation required activation of the transcription factor AP-2. Accordingly, both stimuli activated AP-2, and deletion of the putative AP-2-binding site abrogated ICAM-1 promoter activation in this system. This study identified the AP-2 site as the UVA radiation- and singlet oxygen-responsive element of the human ICAM-1 gene. The capacity of UVA radiation and/or singlet oxygen to induce human gene expression through activation of AP-2 indicates a previously unrecognized role of this transcription factor in the mammalian stress response. 38 refs., 3 figs., 3 tabs

  8. Pallidol, a resveratrol dimer from red wine, is a selective singlet oxygen quencher

    International Nuclear Information System (INIS)

    He Shan; Jiang Liyan; Wu Bin; Pan Yuanjiang; Sun Cuirong

    2009-01-01

    Pallidol is a naturally occurring resveratrol dimer from red wine with antioxidant and antifungal activities. In this report, with the use of the EPR spin-trapping technique, the scavenging and quenching effects of pallidol on reactive oxygen species (ROS) were investigated. The results demonstrated that pallidol showed strong quenching effects on singlet oxygen at very low concentrations, but it was ineffective to scavenge hydroxyl radicals or superoxide anions. Further kinetic study revealed that the reaction of pallidol with singlet oxygen had an extremely high rate constant (k a = 1.71 x 10 10 ). Therefore, pallidol is a potent and selective singlet oxygen quencher in aqueous systems. It may be used in singlet oxygen-mediated diseases as a pharmacological agent, which may contribute to the health beneficial effects of red wine.

  9. Towards photodynamic therapy with ionizing radiation: nanoparticle-mediated singlet oxygen generation (Conference Presentation)

    Science.gov (United States)

    Clement, Sandhya; Deng, Wei; Camilleri, Elizabeth; Wilson, Brian; Goldys, Ewa

    2016-03-01

    Photodynamic therapy (PDT) is a clinically approved method for the treatment of cancer by using singlet oxygen, a highly reactive oxygen generated from a photosensitizer drug upon photoactivation. Limited light penetration depth into to the tissue means that PDT is unsuitable for deep tissue cancer treatments. This can be overcome by using X-ray /gamma rays activated nanoparticles able to trigger the photosensitizer drug and generate singlet oxygen. Additionally, inorganic nanoparticles interact more strongly with X and/or gamma rays than the tissue, allowing to concentrate the effects of radiation near nanoparticle surface and they can also be molecularly targeted to cancer cells. In this work we synthesized and characterized CeF3 nanoparticles, a well-known scintillator material. The nanoparticles were conjugated with Verteporfin, a photosensitizer drug by electrostatic interaction. We assessed the performance of CeF3 and the conjugates to generate singlet oxygen exposed to X-ray radiation. The X-ray singlet oxygen quantum yield of the nanoparticle-photosensitizer system was accurately quantified for the first time. This provided realistic estimates of the singlet oxygen dose taking into consideration the dose partition of the radiation between CeF3 and the tissue. Furthermore, we investigated gold nanoparticle-photosensitizer systems. We confirmed that pure gold nanoparticles itself generate singlet oxygen which is attributed to plasmonic effects. We found enhanced singlet oxygen generation from gold-Rose Bengal conjugates and gold nanorod-verteporfin conjugates. These singlet-oxygen-generating nanomaterials add a new dimension to radiation-assisted PDT.

  10. Kinetics of oxygen species in an electrically driven singlet oxygen generator

    International Nuclear Information System (INIS)

    Azyazov, V.N.; Torbin, A.P.; Pershin, A.A.; Mikheyev, P.A.; Heaven, M.C.

    2015-01-01

    Highlights: • Vibrational excitation of O 3 increases the rate constant for O 3 + O 2 (a) → 2O 2 (X) + O. • Vibrationally excited O 3 is produced by the O + O 2 (X) + M → O 3 + M reaction. • Ozone concentrations are impacted by the reactions of vibrationally excited O 3 . • Relevant to ozone concentrations in oxygen discharges and the upper atmosphere. - Abstract: The kinetics of oxygen species in the gaseous medium of a discharge singlet oxygen generator has been revisited. Vibrationally excited ozone O 3 (υ) formed in O + O 2 recombination is thought to be a significant agent in the deactivation of singlet oxygen O 2 (a 1 Δ), oxygen atom removal and ozone formation. It is shown that the process O 3 (υ ⩾ 2) + O 2 (a 1 Δ) → 2O 2 + O is the main O 2 (a 1 Δ) deactivation channel in the post-discharge zone. If no measures are taken to decrease the oxygen atom concentration, the contribution of this process to the overall O 2 (a 1 Δ) removal is significant, even in the discharge zone. A simplified model for the kinetics of vibrationally excited ozone is proposed. Calculations based on this model yield results that are in good agreement with the experimental data.

  11. Singlet Delta Oxygen: A Quantitative Analysis Using Off-Axis Integrated-Cavity-Output-Spectroscopy (ICOS)

    National Research Council Canada - National Science Library

    Gallagher, Jeffrey E

    2006-01-01

    .... The method is based on off-axis integrated-cavity-output spectroscopy (ICOS). The primary goal for this research effort is to utilize the ICOS technique and demonstrate its ability to provide quantitative data of singlet delta oxygen...

  12. Synthesis of Pyridylanthracenes and Their Reversible Reaction with Singlet Oxygen to Endoperoxides.

    Science.gov (United States)

    Fudickar, Werner; Linker, Torsten

    2017-09-01

    The ortho, meta, and para isomers of 9,10-dipyridylanthracene 1 have been synthesized and converted into their endoperoxides 1-O 2 upon oxidation with singlet oxygen. The kinetics of this reaction can be controlled by the substitution pattern and the solvent: in highly polar solvents, the meta isomer is the most reactive, whereas the ortho isomer is oxidized fastest in nonpolar solvents. Heating of the endoperoxides affords the parent anthracenes by release of singlet oxygen.

  13. Singlet Oxygen-Mediated Oxidation during UVA Radiation Alters the Dynamic of Genomic DNA Replication.

    Directory of Open Access Journals (Sweden)

    Dany Graindorge

    Full Text Available UVA radiation (320-400 nm is a major environmental agent that can exert its deleterious action on living organisms through absorption of the UVA photons by endogenous or exogenous photosensitizers. This leads to the production of reactive oxygen species (ROS, such as singlet oxygen (1O2 and hydrogen peroxide (H2O2, which in turn can modify reversibly or irreversibly biomolecules, such as lipids, proteins and nucleic acids. We have previously reported that UVA-induced ROS strongly inhibit DNA replication in a dose-dependent manner, but independently of the cell cycle checkpoints activation. Here, we report that the production of 1O2 by UVA radiation leads to a transient inhibition of replication fork velocity, a transient decrease in the dNTP pool, a quickly reversible GSH-dependent oxidation of the RRM1 subunit of ribonucleotide reductase and sustained inhibition of origin firing. The time of recovery post irradiation for each of these events can last from few minutes (reduction of oxidized RRM1 to several hours (replication fork velocity and origin firing. The quenching of 1O2 by sodium azide prevents the delay of DNA replication, the decrease in the dNTP pool and the oxidation of RRM1, while inhibition of Chk1 does not prevent the inhibition of origin firing. Although the molecular mechanism remains elusive, our data demonstrate that the dynamic of replication is altered by UVA photosensitization of vitamins via the production of singlet oxygen.

  14. Photodynamic biofilm inactivation by SAPYR--an exclusive singlet oxygen photosensitizer.

    Science.gov (United States)

    Cieplik, Fabian; Späth, Andreas; Regensburger, Johannes; Gollmer, Anita; Tabenski, Laura; Hiller, Karl-Anton; Bäumler, Wolfgang; Maisch, Tim; Schmalz, Gottfried

    2013-12-01

    Prevention and control of biofilm-growing microorganisms are serious problems in public health due to increasing resistances of some pathogens against antimicrobial drugs and the potential of these microorganisms to cause severe infections in patients. Therefore, alternative approaches that are capable of killing pathogens are needed to supplement standard treatment modalities. One alternative is the photodynamic inactivation of bacteria (PIB). The lethal effect of PIB is based on the principle that visible light activates a photosensitizer, leading to the formation of reactive oxygen species, e.g., singlet oxygen, which induces phototoxicity immediately during illumination. SAPYR is a new generation of photosensitizers. Based on a 7-perinaphthenone structure, it shows a singlet oxygen quantum yield ΦΔ of 99% and is water soluble and photostable. Moreover, it contains a positive charge for good adherence to cell walls of pathogens. In this study, the PIB properties of SAPYR were investigated against monospecies and polyspecies biofilms formed in vitro by oral key pathogens. SAPYR showed a dual mechanism of action against biofilms: (I) it disrupts the structure of the biofilm even without illumination; (II) when irradiated, it inactivates bacteria in a polymicrobial biofilm after one single treatment with an efficacy of ≥ 99.99%. These results encourage further investigation on the potential of PIB using SAPYR for the treatment of localized infectious diseases. Copyright © 2013 The Authors. Published by Elsevier Inc. All rights reserved.

  15. Interaction of plasmalogens and their diacyl analogs with singlet oxygen in selected model systems

    Science.gov (United States)

    Broniec, Agnieszka; Klosinski, Radoslaw; Pawlak, Anna; Wrona-Krol, Marta; Thompson, David; Sarna, Tadeusz

    2011-01-01

    Plasmalogens (Plg) are phospholipids containing vinyl ether linkage at the sn-1 position of the glycerophospholipid backbone. In spite of being quite abundant in humans, the biological role of plasmalogens remains speculative. It has been postulated that plasmalogens are physiological antioxidants with the vinyl ether functionality serving as sacrificial trap for free radicals and singlet oxygen. However, no quantitative data on the efficiency of plasmalogens to scavenge these reactive species are available. In this study, rate constants of quenching of singlet oxygen, generated by photosensitized energy transfer, by several plasmalogens and, for comparison, by their diacyl analogs, were determined by time-resolved detection of phosphorescence at 1270 nm. Relative rates of the interaction of singlet oxygen, with plasmalogens and other lipids in solution and liposomal membranes were measured by electron paramagnetic resonance oximetry and product analysis, employing HPLC-EC detection of cholesterol hydroperoxides and iodometric assay of lipid hydroperoxides. Results show that singlet oxygen interacts with plasmalogens significantly faster than with the other lipids, with he corresponding rate constants being by one-two orders of magnitude greater. The quenching of singlet oxygen by plasmalogens is mostly reactive in nature and results from its preferential interaction with the vinyl ether bond. The data suggest that plasmalogens could protect unsaturated membrane lipids against oxidation induced by singlet oxygen, providing that the oxidation products are not excessively cytotoxic. PMID:21236336

  16. Targeted oxidation of Torpedo californica acetylcholinesterase by singlet oxygen.

    Science.gov (United States)

    Weiner, Lev; Roth, Esther; Silman, Israel

    2011-01-01

    The photosensitizer, methylene blue (MB), is a strong reversible inhibitor of Torpedo californica acetylcholinesterase (AChE) in the dark. Under illumination it causes irreversible inactivation. Loss of fluorescence of the singlet oxygen ((1)O(2)) trap, 9,10-dimethylanthracene, was retarded in the presence of AChE, and the rate of photo-inactivation was increased in the presence of D(2)O, indicating that inactivation was due to (1)O(2) generated by the photosensitizer. CD revealed slightly reduced far-UV ellipticity, and slightly enhanced binding of an amphiphilic probe, indicating limited unfolding of the photo-oxidized AChE. However, both near-UV ellipticity and intrinsic fluorescence were markedly reduced, suggesting photo-oxidative damage to tryptophans, (Trp) supported by appearance of novel emission peaks ascribed to N'-formylkynurenine and/or kynurenine. Like other partially unfolded forms, the photo-oxidized AChE was sensitive to proteolysis. Photosensitized inactivation produced exclusively chemically cross-linked dimers, whereas irradiation of a partially unfolded state generated higher-order oligomers. The active-site gorge of AChE contains Trp in inhibitor-binding sites that might be targets for photo-oxidation. Indeed, reversible inhibitors retard photo-inactivation, and photo-inactivation destroys their binding sites. An excess of AChE protects paraoxonase from photo-inactivation by sequestering the photosensitizer. Affinity photo-oxidation of AChE by MB thus provides a valuable model for studying site-specific photo-inactivation of enzymes in both fundamental and clinical contexts. © 2010 The Authors. Photochemistry and Photobiology © 2010 The American Society of Photobiology.

  17. Singlet molecular oxygen on natural snow and ice

    Science.gov (United States)

    Bower, J. P.; Anastasio, C.

    2010-12-01

    Singlet molecular oxygen (1O2*) is a reactive intermediate formed when a chromophore absorbs light and subsequently transfers energy to dissolved oxygen. As an oxidant, 1O2* reacts rapidly with a number of electron-rich environmental pollutants. In our work, we show enhanced kinetics for 1O2* in frozen solutions, where its rate of formation (Rf) and steady state concentration ([1O2*]) can be many orders of magnitude higher than found in the same unfrozen solution. Our goal here is to identify the contribution of 1O2* to the decay of pollutants on snow and ice. We conducted experiments in laboratory solutions made to simulate the concentrations and characteristics of natural snow, as well as in natural snow collected in the Sierra Nevada mountains of California and at Summit, Greenland. Natural snow contains a mixture of inorganic salts and organic species that can function as sources and/or sinks for oxidants, as well as contribute colligative control on the volume of quasi-liquid layers that occur at the surface and grain boundaries of ice. In our experiments, solutions typically contained up to five components: (1) Furfuryl alcohol (FFA), a commonly used probe for 1O2*, (2) Rose Bengal (RB), a 1O2* sensitizer, (3) HOOH, a photochemical precursor for hydroxyl radical (●OH), (4) glycerol to simulate unknown, naturally occurring sinks for ●OH, and (5) sodium sulfate to control the total concentration of solutes. We illuminated samples in a temperature-controlled solar simulator and subsequently measured the loss of FFA using high performance liquid chromatography. To differentiate reactions of 1O2* from other sinks (e.g. ●OH), selective sink species were added to determine the fraction of FFA loss due to direct photolysis, reaction with 1O2*, and reaction with ●OH. We verified reactions of 1O2* with FFA by two methods. First, we utilized the kinetic solvent isotope effect, where an enhancement of FFA loss in a mixture of D2O/water is indicative 1O2* since [1

  18. Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production

    Energy Technology Data Exchange (ETDEWEB)

    Yoshii, Hiroshi, E-mail: yoshii@nirs.go.jp [Research Center for Radiation Emergency Medicine, National Institute of Radiological Science, Chiba 263-8555 (Japan); Faculty of Medical Sciences, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Yoshii, Yukie, E-mail: yukiey@nirs.go.jp [Molecular Imaging Center, National Institute of Radiological Science, Chiba 263-8555 (Japan); Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Asai, Tatsuya [Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Faculty of Engineering, University of Fukui, Fukui 910-8507 (Japan); Furukawa, Takako [Molecular Imaging Center, National Institute of Radiological Science, Chiba 263-8555 (Japan); Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan); Takaichi, Shinichi [Department of Biology, Nippon Medical School, Kawasaki, Kanagawa 211-0063 (Japan); Fujibayashi, Yasuhisa [Molecular Imaging Center, National Institute of Radiological Science, Chiba 263-8555 (Japan); Biomedical Imaging Research Center, University of Fukui, Eiheiji, Fukui 910-1193 (Japan)

    2012-01-06

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

  19. The generation of singlet oxygen (o(2)) by the nitrodiphenyl ether herbicide oxyfluorfen is independent of photosynthesis.

    Science.gov (United States)

    Haworth, P; Hess, F D

    1988-03-01

    The mechanism of action of the p-nitrodiphenyl ether herbicides has remained ambiguous because of conflicting reports in the literature. The diphenyl ether herbicide oxyfluorfen causes a light induced consumption of oxygen which resembles the electron acceptor reaction of paraquat. However, this reaction is not linked to the transport of electrons through photosystem I. This conclusion is based on the observation that the rate of oxygen consumption, in the presence of oxyfluorfen, does not demonstrate a first order rate dependence on light intensity. Using the bleaching of N,N-dimethyl p-nitrosoaniline as a specific detector of singlet oxygen, we demonstrate that oxyfluorfen is a potent generator of this toxic radical. The production of singlet oxygen occurs in the presence of inhibitors of photosynthetic electron transport (oxyfluorfen at 10(-4) molar and paraquat) and also under temperature conditions (3 degrees C) which prevent electron transport. This light induced reaction results in oxygen consumption and is the primary cause of lethality for oxyfluorfen. The production of singlet oxygen occurs rapidly and at low herbicide concentrations (10(-9) molar). The reaction occurs without photosynthetic electron transport but does require an intact thylakoid membrane.

  20. The Generation of Singlet Oxygen (1O2) by the Nitrodiphenyl Ether Herbicide Oxyfluorfen Is Independent of Photosynthesis

    Science.gov (United States)

    Haworth, Phil; Hess, F. Dan

    1988-01-01

    The mechanism of action of the p-nitrodiphenyl ether herbicides has remained ambiguous because of conflicting reports in the literature. The diphenyl ether herbicide oxyfluorfen causes a light induced consumption of oxygen which resembles the electron acceptor reaction of paraquat. However, this reaction is not linked to the transport of electrons through photosystem I. This conclusion is based on the observation that the rate of oxygen consumption, in the presence of oxyfluorfen, does not demonstrate a first order rate dependence on light intensity. Using the bleaching of N,N-dimethyl p-nitrosoaniline as a specific detector of singlet oxygen, we demonstrate that oxyfluorfen is a potent generator of this toxic radical. The production of singlet oxygen occurs in the presence of inhibitors of photosynthetic electron transport (oxyfluorfen at 10−4 molar and paraquat) and also under temperature conditions (3°C) which prevent electron transport. This light induced reaction results in oxygen consumption and is the primary cause of lethality for oxyfluorfen. The production of singlet oxygen occurs rapidly and at low herbicide concentrations (10−9 molar). The reaction occurs without photosynthetic electron transport but does require an intact thylakoid membrane. PMID:16665968

  1. Aerobic photoreactivity of synthetic eumelanins and pheomelanins: generation of singlet oxygen and superoxide anion.

    Science.gov (United States)

    Szewczyk, Grzegorz; Zadlo, Andrzej; Sarna, Michal; Ito, Shosuke; Wakamatsu, Kazumasa; Sarna, Tadeusz

    2016-11-01

    In this work, we examined photoreactivity of synthetic eumelanins, formed by autooxidation of DOPA, or enzymatic oxidation of 5,6-dihydroxyindole-2-carboxylic acid and synthetic pheomelanins obtained by enzymatic oxidation of 5-S-cysteinyldopa or 1:1 mixture of DOPA and cysteine. Electron paramagnetic resonance oximetry and spin trapping were used to measure oxygen consumption and formation of superoxide anion induced by irradiation of melanin with blue light, and time-resolved near-infrared luminescence was employed to determine the photoformation of singlet oxygen between 300 and 600 nm. Both superoxide anion and singlet oxygen were photogenerated by the synthetic melanins albeit with different efficiency. At 450-nm, quantum yield of singlet oxygen was very low (~10 -4 ) but it strongly increased in the UV region. The melanins quenched singlet oxygen efficiently, indicating that photogeneration and quenching of singlet oxygen may play an important role in aerobic photochemistry of melanin pigments and could contribute to their photodegradation and photoaging. © 2016 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  2. Parabanic acid is the singlet oxygen specific oxidation product of uric acid.

    Science.gov (United States)

    Iida, Sayaka; Ohkubo, Yuki; Yamamoto, Yorihiro; Fujisawa, Akio

    2017-11-01

    Uric acid quenches singlet oxygen physically or reacts with it, but the oxidation product has not been previously characterized. The present study determined that the product is parabanic acid, which was confirmed by LC/TOFMS analysis. Parabanic acid was stable at acidic pH (acid at neutral or alkaline pH. The total yields of parabanic acid and oxaluric acid based on consumed uric acid were ~100% in clean singlet oxygen production systems such as UVA irradiation of Rose Bengal and thermal decomposition of 3-(1,4-dihydro-1,4-epidioxy-4-methyl-1-naphthyl)propionic acid. However, the ratio of the amount of uric acid consumed to the total amount of singlet oxygen generated was less than 1/180, indicating that most of the singlet oxygen was physically quenched. The total yields of parabanic acid and oxaluric acid were high in the uric acid oxidation systems with hydrogen peroxide plus hypochlorite or peroxynitrite. They became less than a few percent in peroxyl radical-, hypochlorite- or peroxynitrite-induced oxidation of uric acid. These results suggest that parabanic acid could be an in vivo probe of singlet oxygen formation because of the wide distribution of uric acid in human tissues and extracellular spaces. In fact, sunlight exposure significantly increased human skin levels of parabanic acid.

  3. Singlet-Oxygen Generation From Individual Semiconducting and Metallic Nanostructures During Near-Infrared Laser Trapping

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Bennett E.; Roder, Paden B.; Hanson, Jennifer L.; Manandhar, Sandeep; Devaraj, Arun; Perea, Daniel E.; Kim, Woo-Joong; Kilcoyne, Arthur L.; Pauzauskie, Peter J.

    2015-03-13

    Photodynamic therapy has been used for several decades in the treatment of solid tumors through the generation of reactive singlet-oxygen species (1O2). Recently, nanoscale metallic and semiconducting materials have been reported to act as photosensitizing agents with additional diagnostic and therapeutic functionality. To date there have been no reports of observing the generation of singlet-oxygen at the level of single nanostructures, particularly at near infrared (NIR) wavelengths. Here we demonstrate that NIR laser-tweezers can be used to observe the formation of singlet-oxygen produced from individual silicon and gold nanowires via use of a commercially available reporting dye. The laser trap also induces 2-photon photoexcitation of the dye following a chemical reaction with singlet oxygen. Corresponding 2-photon emission spectra confirms the generation of singlet oxygen from individual silicon nanowires at room temperature (30°C), suggesting a range of applications in understanding the impact of 1O2 on individual cancer cells.

  4. Photosensitized production of singlet oxygen: spatially-resolved optical studies in single cells

    DEFF Research Database (Denmark)

    Breitenbach, Thomas; Kuimova, Marina; Gbur, Peter

    2009-01-01

    be monitored using viability assays. Time- and spatially-resolved optical measurements of both singlet oxygen and its precursor, the excited state sensitizer, reflect the complex and dynamic morphology of the cell. These experiments help elucidate photoinduced, oxygen-dependent events that compromise cell...

  5. Enhanced photocatalytic performance of N-nitrosodimethylamine on TiO2 nanotube based on the role of singlet oxygen.

    Science.gov (United States)

    Guo, Xiaoyan; Li, Qilin; Zhang, Man; Long, Mingce; Kong, Lulu; Zhou, Qixing; Shao, Huaiqi; Hu, Wanli; Wei, Tingting

    2015-02-01

    N-nitrosodimethylamine (NDMA) photocatalytic degradation performance and mechanism were investigated on the TiO2 nanotube prepared from anatase TiO2 nanopowder in terms of the production of reactive oxygen species including hydroxyl radical, singlet oxygen and superoxide radical. Significantly higher NDMA degradation efficiency was obtained on anatase TiO2 nanotube rather than anatase TiO2 nanopowder. The tubular morphology may be responsible for almost 100% NDMA removal on TiO2 nanotube, presumably due to its confinement effect leading to NDMA molecules within the nanotube being attacked by reactive oxygen species such as hydroxyl radical and singlet oxygen, and initiating reaction inside the nanotube. In particular, the ability of the nanotubular structure of TiO2 nanotube to promote a singlet oxygen oxidation pathway contributes much to the enhanced NDMA degradation efficiency and favors the formation of dimethylamine and NO3(-). Such function originating from nanotube morphology could bring new insights for the photocatalytic degradation of organic pollutants. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Singlet Oxygen Generation as a Major Cause for Parasitic Reactions during Cycling of Aprotic Lithium-Oxygen Batteries

    OpenAIRE

    Mahne, Nika; Schafzahl, Bettina; Leypold, Christian; Leypold, Mario; Grumm, Sandra; Leitgeb, Anita; Strohmeier, Gernot A.; Wilkening, Martin; Fontaine, Olivier; Kramer, Denis; Slugovc, Christian; Borisov, Sergey M.; Freunberger, Stefan A.

    2017-01-01

    Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of ...

  7. Molecular Tuning of Phenylene-Vinylene Derivatives for Two-Photon Photosensitized Singlet Oxygen Production

    DEFF Research Database (Denmark)

    Nielsen, Christian B.; Arnbjerg, Jacob; Johnsen, Mette

    2009-01-01

    that can deviate from the norm, a full investigation of the photophysical properties of the system is generally required. For example, it is acknowledged that the introduction of a ketone moiety to the sensitizer chromophore often results in more efficient production of singlet oxygen. However, we show...... here that the introduction of a carbonyl into a given phenylene-vinylene can, rather, have adverse effects on the yield of singlet oxygen produced. Using these molecules, we show that care must also be exercised when using qualitative symmetry-derived arguments to predict the relationship between one...

  8. Inactivation of Neurospora crassa conidia by singlet molecular oxygen generated by a photosensitized reaction

    International Nuclear Information System (INIS)

    Shimizu, M.; Egashira, T.; Takahama, U.

    1979-01-01

    Photodynamic damage of Neurospora crassa conidia was studied in the presence of the photosensitizing dye, toluidine blue O. Conidia which germinated to form colonies decreased in number as irradiation time became longer. The photoinactivation of conidia was suppressed by azide, bovine serum albumin, and histidine, and was stimulated in deuterium oxide. Wild-type conidia were less sensitive to the irradiation that albino conidia. In the wild type, carotenoid-enriched conidia were more resistant against the lethal damage than the conidia which contained small amounts of carotenoids. These results suggest that singlet molecular oxygen causes photodynamic lethal damage to N. crassa conidia and that singlet molecular oxygen is quenched by endogenous carotenoids

  9. Fluorescent proteins as singlet oxygen photosensitizers: mechanistic studies in photodynamic inactivation of bacteria

    Science.gov (United States)

    Ruiz-González, Rubén.; White, John H.; Cortajarena, Aitziber L.; Agut, Montserrat; Nonell, Santi; Flors, Cristina

    2013-02-01

    Antimicrobial photodynamic therapy (aPDT) combines a photosensitizer, light and oxygen to produce reactive oxygen species (ROS), mainly singlet oxygen (1O2), to photo-oxidize important biomolecules and induce cell death. aPDT is a promising alternative to standard antimicrobial strategies, but its mechanisms of action are not well understood. One of the reasons for that is the lack of control of the photosensitizing drugs location. Here we report the use of geneticallyencoded fluorescent proteins that are also 1O2 photosensitizers to address the latter issue. First, we have chosen the red fluorescent protein TagRFP as a photosensitizer, which unlike other fluorescent proteins such as KillerRed, is able to produce 1O2 but not other ROS. TagRFP photosensitizes 1O2 with a small, but not negligible, quantum yield. In addition, we have used miniSOG, a more efficient 1O2 photosensitizing fluorescent flavoprotein that has been recently engineered from phototropin 2. We have genetically incorporated these two photosensitizers into the cytosol of E. coli and demonstrated that intracellular 1O2 is sufficient to kill bacteria. Additional assays have provided further insight into the mechanism of cell death. Photodamage seems to occur primarily in the inner membrane, and extends to the outer membrane if the photosensitizer's efficiency is high enough. These observations are markedly different to those reported for external photosensitizers, suggesting that the site where 1O2 is primarily generated proves crucial for inflicting different types of cell damage.

  10. Optical monitoring of singlet oxygen generation during photodynamic treatment of tumors

    International Nuclear Information System (INIS)

    Optical detection of singlet oxygen production accompanying continuous-wave (CW) laser irradiation of subcutaneous murine tumors at 630 nm following prior intraperitoneal injection of a Photofrin II sensitizer has been demonstrated. In order to separate the spectrally discrete, time-delayed, singlet oxygen emission from the dominant, spectrally diffuse, coherent background provided by the combination of sensitizer infrared fluorescence and tissue-related autofluorescence, chopping of the incident laser beam was required. Using the infrared fluorescence to provide a reference, the singlet oxygen emission is shown to be given directly by the frequency-dependent quadrature component of the detector output. Maximum detector quadrature output for the in vivo case was obtained for a chopping frequency between 10 and 20 kHz. The spectral variation of the emission from the tumor was obtained and identified as that characteristic of singlet oxygen. This demonstration provides the rationale for the development of a clinically useful electro-optical system to provide a realistic means for monitoring treatment effectiveness during the photodynamic therapy of tumors as well as the establishment of much-needed dosimetry standards. It is expected that, in the future, development of this capbility will provide an analytical, quantitative means to remove some of the mysteries now impeding progress in this important area of medicine

  11. Laser-induced generation of singlet oxygen and its role in the cerebrovascular physiology

    Science.gov (United States)

    Semyachkina-Glushkovskaya, O. V.; Sokolovski, S. G.; Goltsov, A.; Gekaluyk, A. S.; Saranceva, E. I.; Bragina, O. A.; Tuchin, V. V.; Rafailov, E. U.

    2017-09-01

    For over 55 years, laser technology has expanded from laboratory research to widespread fields, for example telecommunication and data storage amongst others. Recently application of lasers in biology and medicine presents itself as one of the emerging areas. In this review, we will outline the recent advances in using lasers for the generation of singlet oxygen, traditionally used to kill tumour cells or induce thrombotic stroke model due to damage vascular effects. Over the last two decade, completely new results on cerebrovascular effects of singlet oxygen generated during photodynamic therapy (PDT) have been shown alongside promising applications for delivery of drugs and nanoparticles into the brain for therapy of brain cancer. Furthermore, a ;gold key; has been found to overcome the limitations of PDT, such as low light penetration and high toxicity of photosensitizers, by direct generation of singlet oxygen using quantum-dot laser diodes emitting in the near infrared (NIR) spectral range. It is our motivation to highlight these pioneering results in this review, to improve understanding of the biological role of singlet oxygen and to provide new perspectives for improving clinical application of laser based therapy in further research.

  12. In vivo outcome study of BPD-mediated PDT using a macroscopic singlet oxygen model

    Science.gov (United States)

    Kim, Michele M.; Penjweini, Rozhin; Zhu, Timothy C.

    2015-03-01

    Macroscopic modeling of the apparent reacted singlet oxygen concentration ([1O2]rx) for use with photodynamic therapy (PDT) has been developed and studied for benzoporphryin derivative monoacid ring A (BPD), a common photosensitizer. The four photophysical parameters (ξ, σ, β, δ) and threshold singlet oxygen dose ([1O2]rx, sh) have been investigated and determined using the RIF model of murine fibrosarcomas and interstitial treatment delivery. These parameters are examined and verified further by monitoring tumor growth post-PDT. BPD was administered at 1 mg/kg, and mice were treated 3 hours later with fluence rates ranging between 75 - 150 mW/cm2 and total fluences of 100 - 350 J/cm2. Treatment was delivered superficially using a collimated beam. Changes in tumor volume were tracked following treatment. The tumor growth rate was fitted for each treatment condition group and compared using dose metrics including total light dose, PDT dose, and reacted singlet oxygen. Initial data showing the correlation between outcomes and various dose metrics indicate that reacted singlet oxygen serves as a good dosimetric quantity for predicting PDT outcome.

  13. Voltage-sensitive styryl dyes as singlet oxygen targets on the surface of bilayer lipid membrane.

    Science.gov (United States)

    Sokolov, V S; Gavrilchik, A N; Kulagina, A O; Meshkov, I N; Pohl, P; Gorbunova, Yu G

    2016-08-01

    Photosensitizers are widely used as photodynamic therapeutic agents killing cancer cells by photooxidation of their components. Development of new effective photosensitive molecules requires profound knowledge of possible targets for reactive oxygen species, especially for its singlet form. Here we studied photooxidation of voltage-sensitive styryl dyes (di-4-ANEPPS, di-8-ANEPPS, RH-421 and RH-237) by singlet oxygen on the surface of bilayer lipid membranes commonly used as cell membrane models. Oxidation was induced by irradiation of a photosensitizer (aluminum phthalocyanine tetrasulfonate) and monitored by the change of dipole potential on the surface of the membrane. We studied the drop of the dipole potential both in the case when the dye molecules were adsorbed on the same side of the lipid bilayer as the photosensitizer (cis-configuration) and in the case when they were adsorbed on the opposite side (trans-configuration). Based on a simple model, we determined the rate of oxidation of the dyes from the kinetics of change of the potential during and after irradiation. This rate is proportional to steady-state concentration of singlet oxygen in the membrane under irradiation. Comparison of the oxidation rates of various dyes reveals that compounds of ANEPPS series are more sensitive to singlet oxygen than RH type dyes, indicating that naphthalene group is primarily responsible for their oxidation. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Phosphorescence dynamics of singlet oxygen and Radachlorin photosensitizer in aqueous solution

    Science.gov (United States)

    Belik, V. P.; Beltukova, D. M.; Gadzhiev, I. M.; Semenova, I. V.; Vasyutinskii, O. S.

    2017-07-01

    The luminescence spectrum of aqueous solution of Radachlorin photosensitizer in the near IR spectral range (950-1350 nm) has been determined at the excitation in both the Soret and Q absorption bands. Major sources of the recorded luminescence were analyzed. Kinetics of photosensitizer and singlet oxygen phosphorescence signals were studied by means of time-resolved spectroscopy. The corresponding characteristic lifetimes were determined.

  15. Impact of photosensitized oxidation and singlet oxygen on degradation of stabilized polymers

    Czech Academy of Sciences Publication Activity Database

    Pospíšil, Jan; Nešpůrek, Stanislav; Pilař, Jan

    2008-01-01

    Roč. 93, č. 9 (2008), s. 1681-1688 ISSN 0141-3910 R&D Projects: GA AV ČR IAA100100622; GA AV ČR KAN400720701; GA AV ČR IAA400500804 Institutional research plan: CEZ:AV0Z40500505 Keywords : photosensitized oxidation * singlet molecular oxygen * oxygenation Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.320, year: 2008

  16. CHEMICAL OXYGEN-IODINE LASER BASED ON HIGH PRESSURE SINGLET GENERATOR

    OpenAIRE

    Zagidullin, M.; Nikolaev, V.; Kurov, A.; Svistun, M.; Yerasov, N.

    1991-01-01

    The singlet oxygen generator based on the injection of jets of the base hydrogen peroxide solution into chlorine flow has been developed. The optimal parameters of the jet generator were found to achieve efficient chlorine uti1ization and high [MATH] yield up to the pressures of 30 torr. The chemical oxygen-iodine laser performance without water vapor trap up to 30 torr of the generator pressure has been attained.

  17. Volume 1: The Solid-Gas Singlet Delta Oxygen Generator

    National Research Council Canada - National Science Library

    Alfano, Angelo

    2004-01-01

    ...: a) construction of a Raman diagnostic system for the simultaneous measurement of excited and ground state oxygen in gas-solid reactions between solid peroxides and hydrogen halides or chlorine gas, b...

  18. Singlet oxygen mediated DNA degradation by copper nanoparticles: potential towards cytotoxic effect on cancer cells

    Directory of Open Access Journals (Sweden)

    Sengupta Tapas K

    2011-03-01

    Full Text Available Abstract The DNA degradation potential and anti-cancer activities of copper nanoparticles of 4-5 nm size are reported. A dose dependent degradation of isolated DNA molecules by copper nanoparticles through generation of singlet oxygen was observed. Singlet oxygen scavengers such as sodium azide and Tris [hydroxyl methyl] amino methane were able to prevent the DNA degradation action of copper nanoparticles confirming the involvement of activated oxygen species in the degradation process. Additionally, it was observed that the copper nanoparticles are able to exert cytotoxic effect towards U937 and Hela cells of human histiocytic lymphoma and human cervical cancer origins, respectively by inducing apoptosis. The growth characteristics of U937 and Hela cells were studied applying various concentrations of the copper nanoparticles.

  19. Singlet oxygen mediated DNA degradation by copper nanoparticles: potential towards cytotoxic effect on cancer cells.

    Science.gov (United States)

    Jose, Gregor P; Santra, Subhankar; Mandal, Swadhin K; Sengupta, Tapas K

    2011-03-25

    The DNA degradation potential and anti-cancer activities of copper nanoparticles of 4-5 nm size are reported. A dose dependent degradation of isolated DNA molecules by copper nanoparticles through generation of singlet oxygen was observed. Singlet oxygen scavengers such as sodium azide and Tris [hydroxyl methyl] amino methane were able to prevent the DNA degradation action of copper nanoparticles confirming the involvement of activated oxygen species in the degradation process. Additionally, it was observed that the copper nanoparticles are able to exert cytotoxic effect towards U937 and Hela cells of human histiocytic lymphoma and human cervical cancer origins, respectively by inducing apoptosis. The growth characteristics of U937 and Hela cells were studied applying various concentrations of the copper nanoparticles.

  20. High-sensitivity imaging method of singlet oxygen and superoxide anion in photodynamic and sonodynamic actions

    Science.gov (United States)

    Xing, Da; He, Yonghong; Hao, Min; Chen, Qun

    2004-07-01

    A novel method of photodynamic diagnosis (PDD) of cancer mediated by chemiluminescence (CL) probe is presented. The mechanism for photodynamic therapy (PDT) involves reactive oxygen species (ROS), such as singlet oxygen (1O2) and superoxide (O2-), generated by during the photochemical process. Both 1O2 and O2- can react with Cypridina luciferin analogue (FCLA), a highly selective CL probe for detecting the ROS. Chemiluminescence from the reaction of FCLA with the ROS, at about 530 nm, was detected by a highly sensitive ICCD system. The CL was markedly inhibited by the addition of 10 mmol/L sodium azide (NaN3) in a sample solution. Similar phenomena, with lesser extents of changes, were observed at the additions of 10 μmol/L superoxide dismutase (SOD), 10 mmol/L mannitol, and 100 μg/mL catalase, respectively. This indicates that the detected CL signals were mainly from ROS generated during the photosensitization reactions. Also, the chemiluminescence method was used to detect the ROS during sonodynamic action, both in vitro and in vivo. ROS formation during sonosensitizations of HpD and ATX-70 were detected using our newly-developed imaging technique, in real time, on tumor bearing animals. This method can provide a new means in clinics for tumor diagnosis.

  1. Production of Singlet Oxygen in a Non-Self-Sustained Discharge

    International Nuclear Information System (INIS)

    Vasil'eva, A.N.; Klopovskii, K.S.; Kovalev, A.S.; Lopaev, D.V.; Mankelevich, Yu.A.; Popov, N.A.; Rakhimov, A.T.; Rakhimova, T.V.

    2005-01-01

    The production of O 2 (a 1 Δ g ) singlet oxygen in non-self-sustained discharges in pure oxygen and mixtures of oxygen with noble gases (Ar or He) was studied experimentally. It is shown that the energy efficiency of O 2 (a 1 Δ g ) production can be optimized with respect to the reduced electric field E/N. It is shown that the optimal E/N values correspond to electron temperatures of 1.2-1.4 eV. At these E/N values, a decrease in the oxygen percentage in the mixture leads to an increase in the excitation rate of singlet oxygen because of the increase in the specific energy deposition per O 2 molecule. The onset of discharge instabilities not only greatly reduces the energy efficiency of singlet oxygen production but also makes it impossible to achieve high energy deposition in a non-self-sustained discharge. A model of a non-self-sustained discharge in pure oxygen is developed. It is shown that good agreement between the experimental and computed results for a discharge in oxygen over a wide range of reduced electric fields can be achieved only by taking into account the ion component of the discharge current. The cross section for the electron-impact excitation of O 2 (a 1 Δ g ) and the kinetic scheme of the discharge processes with the participation of singlet oxygen are verified by comparing the experimental and computed data on the energy efficiency of the production of O 2 (a 1 Δ g ) and the dynamics of its concentration. It is shown that, in the dynamics of O 2 (a 1 Δ g ) molecules in the discharge afterglow, an important role is played by their deexcitation in a three-body reaction with the participation of O( 3 P) atoms. At high energy depositions in a non-self-sustained discharge, this reaction can reduce the maximal attainable concentration of singlet oxygen. The effect of a hydrogen additive to an Ar : O 2 mixture is analyzed based on the results obtained using the model developed. It is shown that, for actual electron beam current densities, a

  2. Singlet oxygen production by combining erythrosine and halogen light for photodynamic inactivation of Streptococcus mutans.

    Science.gov (United States)

    Fracalossi, Camila; Nagata, Juliana Yuri; Pellosi, Diogo Silva; Terada, Raquel Sano Suga; Hioka, Noboru; Baesso, Mauro Luciano; Sato, Francielle; Rosalen, Pedro Luiz; Caetano, Wilker; Fujimaki, Mitsue

    2016-09-01

    Photodynamic inactivation of microorganisms is based on a photosensitizing substance which, in the presence of light and molecular oxygen, produces singlet oxygen, a toxic agent to microorganisms and tumor cells. This study aimed to evaluate singlet oxygen quantum yield of erythrosine solutions illuminated with a halogen light source in comparison to a LED array (control), and the photodynamic effect of erythrosine dye in association with the halogen light source on Streptococcus mutans. Singlet oxygen quantum yield of erythrosine solutions was quantified using uric acid as a chemical-probe in an aqueous solution. The in vitro effect of the photodynamic antimicrobial activity of erythrosine in association with the halogen photopolimerizing light on Streptococcus mutans (UA 159) was assessed during one minute. Bacterial cultures treated with erythrosine alone served as negative control. Singlet oxygen with 24% and 2.8% degradation of uric acid in one minute and a quantum yield of 0.59 and 0.63 was obtained for the erythrosine samples illuminated with the halogen light and the LED array, respectively. The bacterial cultures with erythrosine illuminated with the halogen light presented a decreased number of CFU mL(-1) in comparison with the negative control, with minimal inhibitory concentrations between 0.312 and 0.156mgmL(-1). The photodynamic response of erythrosine induced by the halogen light was capable of killing S. mutans. Clinical trials should be conducted to better ascertain the use of erythrosine in association with halogen light source for the treatment of dental caries. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Bactericidal nanofabrics based on photoproduction of singlet oxygen

    Czech Academy of Sciences Publication Activity Database

    Mosinger, Jiří; Jirsák, O.; Kubát, Pavel; Lang, Kamil; Mosinger, B.

    2007-01-01

    Roč. 17, č. 2 (2007), s. 164-166 ISSN 0959-9428 R&D Projects: GA ČR GA203/04/0426; GA ČR(CZ) GA203/06/1244 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : molecular-oxygen * nanofibers * porphyrin Subject RIV: CA - Inorganic Chemistry Impact factor: 4.339, year: 2007

  4. Singlet Oxygen Imaging in Polymeric Nanofibers by Delayed Fluorescence

    Czech Academy of Sciences Publication Activity Database

    Mosinger, J.; Lang, Kamil; Hostomský, Jiří; Franc, Jiří; Sýkora, Jan; Hof, Martin; Kubát, Pavel

    2010-01-01

    Roč. 114, č. 48 (2010), s. 15773-15779 ISSN 1520-6106 R&D Projects: GA ČR GA203/08/0831; GA ČR GAP208/10/1678 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : molecular-oxygen * meso-tetralylporphyrins * photodynamic therapy Subject RIV: CA - Inorganic Chemistry Impact factor: 3.603, year: 2010

  5. Inhibition of glyceraldehyde-3-phosphate dehydrogenase by peptide and protein peroxides generated by singlet oxygen attack

    DEFF Research Database (Denmark)

    Morgan, Philip E; Dean, Roger T; Davies, Michael Jonathan

    2002-01-01

    Reaction of certain peptides and proteins with singlet oxygen (generated by visible light in the presence of rose bengal dye) yields long-lived peptide and protein peroxides. Incubation of these peroxides with glyceraldehyde-3-phosphate dehydrogenase, in the absence of added metal ions, results......, with a stoichiometry of two thiols lost per peroxide consumed. Blocking the thiol residues prevents reaction with the peroxide. This stoichiometry, the lack of metal-ion dependence, and the absence of electron paramagnetic resonance (EPR)-detectable species, is consistent with a molecular (nonradical) reaction between...... inhibited by these peroxides in the absence of added Fe2+-EDTA. The presence of this metal-ion complex enhanced the inhibition observed with these enzymes consistent with the occurrence of radical-mediated reactions. Overall, these studies demonstrate that singlet oxygen-mediated damage to an initial target...

  6. A mechanistic study on the phototoxicity of atorvastatin: singlet oxygen generation by a phenanthrene-like photoproduct.

    Science.gov (United States)

    Montanaro, Sara; Lhiaubet-Vallet, Virginie; Iesce, MariaRosaria Iesce; Previtera, Lucio; Miranda, Miguel Angel

    2009-01-01

    Atorvastatin calcium (ATV) is one of the most frequently prescribed drugs worldwide. Among the adverse effects observed for this lipid-lowering agent, clinical cases of cutaneous adverse reactions have been reported and associated with photosensitivity disorders. Previous work dealing with ATV photochemistry has shown that exposure to natural sunlight in aqueous solution leads to photoproducts resulting from oxidation of the pyrrole ring and from cyclization to a phenanthrene derivative. Laser flash photolysis of ATV, at both 266 and 308 nm, led to a transient spectrum with two maxima at lambda= 360 and lambda= 580 nm (tau= 41 micro), which was assigned to the primary intermediate of the stilbene-like photocyclization. On the basis of the absence of a triplet-triplet absorption, the role of the parent drug as singlet oxygen photosensitizer can be discarded. By contrast, a stable phenanthrene-like photoproduct would be a good candidate to play this role. Laser flash photolysis of this compound showed a triplet-triplet transient absorption at lambdamax = 460 nm with a lifetime of 26 micro, which was efficiently quenched by oxygen (kq = 3 (+/-0.2) x 10(9) M(-1) s(-1)). Its potential to photosensitize formation of singlet oxygen was confirmed by spin trapping experiments, through conversion of TEMP to the stable free radical TEMPO. The photoreactivity of the phenanthrene-like photoproduct was investigated using Trp as a marker. The disappearance of the amino acid fluorescence (lambdamax = 340 nm) after increasing irradiation times at 355 nm was taken as a measurement of photodynamic oxidation. To confirm the involvement of a type II mechanism, the same experiment was also performed in D2O; this resulted in a significant enhancement of the reaction rate. On the basis of the obtained photophysical and photochemical results, the phototoxicity of atorvastatin can be attributed to singlet oxygen formation with the phenanthrene-like photoproduct as a photosensitizer.

  7. Lycopene inhibits the isomerization of β-carotene during quenching of singlet oxygen and free radicals.

    Science.gov (United States)

    Heymann, Thomas; Heinz, Philipp; Glomb, Marcus A

    2015-04-01

    The present study aimed to investigate the influence of singlet oxygen and radical species on the isomerization of carotenoids. On the one hand, lycopene and β-carotene standards were incubated with 1,4-dimethylnaphthalene-1,4-endoperoxide that produced singlet oxygen in situ. (13Z)- and (15Z)-β-carotene were preferentially generated at low concentrations of singlet oxygen, while high concentrations resulted in formation of (9Z)-β-carotene. The addition of different concentrations of lycopene led to the same isomerization progress of β-carotene, but resulted in a decreased formation of (9Z)-β-carotene and retarded degradation of (all-E)-β-carotene. On the other hand, isomerization of β-carotene and lycopene was induced by ABTS-radicals, too. As expected from the literature, chemical quenching was observed especially for lycopene, while physical quenching was preferred for β-carotene. Mixtures of β-carotene and lycopene resulted in a different isomerization progress compared to the separate β-carotene model. As long as lycopene was present, almost no isomerization of β-carotene was triggered; after that, strong formation of (13Z)-, (9Z)-, and (15Z)-β-carotene was initiated. In summary, lycopene protected β-carotene against isomerization during reactions with singlet oxygen and radicals. These findings can explain the pattern of carotenoid isomers analyzed in fruits and vegetables, where lycopene containing samples showed higher (all-E)/(9Z)-β-carotene ratios, and also in in vivo samples such as human blood plasma.

  8. Time and spectral resolved phosphorescence of singlet oxygen and pigments in photosystem II particles

    Czech Academy of Sciences Publication Activity Database

    Dědic, R.; Svoboda, A.; Pšenčík, J.; Lupínková, Lenka; Komenda, Josef; Hála, J.

    2003-01-01

    Roč. 102, - (2003), s. 313-317 ISSN 0022-2313 R&D Projects: GA ČR GA203/00/1257; GA MŠk LN00A141 Grant - others:GA ČR(CZ) GP202/01/D100 Institutional research plan: CEZ:MSM 113200001 Keywords : singlet oxygen phosphorescence * triplet kinetics Subject RIV: BO - Biophysics Impact factor: 1.314, year: 2003

  9. PHOTOGENERATION OF SINGLET OXYGEN AND FREE RADICALS IN DISSOLVED ORGANIC MATTER ISOLATED FROM THE MISSISSIPPI AND ATCHAFALAYA RIVER PLUMES

    Science.gov (United States)

    The photoreactivity to UV light of ultrafiltered dissolved organic matter (DOM) collected during cruises along salinity transects in the Mississippi and Atchafalaya River plumes was examined by measuring photogenerated free radicals and singlet molecular oxygen (1O2) photosensiti...

  10. BODIPY-pyrene and perylene dyads as heavy atom-free singlet oxygen sensitizers

    KAUST Repository

    Filatov, Mikhail A.

    2018-02-23

    Dyads combining BODIPY as an electron acceptor and pyrene or perylene as electron donor subunits were prepared and studied their photophysical properties studied by steady-state and transient spectroscopy. Depending on the structure of the subunits and polarity of the media, the dyads show either bright fluorescence or photo-induced electron transfer (PeT) in solution. Charge-transfer (CT) states formed as a result of PeT and were found to yield triplet excited states of the BODIPY. In the presence of molecular oxygen, the dyads sensitize singlet oxygen (1O2) with quantum yields of up to 0.75.

  11. Singlet oxygen generation during the oxidation of L-tyrosine and L-dopa with mushroom tyrosinase

    Energy Technology Data Exchange (ETDEWEB)

    Miyaji, Akimitsu [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259-G1-14, Nagatsuta-cho, Midori-ku, Yokohama 226-8502 (Japan); Kohno, Masahiro [Department of Bioscience and Biotechnology, Tokyo Institute of Technology, 4259-G1-25 Nagatsuta-cho, Midori-ku, Yokohama 226-8502 (Japan); Inoue, Yoshihiro [Showa Pharmaceutical University, 3-3165 Higashi-tamagawagakuen, Machida, Tokyo 194-8543 (Japan); Baba, Toshihide, E-mail: tbaba@chemenv.titech.ac.jp [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259-G1-14, Nagatsuta-cho, Midori-ku, Yokohama 226-8502 (Japan)

    2016-03-18

    The generation of singlet oxygen during the oxidation of tyrosine and L-dopa using mushroom tyrosinase in a phosphate buffer (pH 7.4), the model of melanin synthesis in melanocytes, was examined. The reaction was performed in the presence of 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP), an acceptor of singlet oxygen and the electron spin resonance (ESR) of the spin adduct, 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy (4-oxo-TEMPO), was measured. An increase in the ESR signal attributable to 4-oxo-TEMPO was observed during the oxidation of tyrosine and L-dopa with tyrosinase, indicating the generation of singlet oxygen. The results suggest that {sup 1}O{sub 2} generation via tyrosinase-catalyzed melanin synthesis occurs in melanocyte. - Highlights: • Generation of singlet oxygen was observed during tyrosinase-catalyzed tyrosine oxidation. • The singlet oxygen generated when tyrosine was converted into dopachrome. • The amount of singlet oxygen is not sufficient for cell toxicity. • It decreased when the hydroxyl radicals and/or superoxide anions were trapped.

  12. Pulsed electron-beam-sustained discharge in oxygen-containing gas mixtures: electrical characteristics, spectroscopy,and singlet oxygen yield

    International Nuclear Information System (INIS)

    Vagin, Nikolai P; Ionin, Andrei A; Klimachev, Yu M; Kotkov, A A; Podmar'kov, Yu P; Seleznev, L V; Sinitsyn, D V; Frolov, M P; Yuryshev, Nikolai N; Kochetov, Igor' V; Napartovich, A P; Hager, G D

    2004-01-01

    The electrical and spectroscopic characteristics of electron-beam-sustained discharge (EBSD) in oxygen and oxygen-containing gas mixtures are studied experimentally under gas pressures up to 100 Torr in a large excitation volume (∼18 L). It is shown that the EBSD in pure oxygen and its mixtures with inert gases is unstable and is characterised by a small specific energy contribution. The addition of small amounts (∼1%-10%) of carbon monoxide or hydrogen to oxygen or its mixtures with inert gases considerably improves the stability of the discharge, while the specific energy contribution W increases by more then an order of magnitude, achieving ∼6.5 kJ L -1 atm -1 per molecular component of the gas mixture. A part of the energy supplied to the EBSD is spent to excite vibrational levels of molecular additives. This was demonstrated experimentally by the initiation of a CO laser based on the O 2 : Ar : CO = 1 : 1 : 0.1 mixture. Experimental results on spectroscopy of the excited electronic states O 2 (a 1 Δ g ) and O 2 (b 1 Σ g + ), of oxygen formed in the EBSD are presented. A technique was worked out for measuring the concentration of singlet oxygen in the O 2 (a 1 Δ g ) state in the afterglow of the pulsed EBSD by comparing with the radiation intensity of singlet oxygen of a given concentration produced in a chemical generator. Preliminary measurements of the singlet-oxygen yield in the EBSD show that its value ∼3% for W ∼ 1.0 kJ L -1 atm -1 is in agreement with the theoretical estimate. Theoretical calculations performed for W ∼ 6.5 kJ L -1 atm -1 at a fixed temperature show that the singlet-oxygen yield may be ∼20%, which is higher than the value required to achieve the lasing threshold in an oxygen-iodine laser at room temperature. (laser applications and other topics in quantum electronics)

  13. Efficiency factors of singlet oxygen generation from core-modified expanded porphyrin: tetrathiarubyrin in ethanol

    CERN Document Server

    Ha, J H; Kim, Y R; Jung, G Y; Lee, Y H; Shin, K

    2001-01-01

    The photophysical properties and the singlet oxygen generation efficiency of tetrathiarubyrin have been investigated to elucidate the possibility of its use as a photodynamic therapy (PDT) photosensitizer by steady-state and time-resolved spectroscopic methods. The observed photophysical properties were affected by various molecular aspects, such as extended pi conjugation, structural distortion, and internal heavy atom. The steady-state electronic absorption spectrum was red-shifted due to the extended pi-conjugation, and the spin orbital coupling was enhanced by the structural distortion and the internal heavy atom effect. As a result of the enhanced spin orbital coupling, the triplet quantum yield increased to 0.90 +- 0.10 and the triplet state lifetime was shortened to 7.0 +- 1.2 mu s. Since the triplet state decays at a relatively faster rate, the efficiency of the oxygen quenching of the triplet state decreases. The singlet oxygen quantum yield was estimated to be 0.52 +- 0.02, which is somewhat lower t...

  14. Deletion of CGLD1 Impairs PSII and Increases Singlet Oxygen Tolerance of Green Alga Chlamydomonas reinhardtii

    Directory of Open Access Journals (Sweden)

    Jiale Xing

    2017-12-01

    Full Text Available The green alga Chlamydomonas reinhardtii is a key model organism for studying photosynthesis and oxidative stress in unicellular eukaryotes. Using a forward genetics approach, we have identified and characterized a mutant x32, which lacks a predicted protein named CGLD1 (Conserved in Green Lineage and Diatom 1 in GreenCut2, under normal and stress conditions. We show that loss of CGLD1 resulted in minimal photoautotrophic growth and PSII activity in the organism. We observed reduced amount of PSII complex and core subunits in the x32 mutant based on blue-native (BN/PAGE and immunoblot analysis. Moreover, x32 exhibited increased sensitivity to high-light stress and altered tolerance to different reactive oxygenic species (ROS stress treatments, i.e., decreased resistance to H2O2/or tert-Butyl hydroperoxide (t-BOOH and increased tolerance to neutral red (NR and rose bengal (RB that induce the formation of singlet oxygen, respectively. Further analysis via quantitative real-time PCR (qRT-PCR indicated that the increased singlet-oxygen tolerance of x32 was largely correlated with up-regulated gene expression of glutathione-S-transferases (GST. The phenotypical and physiological implications revealed from our experiments highlight the important roles of CGLD1 in maintaining structure and function of PSII as well as in protection of Chlamydomonas under photo-oxidative stress conditions.

  15. Monitoring of singlet oxygen luminescence and mitochondrial autofluorescence after illumination of hypericin/mitochondria complex

    DEFF Research Database (Denmark)

    Petrovajova, D; Jancura, D; Miskovsky, P

    2013-01-01

    and mitochondria was studied by steady-state and time-resolved UV–vis absorption and fluorescence spectroscopy. A high concentration of Hyp leads to the aggregation of this compound inside the mitochondria and the relative population of the monomeric (biologically active) form of Hyp decreases concomitantly......A study of hypericin (Hyp) interaction with mitochondria isolated from U-87 MG glioma cells as well as the time-resolved measurement of singlet oxygen (1O2) formation and annihilation after illumination of the Hyp/mitochondria complex is presented in this work. Interaction between Hyp...

  16. Single Molecule Atomic Force Microscopy Studies of Photosensitized Singlet Oxygen Behavior on a DNA Origami Template

    DEFF Research Database (Denmark)

    Helmig, Sarah Wendelboe; Rotaru, Alexandru; Arian, Dumitru

    2010-01-01

    DNA origami, the folding of a long single-stranded DNA sequence (scaffold strand) by hundreds of short synthetic oligonucleotides (staple strands) into parallel aligned helices, is a highly efficient method to form advanced self-assembled DNA-architectures. Since molecules and various materials can...... be conjugated to each of the short staple strands, the origami method offers a unique possibility of arranging molecules and materials in well-defined positions on a structured surface. Here we combine the action of light with AFM and DNA nanostructures to study the production of singlet oxygen from a single...

  17. The participation of singlet oxygen in a photocitotoxicity of extract from amazon plant to cancer cells

    Science.gov (United States)

    Tcibulnikova, Anna V.; Degterev, Igor A.; Bryukhanov, Valery V.; Roberto, Mantuanelly M.; Campos Pereira, F. D.; Marin-Morales, M. A.; Slezhkin, Vasily A.; Samusev, Ilya G.

    2018-01-01

    We have been searching for new photosensitizers (PS) for photodynamic therapy (PDT) of cancer based on extracts from Amazonian plants since 2009. In this paper, we demonstrate that, under certain conditions, the extract from fruits of the Amazonian palm Euterpe oleraceae (popular name Açaí) can serve as a PS for PDT treatment of murine breast cancer cells (4T1 cell line). We have been first to show directly that the photodynamic effect of plant PS is due to singlet oxygen.

  18. Singlet oxygen-induced mutations in M13 lacZ phage DNA.

    OpenAIRE

    Decuyper-Debergh, D; Piette, J; Van de Vorst, A

    1987-01-01

    The mutagenic consequences of damages to M13 mp19 RF DNA produced by singlet oxygen have been determined in a forward mutational system capable of detecting all classes of mutagenic events. When the damaged M13 mp19 RF DNA is used to transfect competent E. coli JM105 cells, a 16.6-fold increase in mutation frequency is observed at 5% survivors when measured as a loss of alpha-complementation. The enhanced mutagenicity is largely due to single-nucleotide substitutions, frameshift events and do...

  19. Explicit macroscopic singlet oxygen modeling for benzoporphyrin derivative monoacid ring A (BPD)-mediated photodynamic therapy.

    Science.gov (United States)

    Kim, Michele M; Penjweini, Rozhin; Liang, Xing; Zhu, Timothy C

    2016-11-01

    Photodynamic therapy (PDT) is an effective non-ionizing treatment modality that is currently being used for various malignant and non-malignant diseases. In type II PDT with photosensitizers such as benzoporphyrin monoacid ring A (BPD), cell death is based on the creation of singlet oxygen ( 1 O 2 ). With a previously proposed empirical five-parameter macroscopic model, the threshold dose of singlet oxygen ([ 1 O 2 ] rx,sh ]) to cause tissue necrosis in tumors treated with PDT was determined along with a range of the magnitude of the relevant photochemical parameters: the photochemical oxygen consumption rate per light fluence rate and photosensitizer concentration (ξ), the probability ratio of 1 O 2 to react with ground state photosensitizer compared to a cellular target (σ), the ratio of the monomolecular decay rate of the triplet state photosensitizer (β), the low photosensitizer concentration correction factor (δ), and the macroscopic maximum oxygen supply rate (g). Mice bearing radiation-induced fibrosarcoma (RIF) tumors were treated interstitially with a linear light source at 690nm with total energy released per unit length of 22.5-135J/cm and source power per unit length of 12-150mW/cm to induce different radii of necrosis. A fitting algorithm was developed to determine the photochemical parameters by minimizing the error function involving the range between the calculated reacted singlet oxygen ([ 1 O 2 ] rx ) at necrosis radius and the [ 1 O 2 ] rx,sh . [ 1 O 2 ] rx was calculated based on explicit dosimetry of the light fluence distribution, the tissue optical properties, and the BPD concentration. The initial ground state oxygen concentration ([ 3 O 2 ] 0 ) was set to be 40μM in this study. The photochemical parameters were found to be ξ=(55±40)×10 -3 cm 2 mW -1 s -1 , σ=(1.8±3)×10 -5 μM -1 , and g=1.7±0.7μMs -1 . We have taken the literature values for δ=33μM, and β=11.9μM. [ 1 O 2 ] rx has shown promise to be a more effective

  20. Singlet Oxygen Photophysics in Liquid Solvents: Converging on a Unified Picture.

    Science.gov (United States)

    Bregnhøj, Mikkel; Westberg, Michael; Minaev, Boris F; Ogilby, Peter R

    2017-08-15

    Singlet oxygen, O 2 (a 1 Δ g ), the lowest excited electronic state of molecular oxygen, is an omnipresent part of life on earth. It is readily formed through a variety of chemical and photochemical processes, and its unique reactions are important not just as a tool in chemical syntheses but also in processes that range from polymer degradation to signaling in biological cells. For these reasons, O 2 (a 1 Δ g ) has been the subject of intense activity in a broad distribution of scientific fields for the past ∼50 years. The characteristic reactions of O 2 (a 1 Δ g ) kinetically compete with processes that deactivate this excited state to the ground state of oxygen, O 2 (X 3 Σ g - ). Moreover, O 2 (a 1 Δ g ) is ideally monitored using one of these deactivation channels: O 2 (a 1 Δ g ) → O 2 (X 3 Σ g - ) phosphorescence at 1270 nm. Thus, there is ample justification to study and control these competing processes, including those mediated by solvents, and the chemistry community has likewise actively tackled this issue. In themselves, the solvent-mediated radiative and nonradiative transitions between the three lowest-lying electronic states of oxygen [O 2 (X 3 Σ g - ), O 2 (a 1 Δ g ), and O 2 (b 1 Σ g + )] are relevant to issues at the core of modern chemistry. In the isolated oxygen molecule, these transitions are forbidden by quantum-mechanical selection rules. However, solvent molecules perturb oxygen in such a way as to make these transitions more probable. Most interestingly, the effect of a series of solvents on the O 2 (X 3 Σ g - )-O 2 (b 1 Σ g + ) transition, for example, can be totally different from the effect of the same series of solvents on the O 2 (X 3 Σ g - )-O 2 (a 1 Δ g ) transition. Moreover, a given solvent that appreciably increases the probability of a radiative transition generally does not provide a correspondingly viable pathway for nonradiative energy loss, and vice versa. The ∼50 years of experimental work leading to

  1. Influence of nitrogen oxides NO and NO2 on singlet delta oxygen production in pulsed discharge

    International Nuclear Information System (INIS)

    Ionin, A A; Klimachev, Yu M; Kozlov, A Yu; Kotkov, A A; Rulev, O A; Seleznev, L V; Sinitsyn, D V; Vagin, N P; Yuryshev, N N; Kochetov, I V; Napartovich, A P

    2009-01-01

    The influence of nitrogen oxides NO and NO 2 on the specific input energy (SIE) and the time behaviour of singlet delta oxygen (SDO) luminescence excited by a pulsed e-beam sustained discharge in oxygen were experimentally and theoretically studied. NO and NO 2 addition into oxygen results in a small increase and decrease in the SIE, respectively, the latter being connected with a large energy of electron affinity to NO 2 . The addition of 0.1-0.3% nitrogen oxides was experimentally and theoretically demonstrated to result in a notable enhancement of the SDO lifetime, which is related to a decrease in the atomic oxygen concentration in afterglow. It was experimentally demonstrated that to get a high SDO concentration at the gas pressure 30-60 Torr for a time interval of less than ∼0.5 s one needs to add not less than 0.2% nitrogen oxides into oxygen. The temperature dependence of the relaxation constant for SDO quenching by unexcited oxygen was estimated by using experimental data on the time behaviour of SDO luminescence.

  2. UVA Photoirradiation of Oxygenated Benz[a]anthracene and 3-Methylcholanthene - Generation of Singlet Oxygen and Induction of Lipid Peroxidation

    Directory of Open Access Journals (Sweden)

    Diógenes Herreño Sáenz

    2008-03-01

    Full Text Available Polycyclic aromatic hydrocarbons (PAHs are widespread genotoxic environmental pollutants and potentially pose a health risk to humans. Although the biological and toxicological activities, including metabolism, mutagenicity, and carcinogenicity, of PAHs have been thoroughly studied, their phototoxicity and photo-induced biological activity have not been well examined. We have long been interested in phototoxicity of PAHs and their derivatives induced by irradiation with UV light. In this paper we report the photoirradiation of a series of oxygenated benz[a]anthracene (BA and 3-methylcholanthene (3-MC by UVA light in the presence of a lipid, methyl linoleate. The studied PAHs include 2-hydroxy-BA (2-OH-BA, 3-hydroxy-BA (3-OH-BA, 5-hydroxymethyl-BA (5-CH2OH-BA, 7-hydroxymethyl-BA (7-CH2OH-BA, 12-hydroxymethyl-BA (12-CH2OH-BA, 7-hydroxymethyl-12-methyl-BA (7-CH2OH-12-MBA, 5-formyl-BA (5-CHO-BA, BA 5,6-cis-dihydrodiol (BA 5,6-cis-diol, 1-hydroxy-3- methylcholanthene (1-OH-3-MC, 1-keto-3-methylcholanthene (1-keto-3-MC, and 3-MC 1,2-diol. The results indicate that upon photoirradiation by UVA at 7 and 21 J/cm2, respectively all these compounds induced lipid peroxidation and exhibited a relationship between the dose of the light and the level of lipid peroxidation induced. To determine whether or not photoirradiation of these compounds by UVA light produces ROS, an ESR spin-trap technique was employed to provide direct evidence. Photoirradiation of 3-keto-3-MC by UVA (at 389 nm in the presence of 2,2,6,6-tetramethylpiperidine (TEMP, a specific probe for singlet oxygen, resulted in the formation of TEMPO, indicating that singlet oxygen was generated. These overall results suggest that UVA photoirradiation of oxygenated BA and 3-methylcholanthrene generates singlet oxygen, one of the reactive oxygen species (ROS, which induce lipid peroxidation.

  3. Efficiencies of singlet oxygen production and rate constants for oxygen quenching in the S1 state of dicyanonaphthalenes and related compounds.

    Science.gov (United States)

    Tanaka, Fujio; Tsumura, Kazuyuki; Furuta, Tomoaki; Iwamoto, Kenichi; Okamoto, Masami

    2008-01-01

    The quantum yield of singlet oxygen ((1)O(2) ((1)Delta(g))) production (Phi(Delta)) in the oxygen quenching of photoexcited states for 1,2-dicyanonaphthalene (1,2-DCNN), 1,4-dicyanonaphthalene (1,4-DCNN) and 2,3-dicyanonaphthalene (2,3-DCNN) in cyclohexane, benzene, and acetonitrile was measured using a time-resolved thermal lens (TRTL) technique, in order to determine the efficiency of singlet oxygen ((1)Delta(g)) production in the first excited singlet state (S(1)), (f(Delta)(S)). The efficiencies of singlet oxygen ((1)Delta(g)) production from the lowest triplet state (T(1)), (f(Delta)(T)), were nearly unity for all DCNNs in all the solvents. The values of f(Delta)(S) were fairly large for 1,2-DCNN (0.33-0.57) and 1,4-DCNN (0.33-0.66), but were close to zero for 2,3-DCNN. Rate constants for oxygen quenching in the S(1) state (k(q)(S)) obtained for these compounds were significantly smaller than diffusion-controlled rate constants. The kinetics for processes leading to production and no production of singlet oxygen is discussed on the basis of the values of f(Delta)(S) and k(q)(S). The results obtained regarding phenanthrene (PH), 9-cyanophenanthrene (9-CNPH), pyrene (PY) and 1-cyanopyrene (1-CNPY) are also discussed.

  4. Influence of clay minerals on curcumin properties: Stability and singlet oxygen generation

    Science.gov (United States)

    Gonçalves, Joyce L. S.; Valandro, Silvano R.; Poli, Alessandra L.; Schmitt, Carla C.

    2017-09-01

    Curcumin (CUR) has showed promising photophysical properties regarding to biological and chemical sciences. However, the main barrier for those applications are their low solubility and stability in aqueous solution. The effects of two different clay minerals, the montmorillonite (SWy-2) and the Laponite RD (Lap) nanoclay, on the stabilization of Curcumin were investigated. Their effects were compared with two well-established environments (acidic and neutral aqueous media). CUR/clay hybrids were prepared using a simple and fast method, where CUR solution was added into clay suspensions, to obtain well dispersed hybrids in water. The degradation process of CUR and CUR/clays hybrids was investigated using UV-Vis spectroscopic. For both studied hybrids, the CUR degradation process was suppressed by the presence of the clay particles. Furthermore, the Lap showed a great stabilization effect than SWy-2. This behavior was due to the smaller particle size and higher exfoliation ability of Lap, providing a large surface for CUR adsorption compared to SWy-2. The degradation process of CUR solutions and CUR/clay hybrids was also studied in the presence of light. CUR photodegradation process was faster not only in the aqueous solution but also in the clay suspension compared to those studied in the dark. The presence of clay particles accelerated the photodegradation of CUR due to the products formation in the reactions between CUR and oxygen radicals. Our results showed that the singlet oxygen quantum yield (ΦΔ) of CUR were about 59% higher in the clay suspensions than CUR in aqueous solution. Therefore, the formation of CUR/clay hybrids, in particularly with Lap, suppressed the degradation in absence light of CUR and increased the singlet oxygen generation, which makes this hybrids of CUR/clay a promising material to enlarge the application of CUR in the biological sciences.

  5. Time-resolved EPR study of singlet oxygen in the gas phase.

    Science.gov (United States)

    Ruzzi, Marco; Sartori, Elena; Moscatelli, Alberto; Khudyakov, Igor V; Turro, Nicholas J

    2013-06-27

    X-band EPR spectra of singlet O2((1)Δg) and triplet O2((3)Σg(-)) were observed in the gas phase under low molecular-oxygen pressures PO2 = 0.175-0.625 Torr, T = 293-323 K. O2((1)Δg) was produced by quenching of photogenerated triplet sensitizers naphthalene C8H10, perdeuterated naphthalene, and perfluoronaphthalene in the gas phase. The EPR spectrum of O2((1)Δg) was also observed under microwave discharge. Integrated intensities and line widths of individual components of the EPR spectrum of O2((3)Σg(-)) were used as internal standards for estimating the concentration of O2 species and PO2 in the EPR cavity. Time-resolved (TR) EPR experiments of C8H10 were the main focus of this Article. Pulsed irradiation of C8H10 in the presence of O2((3)Σg(-)) allowed us to determine the kinetics of formation and decay for each of the four components of the O2((1)Δg) EPR signal, which lasted for only a few seconds. We found that the kinetics of EPR-component decay fit nicely to a biexponential kinetics law. The TR EPR 2D spectrum of the third component of the O2((1)Δg) EPR spectrum was examined in experiments using C8H10. This spectrum vividly presents the time evolution of an EPR component. The largest EPR signal and the longest lifetime of O2((1)Δg), τ = 0.4 s, were observed at medium pressure PO2 = 0.4 Torr, T = 293 K. The mechanism of O2((1)Δg) decay in the presence of photosensitizers is discussed. EPR spectra of O2((1)Δg) evidence that the spin-rotational states of O2((1)Δg) are populated according to Boltzmann distribution in the studied time range of 10-100 ms. We believe that this is the first report dealing with the dependence of O2((1)Δg) EPR line width on PO2 and T.

  6. A graphene quantum dot photodynamic therapy agent with high singlet oxygen generation.

    Science.gov (United States)

    Ge, Jiechao; Lan, Minhuan; Zhou, Bingjiang; Liu, Weimin; Guo, Liang; Wang, Hui; Jia, Qingyan; Niu, Guangle; Huang, Xing; Zhou, Hangyue; Meng, Xiangmin; Wang, Pengfei; Lee, Chun-Sing; Zhang, Wenjun; Han, Xiaodong

    2014-08-08

    Clinical applications of current photodynamic therapy (PDT) agents are often limited by their low singlet oxygen ((1)O2) quantum yields, as well as by photobleaching and poor biocompatibility. Here we present a new PDT agent based on graphene quantum dots (GQDs) that can produce (1)O2 via a multistate sensitization process, resulting in a quantum yield of ~1.3, the highest reported for PDT agents. The GQDs also exhibit a broad absorption band spanning the UV region and the entire visible region and a strong deep-red emission. Through in vitro and in vivo studies, we demonstrate that GQDs can be used as PDT agents, simultaneously allowing imaging and providing a highly efficient cancer therapy. The present work may lead to a new generation of carbon-based nanomaterial PDT agents with overall performance superior to conventional agents in terms of (1)O2 quantum yield, water dispersibility, photo- and pH-stability, and biocompatibility.

  7. Stability of O/W Emulsion with Synthetic Perfumes Oxidized by Singlet Oxygen

    Directory of Open Access Journals (Sweden)

    Naoki Watabe

    2013-01-01

    Full Text Available We prepared O/W emulsion composed of a synthetic perfume, n-dodecane, protoporphyrin IX disodium salt (PpIX-2Na, sodium dodecyl sulfate, and water and investigated oxidative decomposition of the synthetic perfume in the emulsion and change in the stability of the emulsion by singlet oxygen (1O2 generated by photosensitization of PpIX-2Na. We used eugenol, linalool, benzyl acetate, α-ionone, α-hexylcinnamaldehyde, and d-limonene as a synthetic perfume. The stability of the O/W emulation including eugenol and linalool significantly decreased with increasing light irradiation time. The decrease in the emulsion stability may be attributable to oxidative decomposition of eugenol and linalool by 1O2 and enlargement of the oil droplet size.

  8. Nuclear spin singlet states as a contrast mechanism for NMR spectroscopy.

    Science.gov (United States)

    Devience, Stephen J; Walsworth, Ronald L; Rosen, Matthew S

    2013-10-01

    Nuclear magnetic resonance (NMR) spectra of complex chemical mixtures often contain unresolved or hidden spectral components, especially when strong background signals overlap weaker peaks. In this article we demonstrate a quantum filter utilizing nuclear spin singlet states, which allows undesired NMR spectral background to be removed and target spectral peaks to be uncovered. The quantum filter is implemented by creating a nuclear spin singlet state with spin quantum numbers j = 0, mz  = 0 in a target molecule, applying a continuous RF field to both preserve the singlet state and saturate the magnetization of undesired molecules and then mapping the target molecule singlet state back into an NMR observable state so that its spectrum can be read out unambiguously. The preparation of the target singlet state can be carefully controlled with pulse sequence parameters, so that spectral contrast can be achieved between molecules with very similar structures. We name this NMR contrast mechanism 'Suppression of Undesired Chemicals using Contrast-Enhancing Singlet States' (SUCCESS) and we demonstrate it in vitro for three target molecules relevant to neuroscience: aspartate, threonine and glutamine. Copyright © 2013 John Wiley & Sons, Ltd.

  9. A Possible Role for Singlet Oxygen in the Degradation of Various Antioxidants. A Meta-Analysis and Review of Literature Data.

    Science.gov (United States)

    Petrou, Athinoula L; Petrou, Petros L; Ntanos, Theodoros; Liapis, Antonis

    2018-02-27

    The thermodynamic parameters E act , ΔH ≠ , ΔS ≠ , and ΔG ≠ for various processes involving antioxidants were calculated using literature kinetic data (k, T). The ΔG ≠ values of the antioxidants' processes vary in the range 91.27-116.46 kJmol -1 at 310 K. The similarity of the ΔG ≠ values (for all of the antioxidants studied) is supported to be an indication that a common mechanism in the above antioxidant processes may be taking place. A value of about 10-30 kJmol -1 is the activation energy for the diffusion of reactants depending on the reaction and the medium. The energy 92 kJmol -1 is needed for the excitation of O₂ from the ground to the first excited state (¹Δ g , singlet oxygen). We suggest the same role of the oxidative stress and specifically of singlet oxygen to the processes of antioxidants as in the processes of proteinaceous diseases. We therefore suggest a competition between the various antioxidants and the proteins of proteinaceous diseases in capturing singlet oxygen's empty π* orbital. The concentration of the antioxidants could be a crucial factor for the competition. Also, the structures of the antioxidant molecules play a significant role since the various structures have a different number of regions of high electron density.

  10. Gold nanoring-enhanced generation of singlet oxygen: an intricate correlation with surface plasmon resonance and polyelectrolyte bilayers

    Czech Academy of Sciences Publication Activity Database

    Hu, Y.; Kaňka, Jiří; Liu, K.; Yang, Y.; Wang, H.; Du, H.

    2016-01-01

    Roč. 6, č. 106 (2016), s. 104819-104826 ISSN 2046-2069 R&D Projects: GA ČR(CZ) GBP205/12/G118 Institutional support: RVO:67985882 Keywords : Singlet oxygen * Fluorescence * Gold nanorings Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 3.108, year: 2016

  11. Lysozyme oxidation by singlet molecular oxygen: Peptide characterization using [18 O]-labeling oxygen and nLC-MS/MS.

    Science.gov (United States)

    Marques, Emerson Finco; Medeiros, Marisa H G; Di Mascio, Paolo

    2017-11-01

    Singlet molecular oxygen ( 1 O 2 ) is generated in biological systems and reacts with different biomolecules. Proteins are a major target for 1 O 2 , and His, Tyr, Met, Cys, and Trp are oxidized at physiological pH. In the present study, the modification of lysozyme protein by 1 O 2 was investigated using mass spectrometry approaches. The experimental findings showed methionine, histidine, and tryptophan oxidation. The experiments were achieved using [ 18 O]-labeled 1 O 2 released from thermolabile endoperoxides in association with nano-scale liquid chromatography coupled to electrospray ionization mass spectrometry. The structural characterization by nLC-MS/MS of the amino acids in the tryptic peptides of the proteins showed addition of [ 18 O]-labeling atoms in different amino acids. Copyright © 2017 John Wiley & Sons, Ltd.

  12. Singlet oxygen explicit dosimetry to predict local tumor control for HPPH-mediated photodynamic therapy

    Science.gov (United States)

    Penjweini, Rozhin; Kim, Michele M.; Ong, Yi Hong; Zhu, Timothy C.

    2017-02-01

    This preclinical study examines four dosimetric quantities (light fluence, photosensitizer photobleaching ratio, PDT dose, and reacted singlet oxygen ([1O2]rx)) to predict local control rate (LCR) for 2-(1-Hexyloxyethyl)-2-devinyl pyropheophorbide (HPPH)-mediated photodynamic therapy (PDT). Mice bearing radiation-induced fibrosarcoma (RIF) tumors were treated with different in-air fluences (135, 250 and 350 J/cm2) and in-air fluence rates (50, 75 and 150 mW/cm2) at 0.25 mg/kg HPPH and a drug-light interval of 24 hours using a 1 cm diameter collimated laser beam at 665 nm wavelength. A macroscopic model was used to calculate ([1O2]rx)) based on in vivo explicit dosimetry of the initial tissue oxygenation, photosensitizer concentration, and tissue optical properties. PDT dose was defined as a temporal integral of drug concentration and fluence rate (φ) at a 3 mm tumor depth. Light fluence rate was calculated throughout the treatment volume based on Monte-Carlo simulation and measured tissue optical properties. The tumor volume of each mouse was tracked for 30 days after PDT and Kaplan-Meier analyses for LCR were performed based on a tumor volume <=100 mm3, for four dose metrics: fluence, HPPH photobleaching rate, PDT dose, and ([1O2]rx)). The results of this study showed that ([1O2]rx)) is the best dosimetric quantity that can predict tumor response and correlate with LCR.

  13. Developments in PDT Sensitizers for Increased Selectivity and Singlet Oxygen Production

    Directory of Open Access Journals (Sweden)

    Nahid Mehraban

    2015-07-01

    Full Text Available Photodynamic therapy (PDT is a minimally-invasive procedure that has been clinically approved for treating certain types of cancers. This procedure takes advantage of the cytotoxic activity of singlet oxygen (1O2 and other reactive oxygen species (ROS produced by visible and NIR light irradiation of dye sensitizers following their accumulation in malignant cells. The main two concerns associated with certain clinically-used PDT sensitizers that have been influencing research in this arena are low selectivity toward malignant cells and low levels of 1O2 production in aqueous media. Solving the selectivity issue would compensate for photosensitizer concerns such as dark toxicity and aggregation in aqueous media. One main approach to enhancing dye selectivity involves taking advantage of key methods used in pharmaceutical drug delivery. This approach lies at the heart of the recent developments in PDT research and is a point of emphasis in the present review. Of particular interest has been the development of polymeric micelles as nanoparticles for delivering hydrophobic (lipophilic and amphiphilic photosensitizers to the target cells. This review also covers methods employed to increase 1O2 production efficiency, including the design of two-photon absorbing sensitizers and triplet forming cyclometalated Ir(III complexes.

  14. A Possible Role for Singlet Oxygen in the Degradation of Various Antioxidants. A Meta-Analysis and Review of Literature Data

    Science.gov (United States)

    Petrou, Athinoula L.; Petrou, Petros L.; Ntanos, Theodoros; Liapis, Antonis

    2018-01-01

    The thermodynamic parameters Eact, ΔH≠, ΔS≠, and ΔG≠ for various processes involving antioxidants were calculated using literature kinetic data (k, T). The ΔG≠ values of the antioxidants’ processes vary in the range 91.27–116.46 kJmol−1 at 310 K. The similarity of the ΔG≠ values (for all of the antioxidants studied) is supported to be an indication that a common mechanism in the above antioxidant processes may be taking place. A value of about 10–30 kJmol−1 is the activation energy for the diffusion of reactants depending on the reaction and the medium. The energy 92 kJmol−1 is needed for the excitation of O2 from the ground to the first excited state (1Δg, singlet oxygen). We suggest the same role of the oxidative stress and specifically of singlet oxygen to the processes of antioxidants as in the processes of proteinaceous diseases. We therefore suggest a competition between the various antioxidants and the proteins of proteinaceous diseases in capturing singlet oxygen’s empty π* orbital. The concentration of the antioxidants could be a crucial factor for the competition. Also, the structures of the antioxidant molecules play a significant role since the various structures have a different number of regions of high electron density. PMID:29495515

  15. Singlet oxygen generation in a high pressure non-self-sustained electric discharge

    International Nuclear Information System (INIS)

    Hicks, Adam; Norberg, Seth; Shawcross, Paul; Lempert, Walter R; Rich, J William; Adamovich, Igor V

    2005-01-01

    This paper presents results of singlet oxygen generation experiments in a high-pressure, non-self-sustained crossed discharge. The discharge consists of a high-voltage, short pulse duration, high repetition rate pulsed discharge, which produces ionization in the flow, and a low-voltage dc discharge which sustains current in a decaying plasma between the pulses. The sustainer voltage can be independently varied to maximize the energy input into electron impact excitation of singlet delta oxygen (SDO). The results demonstrate operation of a stable and diffuse crossed discharge in O 2 -He mixtures at static pressures of at least up to P 0 = 380 Torr and sustainer discharge powers of at least up to 1200 W, achieved at P 0 = 120 Torr. The reduced electric field in the positive column of the sustainer discharge varies from E/N = 0.3 x 10 -16 to 0.65 X 10 -16 V cm 2 , which is significantly lower than E/N in self-sustained discharges and close to the theoretically predicted optimum value for O 2 (a 1 Δ) excitation. Measurements of visible emission spectra O 2 (b 1 Σ → X 3 Σ) in the discharge afterglow show the O 2 (b 1 Σ) concentration to increase with the sustainer discharge power and to decrease as the O 2 fraction in the flow is increased. Rotational temperatures inferred from these spectra in 10% O 2 -90% He flows at P 0 = 120 Torr and mass flow rates of m-dot = 2.2 are 365-465 K. SDO yield at these conditions, 1.7% to 4.4%, was inferred from the integrated intensity of the (0, 0) band of the O 2 (a 1 Δ → X 3 Σ) infrared emission spectra calibrated using a blackbody source. The yield remains nearly constant in the discharge afterglow, up to at least 15 cm distance from the discharge. Kinetic modelling calculations using a quasi-one-dimensional nonequilibrium pulser-sustainer discharge model coupled with the Boltzmann equation for plasma electrons predict gas temperature rise in the discharge in satisfactory agreement with the experimental measurements

  16. Fluorescent polyurethane nanofabrics: A source of singlet oxygen and oxygen sensing

    Czech Academy of Sciences Publication Activity Database

    Mosinger, J.; Lang, Kamil; Plištil, L.; Jesenská, S.; Hostomský, Jiří; Zelinger, Zdeněk; Kubát, Pavel

    2010-01-01

    Roč. 26, č. 12 (2010), s. 10050-10056 ISSN 0743-7463 R&D Projects: GA ČR GA203/08/0831; GA ČR GAP208/10/1678; GA ČR GAP207/10/1447 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : sensitized delayed fluorescence * molecular-oxygen * photophysical properties Subject RIV: CA - Inorganic Chemistry Impact factor: 4.269, year: 2010

  17. Key players of singlet oxygen-induced cell death in plants.

    Science.gov (United States)

    Laloi, Christophe; Havaux, Michel

    2015-01-01

    The production of reactive oxygen species (ROS) is an unavoidable consequence of oxygenic photosynthesis. Singlet oxygen ((1)O2) is a highly reactive species to which has been attributed a major destructive role during the execution of ROS-induced cell death in photosynthetic tissues exposed to excess light. The study of the specific biological activity of (1)O2 in plants has been hindered by its high reactivity and short lifetime, the concurrent production of other ROS under photooxidative stress, and limited in vivo detection methods. However, during the last 15 years, the isolation and characterization of two (1)O2-overproducing mutants in Arabidopsis thaliana, flu and ch1, has allowed the identification of genetically controlled (1)O2 cell death pathways and a (1)O2 acclimation pathway that are triggered at sub-cytotoxic concentrations of (1)O2. The study of flu has revealed the control of cell death by the plastid proteins EXECUTER (EX)1 and EX2. In ch1, oxidized derivatives of β-carotene, such as β-cyclocitral and dihydroactinidiolide, have been identified as important upstream messengers in the (1)O2 signaling pathway that leads to stress acclimation. In both the flu and ch1 mutants, phytohormones act as important promoters or inhibitors of cell death. In particular, jasmonate has emerged as a key player in the decision between acclimation and cell death in response to (1)O2. Although the flu and ch1 mutants show many similarities, especially regarding their gene expression profiles, key differences, such as EXECUTER-independent cell death in ch1, have also been observed and will need further investigation to be fully understood.

  18. Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal-Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard.

    Science.gov (United States)

    Howarth, Ashlee J; Buru, Cassandra T; Liu, Yangyang; Ploskonka, Ann M; Hartlieb, Karel J; McEntee, Monica; Mahle, John J; Buchanan, James H; Durke, Erin M; Al-Juaid, Salih S; Stoddart, J Fraser; DeCoste, Jared B; Hupp, Joseph T; Farha, Omar K

    2017-01-01

    A fullerene-based photosensitizer is incorporated postsynthetically into a Zr 6 -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11 min. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Flavonoids in Microheterogeneous Media, Relationship between Their Relative Location and Their Reactivity towards Singlet Oxygen

    Science.gov (United States)

    Günther, Germán; Berríos, Eduardo; Pizarro, Nancy; Valdés, Karina; Montero, Guillermo; Arriagada, Francisco; Morales, Javier

    2015-01-01

    In this work, the relationship between the molecular structure of three flavonoids (kaempferol, quercetin and morin), their relative location in microheterogeneous media (liposomes and erythrocyte membranes) and their reactivity against singlet oxygen was studied. The changes observed in membrane fluidity induced by the presence of these flavonoids and the influence of their lipophilicity/hydrophilicity on the antioxidant activity in lipid membranes were evaluated by means of fluorescent probes such as Laurdan and diphenylhexatriene (DPH). The small differences observed for the value of generalized polarization of Laurdan (GP) curves in function of the concentration of flavonoids, indicate that these three compounds promote similar alterations in liposomes and erythrocyte membranes. In addition, these compounds do not produce changes in fluorescence anisotropy of DPH, discarding their location in deeper regions of the lipid bilayer. The determined chemical reactivity sequence is similar in all the studied media (kaempferol < quercetin < morin). Morin is approximately 10 times more reactive than quercetin and 20 to 30 times greater than kaempferol, depending on the medium. PMID:26098745

  20. Parameter determination for singlet oxygen modeling of BPD-mediated PDT

    Science.gov (United States)

    McMillan, Dayton D.; Chen, Daniel; Kim, Michele M.; Liang, Xing; Zhu, Timothy C.

    2013-03-01

    Photodynamic therapy (PDT) offers a cancer treatment modality capable of providing minimally invasive localized tumor necrosis. To accurately predict PDT treatment outcome based on pre-treatment patient specific parameters, an explicit dosimetry model is used to calculate apparent reacted 1O2 concentration ([1O2]rx) at varied radial distances from the activating light source inserted into tumor tissue and apparent singlet oxygen threshold concentration for necrosis ([1O2]rx, sd) for type-II PDT photosensitizers. Inputs into the model include a number of photosensitizer independent parameters as well as photosensitizer specific photochemical parameters ξ σ, and β. To determine the specific photochemical parameters of benzoporphyrin derivative monoacid A (BPD), mice were treated with BPDPDT with varied light source strengths and treatment times. All photosensitizer independent inputs were assessed pre-treatment and average necrotic radius in treated tissue was determined post-treatment. Using the explicit dosimetry model, BPD specific ξ σ, and β photochemical parameters were determined which estimated necrotic radii similar to those observed in initial BPD-PDT treated mice using an optimization algorithm that minimizes the difference between the model and that of the measurements. Photochemical parameters for BPD are compared with those of other known photosensitizers, such as Photofrin. The determination of these BPD specific photochemical parameters provides necessary data for predictive treatment outcome in clinical BPD-PDT using the explicit dosimetry model.

  1. Fluorescence behavior and singlet oxygen generating abilities of aluminum phthalocyanine in the presence of anisotropic gold nanoparticles

    International Nuclear Information System (INIS)

    Mthethwa, Thandekile; Nyokong, Tebello

    2015-01-01

    Gold nanoparticles (spheres, rods and bipyramids) were synthesized. The nanocrystals were characterized by UV–visible spectrometry, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). The as prepared gold nanoparticles were then conjugated to a quaternized 2,(3)-tetra [2-(dimethylamino) ethanethio] substituted Al(OH) phthalocyanine (complex 1). The conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields and lifetimes. Conversely, an increase in the singlet oxygen quantum yields was observed for the conjugated complex 1 in the presence of AuNPs. - Highlights: • Gold nanoparticles (spheres, rods and bipyramids) were synthesized. • Gold nanoparticles were then conjugated to a quaternized ClAl phthalocyanine. • Conjugation of phthalocyanines with gold nanoparticles resulted in a decrease in the fluorescence quantum yields. • An increase in the singlet oxygen quantum yields was observed for the phthalocyanine in the presence of nanoparticles

  2. One-Pot Synthesis of (+)-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst

    OpenAIRE

    Bing Hong; Raphaël Lebeuf; Stéphanie Delbaere; Paul L. Alsters; Véronique Nardello-Rataj

    2016-01-01

    Efficient one-pot catalytic synthesis of (+)-nootkatone was performed from (+)-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i) singlet oxygenation of valencene according to the ene reaction; (ii) Schenck rearrangement of one hydroperoxide into the secondary β-hydroperoxide; and (iii) dehydration of the hydroperoxide into the desired (+)-nootkatone. The solvent effect on the hydroperoxide rearr...

  3. Oxidative damage of U937 human leukemic cells caused by hydroxyl radical results in singlet oxygen formation.

    Directory of Open Access Journals (Sweden)

    Marek Rác

    Full Text Available The exposure of human cells to oxidative stress leads to the oxidation of biomolecules such as lipids, proteins and nuclei acids. In this study, the oxidation of lipids, proteins and DNA was studied after the addition of hydrogen peroxide and Fenton reagent to cell suspension containing human leukemic monocyte lymphoma cell line U937. EPR spin-trapping data showed that the addition of hydrogen peroxide to the cell suspension formed hydroxyl radical via Fenton reaction mediated by endogenous metals. The malondialdehyde HPLC analysis showed no lipid peroxidation after the addition of hydrogen peroxide, whereas the Fenton reagent caused significant lipid peroxidation. The formation of protein carbonyls monitored by dot blot immunoassay and the DNA fragmentation measured by comet assay occurred after the addition of both hydrogen peroxide and Fenton reagent. Oxidative damage of biomolecules leads to the formation of singlet oxygen as conformed by EPR spin-trapping spectroscopy and the green fluorescence of singlet oxygen sensor green detected by confocal laser scanning microscopy. It is proposed here that singlet oxygen is formed by the decomposition of high-energy intermediates such as dioxetane or tetroxide formed by oxidative damage of biomolecules.

  4. Comparison of killing of gram-negative and gram-positive bacteria by pure singlet oxygen. [Salmonella typhimurium; Escherichia coli; Sarcina lutea; Staphylococcus aureus; Streptococcus lactis; Streptococcus faecalis

    Energy Technology Data Exchange (ETDEWEB)

    Dahl, T.A.; Midden, W.R. (Bowling Green State Univ., OH (USA)); Hartman, P.E. (Johns Hopkins Univ., Baltimore, MD (USA))

    1989-04-01

    Gram-negative and gram-positive bacteria were found to display different sensitivities to pure singlet oxygen generated outside of cells. Killing curves for Salmonella typhimurium and Escherichia coli strains were indicative of multihit killing, whereas curves for Sarcina lutea, Staphylococcus aureus, Streptococcus lactis, and Streptococcus faecalis exhibited single-hit kinetics. The S. typhimurium deep rough strain TA1975, which lacks nearly all of the cell wall lipopolysaccharide coat and manifests concomitant enhancement of penetration by some exogenous substances, responded to singlet oxygen with initially faster inactivation than did the S. typhimurium wild-type strain, although the maximum rates of killing appeared to be quite similar. The structure of the cell wall thus plays an important role in susceptibility to singlet oxygen. The outer membrane-lipopolysaccharide portion of the gram-negative cell wall initially protects the bacteria from extracellular singlet oxygen, although it may also serve as a source for secondary reaction products which accentuate the rates of cell killing. S. typhimurium and E. coli strains lacking the cellular antioxidant, glutathione, showed no difference from strains containing glutathione in response to the toxic effects of singlet oxygen. Strains of Sarcina lutea and Staphylococcus aureus that contained carotenoids, however, were far more resistant to singlet oxygen lethality than were both carotenoidless mutants of the same species and other gram-positive species lacking high levels of protective carotenoids.

  5. Generation and suppression of singlet oxygen in hair by photosensitization of melanin.

    Science.gov (United States)

    Chiarelli-Neto, Orlando; Pavani, Christiane; Ferreira, Alan S; Uchoa, Adjaci F; Severino, Divinomar; Baptista, Maurício S

    2011-09-15

    We have studied the spectroscopic properties of hair (white, blond, red, brown, and black) under illumination with visible light, giving special emphasis to the photoinduced generation of singlet oxygen ((1)O(2)). Irradiation of hair shafts (λ(ex)>400 nm) changed their properties by degrading the melanin. Formation of C3 hydroperoxides in the melanin indol groups was proven by (1)H NMR. After 532-nm excitation, all hair shafts presented the characteristic (1)O(2) emission (λ(em)=1270 nm), whose intensity varied inversely with the melanin content. (1)O(2) lifetime was also shown to vary with hair type, being five times shorter in black hair than in blond hair, indicating the role of melanin as a (1)O(2) suppressor. Lifetime ranged from tenths of a nanosecond to a few microseconds, which is much shorter than the lifetime expected for (1)O(2) in the solvents in which the hair shafts were suspended, indicating that (1)O(2) is generated and suppressed inside the hair structure. Both eumelanin and pheomelanin were shown to produce and to suppress (1)O(2), with similar efficiencies. The higher amount of (1)O(2) generated in blond hair and its longer lifetime is compatible with the stronger damage that light exposure causes in blond hair. We propose a model to explain the formation and suppression of (1)O(2) in hair by photosensitization of melanin with visible light and the deleterious effects that an excess of visible light may cause in hair and skin. Copyright © 2011. Published by Elsevier Inc.

  6. Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

    Directory of Open Access Journals (Sweden)

    Ashraf Khademzadeh

    2014-01-01

    Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

  7. Relationship between symmetry of porphyrinic pi-conjugated systems and singlet oxygen (1Delta g) yields: low-symmetry tetraazaporphyrin derivatives.

    Science.gov (United States)

    Ishii, Kazuyuki; Itoya, Hatsumi; Miwa, Hideya; Fujitsuka, Mamoru; Ito, Osamu; Kobayashi, Nagao

    2005-07-07

    We have investigated the excited-state properties and singlet oxygen ((1)Delta(g)) generation mechanism in phthalocyanines (4M; M = H(2), Mg, or Zn) and in low-symmetry metal-free, magnesium, and zinc tetraazaporphyrins (TAPs), that is, monobenzo-substituted (1M), adjacently dibenzo-substituted (2AdM), oppositely dibenzo-substituted (2OpM), and tribenzo-substituted (3M) TAP derivatives, whose pi conjugated systems were altered by fusing benzo rings. The S(1)(x) and S(1)(y) states (these lowest excited singlet states are degenerate in D(4)(h) symmetry) split in the low-symmetry TAP derivatives. The excited-state energies were quantitatively determined from the electronic absorption spectra. The lowest excited triplet (T(1)(x)) energies were also determined from phosphorescence spectra, while the second lowest excited triplet (T(1)(y)) states were evaluated by using the energy splitting between the T(1)(x) and T(1)(y) states previously reported (Miwa, H.; Ishii, K.; Kobayashi, N. Chem. Eur. J. 2004, 10, 4422-4435). The singlet oxygen quantum yields (Phi(Delta)) are strongly dependent on the pi conjugated system. In particular, while the Phi(Delta) value of 2AdH(2) is smallest in our system, that of 2OpH(2), an isomer of 2AdH(2), is larger than that of 4Zn, in contrast to the heavy atom effect. The relationship between the molecular structure and Phi(Delta) values can be transformed into a relationship between the S(1)(x) --> T(1)(y) intersystem crossing rate constant (k(ISC)) and the energy difference between the S(1)(x) and T(1)(y) states (DeltaE(S)(x)(T)(y)). In each of the Zn, Mg, and metal-free compounds, the Phi(Delta)/tau(F) values (tau(F): fluorescence lifetime), which are related to the k(ISC) values, are proportional to exp(-DeltaE(S)(x)(T)(y)), indicating that singlet oxygen ((1)Delta(g)) is produced via the T(1)(y) state and that the S(1)(x) --> T(1)(y) ISC process follows the energy-gap law. From the viewpoint of photodynamic therapy, our methodology

  8. Water vapor concentration measurement in singlet oxygen generator by using emission spectroscopy method and absorption at 1392nm

    Science.gov (United States)

    Zhao, Weili; Wang, Zengqiang; Fang, Benjie; Li, Qingwei; Jin, Yuqi; Sang, Fengting

    2005-12-01

    By using emission spectroscopy method and absorption at 1392nm, partial water pressure at the exit of a square pipe-array jet-type singlet oxygen generator (SPJSOG) for chemical oxygen-iodine laser (COIL) was measured. The water vapor fraction was calculated from the partial water pressure in the diagnostic cell when we assumed the water vapor fraction in the diagnostic cell is the same as that in the generator. The results from the two methods showed that the water vapor concentration is less than 0.08 in this SPJSOG during normal operation. The water vapor fraction decreases with the increasing of the pressure in the generator and rises with the increasing of buffer gas flow rate and the basic hydrogen peroxide (BHP) temperature in the case of constant chlorine flow rate. Measurements showed that the change of water vapor fraction due to BHP temperature could be ignored during normal operation. It is indicated that the gas flow velocity is the main reason that affects on the water vapor fraction in COIL. It is proved that the emission spectroscopy method is one of the simple and convenient ways to measure the water vapor concentration in singlet oxygen generator (SOG), especially in real time measurements. But absorption spectroscopy method, as a direct measurement, can give the more factual results of the water concentration.

  9. Irradiation- and Sensitizer-Dependent Changes in the Lifetime of Intracellular Singlet Oxygen Produced in a Photosensitized Process

    DEFF Research Database (Denmark)

    Silva, Elsa; Pedersen, Brian Wett; Breitenbach, Thomas

    2012-01-01

    Singlet oxygen, O2(a1Δg), was produced upon pulsed-laser irradiation of an intracellular photosensitizer and detected by its 1275 nm O2(a1Δg) →O2(X3Σg-) phosphorescence in time-resolved experiments using (1) individual mammalian cells on the stage of a microscope and (2) suspensions of mammalian...... appreciably as the cell progresses towards death. The results obtained from cell suspensions reflect key features that differentiate cell ensemble from single cell experiments (e.g., the ensemble experiment is more susceptible to the effects of sensitizer that has leaked out of the cell). Overall, the data...

  10. Study of the metastable singlet of molecular nitrogen and of oxygen atoms in discharges and post-discharges

    International Nuclear Information System (INIS)

    Magne, Lionel

    1991-01-01

    Whereas discharges in nitrogen, in oxygen and in their mixtures are used in many different industrial processes (surface treatment, nitridation, oxidation, and so on), in order to get a better knowledge on nitrogen electronic states, this research thesis reports the study of the metastable singlet state of molecular nitrogen, and of oxygen atoms in their fundamental state. The molecular metastable has been observed by far-UV optical emission spectroscopy, in the positive column of a continuous discharge and in time post-discharge. As far as continuous discharge is concerned, the author measured the vibrational distribution of this state. A kinetic model has been developed, and calculated vibrational distributions are in good agreement with measurements. The density of oxygen atoms in fundamental state in time post-discharge has been measured by far-UV absorption optical spectroscopy. The probability of atom re-association of glass walls is deduced from the obtained results [fr

  11. Aqueous singlet oxygen reaction kinetics of furfuryl alcohol: effect of temperature, pH, and salt content.

    Science.gov (United States)

    Appiani, Elena; Ossola, Rachele; Latch, Douglas E; Erickson, Paul R; McNeill, Kristopher

    2017-04-19

    The rate constant for the reaction between furfuryl alcohol (FFA) and singlet oxygen ( 1 O 2 ) in aqueous solution was measured as a function of temperature, pH and salt content employing both steady-state photolysis (β value determination) and time-resolved singlet oxygen phosphorescence methods. The latter provided more precise and reproducible data. The reaction rate constant, k rxn,FFA , had a relatively small temperature dependence, no pH dependence and showed a small increase in the presence of high salt concentrations (+19% with 1 M NaCl). A critical review of the available literature suggested that the widely used value of 1.2 × 10 8 M -1 s -1 is likely overestimated. Therefore, we recommend the use of 1.00 × 10 8 M -1 s -1 for reactions performed in low ionic strength aqueous solutions (freshwater) at 22 °C. Furthermore, corrections are provided that should be applied when working at higher or lower temperatures, and/or at high salt concentrations (seawater).

  12. Photogeneration of singlet oxygen by the phenothiazine derivatives covalently bound to the surface-modified glassy carbon

    Energy Technology Data Exchange (ETDEWEB)

    Blacha-Grzechnik, Agata, E-mail: agata.blacha@polsl.pl [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Piwowar, Katarzyna; Krukiewicz, Katarzyna [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland); Koscielniak, Piotr; Szuber, Jacek [Institute of Electronics, Silesian University of Technology, Akademicka 16, 44-100 Gliwice (Poland); Zak, Jerzy K. [Faculty of Chemistry, Silesian University of Technology, Strzody 9, 44-100 Gliwice (Poland)

    2016-05-15

    Highlights: • The selected group of four NH{sub 2}-derivatives of phenothiazine was grafted to Glassy Carbon (GC) surface. • The grafted phenothiazines are able to generate {sup 1}O{sub 2} when activated by the radiation. • Such modified solid surfaces may find their application in the wastewater treatment. - Abstract: The selected group of four amine-derivatives of phenothiazine was covalently grafted to the glassy carbon surface in the four-step procedure consisting of the electrochemical reduction of the diazonium salt followed by the electrochemical and chemical post-modification steps. The proposed strategy involves the bonding of linker molecule to which the photosensitizer is attached. The synthesized organic layers were characterized by means of cyclic voltammetry, XPS and Raman Spectroscopy. It was shown that the phenothiazines immobilized via proposed strategy retain their photochemical properties and are able to generate {sup 1}O{sub 2} when activated by the laser radiation. The effectiveness of in situ singlet oxygen generation by those new solid photoactive materials was determined by means of UVVis spectroscopy. The reported, covalently modified solid surfaces may find their application as the singlet oxygen photogenerators in the fine chemicals’ synthesis or in the wastewater treatment.

  13. Light absorption and the photoformation of hydroxyl radical and singlet oxygen in fog waters

    Science.gov (United States)

    Kaur, R.; Anastasio, C.

    2017-09-01

    The atmospheric aqueous-phase is a rich medium for chemical transformations of organic compounds, in part via photooxidants generated within the drops. Here we measure light absorption, photoformation rates and steady-state concentrations of two photooxidants - hydroxyl radical (•OH) and singlet molecular oxygen (1O2*) - in 8 illuminated fog waters from Davis, California and Baton Rouge, Louisiana. Mass absorption coefficients for dissolved organic compounds (MACDOC) in the samples are large, with typical values of 10,000-15,000 cm2 g-C-1 at 300 nm, and absorption extends to wavelengths as long as 450-600 nm. While nitrite and nitrate together account for an average of only 1% of light absorption, they account for an average of 70% of •OH photoproduction. Mean •OH photoproduction rates in fogs at the two locations are very similar, with an overall mean of 1.2 (±0.7) μM h-1 under Davis winter sunlight. The mean (±1σ) lifetime of •OH is 1.6 (±0.6) μs, likely controlled by dissolved organic compounds. Including calculated gas-to-drop partitioning of •OH, the average aqueous concentration of •OH is approximately 2 × 10-15 M (midday during Davis winter), with aqueous reactions providing approximately one-third of the hydroxyl radical source. At this concentration, calculated lifetimes of aqueous organics are on the order of 10 h for compounds with •OH rate constants of 1 × 1010 M-1 s-1 or higher (e.g., substituted phenols such as syringol (6.4 h) and guaiacol (8.4 h)), and on the order of 100 h for compounds with rate constants near 1 × 109 M-1 s-1 (e.g., isoprene oxidation products such as glyoxal (152 h), glyoxylic acid (58 h), and pyruvic acid (239 h)). Steady-state concentrations of 1O2* are approximately 100 times higher than those of •OH, in the range of (0.1-3.0) × 10-13 M. Since 1O2* is a more selective oxidant than •OH, it will only react appreciably with electron-rich species such as dimethyl furan (lifetime of 2.0 h) and

  14. Isomer distribution of hydroxyoctadecadienoates (HODE) and hydroxyeicosatetraenoates (HETE) produced in the plasma oxidation mediated by peroxyl radical, peroxynitrite, hypochlorite, 15-lipoxygenase, and singlet oxygen.

    Science.gov (United States)

    Umeno, Aya; Morita, Mayuko; Yoshida, Yasukazu; Naito, Yuji; Niki, Etsuo

    2017-12-01

    Free and ester forms of unsaturated fatty acids and cholesterol are oxidized in vivo by multiple oxidants to give diverse products. Some lipid oxidation is mediated by enzymes to selectively give specific products, while others proceed randomly to produce mixtures of many kinds of regioisomers and stereoisomers. The efficacy of antioxidants against lipid oxidation depends on the nature of the oxidants and therefore the identification of oxidant is important for understanding the roles and effects of lipid oxidation and antioxidants in vivo. In the present study, the isomer distribution of hydro(pero)xyoctadecadienoates (H(p)ODEs) and hydro(pero)xyeicosatetraenoates (H(p)ETEs), the most abundant lipid oxidation products found in human plasma, produced in the oxidation of plasma by peroxyl radicals, peroxynitrite, hypochlorite, 15-lipoxygenase, and singlet oxygen were examined. It was shown that 9- and 13-(E,E)-HODEs, 13(S)-(Z,E)-HODE, and 10- and 12-(Z,E)-HODEs were specific lipid oxidation products by free radical, 15-lipoxygenase, and singlet oxygen, respectively. The isomer distribution of HODEs produced by peroxynitrite was similar to that by peroxyl radical, suggesting that the peroxynitrite mediated lipid oxidation proceeds by free radical mechanisms. The production of HODEs and HETEs by hypochlorite was very small. HODEs may be a better biomarker than HETEs since linoleates are oxidized by simpler mechanisms than arachidonates and all the HODEs isomers can be quantified more easily. These products may be used as specific biomarkers for the identification of responsible oxidants and for the assessment of oxidant-specific lipid oxidation levels and effects of antioxidants in vivo. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Scavenging or Quenching Effect of Melanin on Superoxide Anion and Singlet Oxygen

    Science.gov (United States)

    Tada, Mika; Kohno, Masahiro; Niwano, Yoshimi

    2010-01-01

    Although photoprotective properties of skin melanin have been well documented, a few studies on the effect of melanin on reactive oxygen species (ROS) generated by ultraviolet (UV) irradiation have been reported. To study the interaction of melanin with ROS, scavenging or quenching effect of melanin on O2•− and 1O2 was examined by electron spin resonance (ESR)-spin trapping methods and a spectrophotometric method, respectively. Melanin potently interacted with O2•− generated in a hypoxanthine (HPX)-xanthine oxidase (XOD) reaction, and with 1O2 generated from a peroxidase, H2O2, and halide system. In the HPX-XOD reaction, it was proved that melanin doses not interfere with the enzyme reaction. It is confirmed that one of the mechanisms by which melanin protects UV-induced skin damage is likely scavenging or quenching activity against ROS such as O2•− and 1O2. PMID:20490317

  16. Influence of chemically produced singlet delta oxygen molecules on thermal ignition of O2-H2 mixtures

    Science.gov (United States)

    Vagin, N. P.; Kochetov, I. V.; Napartovich, A. P.; Yuryshev, N. N.

    2016-02-01

    Thermal ignition of the H2-O2 mixture with O2(a 1Δ g ) addition is studied experimentally and theoretically. The singlet delta oxygen was produced in a chemical generator. In this way, the competing chemical processes involving plasma produced chemically active O atoms and ozone (O3) were excluded. A satisfactory agreement is achieved between experimentally observed and numerically predicted values of the ignition time at the initial gas temperature (900-950) K and gas pressure (9-10) Torr. The percentage of the reactive channel in the binary collisions O2(a 1Δg) H is evaluated on the level (10-20)% for the H2-O2 mixture.

  17. Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal-organic framework.

    Science.gov (United States)

    Liu, Yangyang; Buru, Cassandra T; Howarth, Ashlee J; Mahle, John J; Buchanan, James H; DeCoste, Jared B; Hupp, Joseph T; Farha, Omar K

    2016-01-01

    A pyrene-based metal-organic framework (MOF) NU-1000 was used as a heterogeneous photocatalyst for the degradation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Using irradiation from a commercially available and inexpensive ultraviolet (UV) light-emitting diode (LED), singlet oxygen ( 1 O 2 ) is generated by NU-1000 and selectively oxidizes CEES to the nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO). More importantly, this method was tested on the warfare agent sulfur mustard (HD) for the first time using 1 O 2 and a MOF catalyst, and this method proved to be effective in oxidizing sulfur mustard to nontoxic products without forming the toxic sulfone by-product.

  18. One-Pot Synthesis of (+-Nootkatone via Dark Singlet Oxygenation of Valencene: The Triple Role of the Amphiphilic Molybdate Catalyst

    Directory of Open Access Journals (Sweden)

    Bing Hong

    2016-11-01

    Full Text Available Efficient one-pot catalytic synthesis of (+-nootkatone was performed from (+-valencene using only hydrogen peroxide and amphiphilic molybdate ions. The process required no solvent and proceeded in three cascade reactions: (i singlet oxygenation of valencene according to the ene reaction; (ii Schenck rearrangement of one hydroperoxide into the secondary β-hydroperoxide; and (iii dehydration of the hydroperoxide into the desired (+-nootkatone. The solvent effect on the hydroperoxide rearrangement is herein discussed. The amphiphilic dimethyldioctyl ammonium molybdate, which is also a balanced surfactant, played a triple role in this process, as molybdate ions catalyzed at both Step 1 and Step 3 and it allowed the rapid formation of a three-phase microemulsion system that highly facilitates product recovery. Preparative synthesis of the high added value (+-nootkatone was thus performed at room temperature with an isolated yield of 46.5%. This is also the first example of a conversion of allylic hydroperoxides into ketones catalyzed by molybdate ions.

  19. Two-Photon Irradiation of an Intracellular Singlet Oxygen Photosensitizer: Achieving Localized Sub-Cellular Excitation in Spatially-Resolved Experiments

    DEFF Research Database (Denmark)

    Pedersen, Brian Wett; Breitenbach, Thomas; Redmond, Robert W.

    2010-01-01

    The response of a given cell to spatially-resolved sub-cellular irradiation of a singlet oxygen photosensitizer (protoporphyrin IX, PpIX) using a focused laser was assessed. In these experiments, incident light was scattered over a volume greater than that defi ned by the dimensions of the laser...

  20. Preliminary study on singlet oxygen production using CeF.sub.3./sub.:Tb.sup.3+./sup.@SiO.sub.2./sub.-PpIX

    Czech Academy of Sciences Publication Activity Database

    Popovich, K.; Procházková, L.; Pelikánová, I.T.; Vlk, M.; Palkovský, M.; Jarý, Vítězslav; Nikl, Martin; Múčka, V.; Mihóková, Eva; Čuba, V.

    2016-01-01

    Roč. 90, Jul (2016), s. 325-328 ISSN 1350-4487 R&D Projects: GA ČR GA13-09876S; GA ČR GA13-28721S Institutional support: RVO:68378271 Keywords : singlet oxygen * cerium fluoride * photodynamic therapy * biofunctionalization * scintillator Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.442, year: 2016

  1. Singlet oxygen explicit dosimetry to predict long-term local tumor control for Photofrin-mediated photodynamic therapy

    Science.gov (United States)

    Penjweini, Rozhin; Kim, Michele M.; Ong, Yi Hong; Zhu, Timothy C.

    2017-02-01

    Although photodynamic therapy (PDT) is an established modality for the treatment of cancer, current dosimetric quantities do not account for the variations in PDT oxygen consumption for different fluence rates (φ). In this study we examine the efficacy of reacted singlet oxygen concentration ([1O2]rx) to predict long-term local control rate (LCR) for Photofrin-mediated PDT. Radiation-induced fibrosarcoma (RIF) tumors in the right shoulders of female C3H mice are treated with different in-air fluences of 225-540 J/cm2 and in-air fluence rate (φair) of 50 and 75 mW/cm2 at 5 mg/kg Photofrin and a drug-light interval of 24 hours using a 1 cm diameter collimated laser beam at 630 nm wavelength. [1O2]rx is calculated by using a macroscopic model based on explicit dosimetry of Photofrin concentration, tissue optical properties, tissue oxygenation and blood flow changes during PDT. The tumor volume of each mouse is tracked for 90 days after PDT and Kaplan-Meier analyses for LCR are performed based on a tumor volume <=100 mm3, for the four dose metrics light fluence, photosensitizer photobleaching rate, PDT dose and [1O2]rx. PDT dose is defined as a temporal integral of photosensitizer concentration and Φ at a 3 mm tumor depth. φ is calculated throughout the treatment volume based on Monte-Carlo simulation and measured tissue optical properties. Our preliminary studies show that [1O2]rx is the best dosimetric quantity that can predict tumor response and correlate with LCR. Moreover, [1O2]rx calculated using the blood flow changes was in agreement with [1O2]rx calculated based on the actual tissue oxygenation.

  2. Evaluation of singlet oxygen explicit dosimetry for predicting treatment outcomes of benzoporphyrin derivative monoacid ring A-mediated photodynamic therapy

    Science.gov (United States)

    Kim, Michele M.; Penjweini, Rozhin; Zhu, Timothy C.

    2017-02-01

    Existing dosimetric quantities do not fully account for the dynamic interactions between the key components of photodynamic therapy (PDT) or the varying PDT oxygen consumption rates for different fluence rates. Using a macroscopic model, reacted singlet oxygen ([) was calculated and evaluated for its effectiveness as a dosimetric metric for PDT outcome. Mice bearing radiation-induced fibrosarcoma tumors were treated with benzoporphyrin derivative monoacid ring A (BPD) at a drug-light interval of 3 h with various in-air fluences (30 to 350 J/cm2) and in-air fluence rates (50 to 150 mW/cm2). Explicit measurements of BPD concentration and tissue optical properties were performed and used to calculate [, photobleaching ratio, and PDT dose. For four mice, in situ measurements of O23 and BPD concentration were monitored in real time and used to validate the in-vivo photochemical parameters. Changes in tumor volume following treatment were used to determine the cure index, CI=1-k/kctr, where k and kctr are the tumor regrowth rates with PDT and without PDT, respectively. The correlation between CI and the dose metrics showed that the calculated [ at 3 mm is an effective dosimetric quantity for predicting treatment outcome and a clinically relevant tumor regrowth endpoint.

  3. Determination of singlet oxygen quenching and protection of biological systems by various extracts from seed of Rumex crispus L.

    Science.gov (United States)

    Suh, Hwa-Jin; Lee, Kyung-Seok; Kim, Seong-Ryul; Shin, Myoung-Ho; Park, Sanggyu; Park, Shin

    2011-02-07

    The 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging effect and total phenolic contents were evaluated for the screening of singlet oxygen ((1)O(2)) quenching efficacy of various seed extracts from Rumex crispus L. The butanol and ethyl-acetate extracts displayed remarkable effect of DPPH as compared to positive control ascorbic acid. The concentrations (QC(50)) of butanol and ethyl-acetate extracts required to exert 50% reducing effect on (1)O(2) were found to be 116 and 82 μg mL(-1), respectively. Both extracts were also found to protect the in vitro biological system from the detrimental effect of (1)O(2) on type II photosensitization in Escherichia coli, red blood cell, lactate dehydrogenase and histidine. Among all the tested extracts, the ethyl-acetate and butanol extracts contained higher amount of total phenolic contents. The results suggest that our study may contribute to the development of new bioactive products with potential applications to reduce photo-produced oxidative stress involving reactive oxygen species in living organisms. Copyright © 2010 Elsevier B.V. All rights reserved.

  4. Mechanisms of oxygen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Radmer, R; Cheniae, G

    1976-08-01

    The production of O/sub 2/ from water requires the collaboration of four oxidizing equivalents. When dark-adapted O/sub 2/ evolving photosynthetic material is illuminated by a sequence of short (less than 2 ..mu..sec) saturating flashes, the amount of O/sub 2/ evolved per flash oscillates with a period of four. This indicates that a charge-collector, operating with its own reaction center, successively collects and stores four oxidizing equivalents, which are used in a concerted oxidation of two water molecules. Luminescence, fluorescence, and pH changes also reflect this cycle of four. The O/sub 2/ precursor states are quite stable; under some conditions they can have a lifetime of several minutes. The O/sub 2/-yielding reactions and reactions associated with trap recovery are fast relative to the rate-limiting step of photosynthesis. The molecular identity of the charge-collector is unknown, but correlative evidence suggests that a manganese containing catalyst (approximately 4 Mn/charge collector) participates, possibly directly. Formation of the active Mn-containing catalyst occurs via a multi-quantum process occurring within the System II reaction center. The photoactivated catalyst, located on the inner face of the thylakoid membrane, remains permanently active and essentially inaccessible to chemicals other than analogs of H/sub 2/O (e.g., NH/sub 3/, NH/sub 2/OH). This O/sub 2/ evolving catalyst can be deactivated by a variety of treatments that do not alter the system II reaction center. Anions such as chloride seem to participate rather directly in the O/sub 2/ evolution process via unknown mechanism(s).

  5. Singlet oxygen explicit dosimetry to predict long-term local tumor control for BPD-mediated photodynamic therapy

    Science.gov (United States)

    Kim, Michele M.; Penjweini, Rozhin; Ong, Yi Hong; Zhu, Timothy C.

    2017-02-01

    Photodynamic therapy (PDT) is a well-established treatment modality for cancer and other malignant diseases; however, quantities such as light fluence, photosensitizer photobleaching rate, and PDT dose do not fully account for all of the dynamic interactions between the key components involved. In particular, fluence rate (Φ) effects are not accounted for, which has a large effect on the oxygen consumption rate. In this preclinical study, reacted singlet oxygen [1O2]rx was investigated as a dosimetric quantity for PDT outcome. The ability of [1O2]rx to predict the long-term local tumor control rate (LCR) for BPD-mediated PDT was examined. Mice bearing radioactivelyinduced fibrosarcoma (RIF) tumors were treated with different in-air fluences (250, 300, and 350 J/cm2) and in-air ϕ (75, 100, and150 mW/cm2) with a BPD dose of 1 mg/kg and a drug-light interval of 3 hours. Treatment was delivered with a collimated laser beam of 1 cm diameter at 690 nm. Explicit dosimetry of initial tissue oxygen concentration, tissue optical properties, and BPD concentration was used to calculate [1O2]rx. Φ was calculated for the treatment volume based on Monte-Carlo simulations and measured tissue optical properties. Kaplan-Meier analyses for LCR were done for an endpoint of tumor volume <= 100 mm3 using four dose metrics: light fluence, photosensitizer photobleaching rate, PDT dose, and [1O2]rx. PDT dose was defined as the product of the timeintegral of photosensitizer concentration and Φ at a 3 mm tumor depth. Preliminary studies show that [1O2]rx better correlates with LCR and is an effective dosimetric quantity that can predict treatment outcome.

  6. X-ray Inducible Luminescence and Singlet Oxygen Sensitization by an Octahedral Molybdenum Cluster Compound: A New Class of Nanoscintillators.

    Science.gov (United States)

    Kirakci, Kaplan; Kubát, Pavel; Fejfarová, Karla; Martinčík, Jiří; Nikl, Martin; Lang, Kamil

    2016-01-19

    Newly synthesized octahedral molybdenum cluster compound (n-Bu4N)2[Mo6I8(OOC-1-adamantane)6] revealed uncharted features applicable for the development of X-ray inducible luminescent materials and sensitizers of singlet oxygen, O2((1)Δg). The compound exhibits a red-NIR luminescence in the solid state and in solution (e.g., quantum yield of 0.76 in tetrahydrofuran) upon excitation by UV-vis light. The luminescence originating from the excited triplet states is quenched by molecular oxygen to produce O2((1)Δg) with a high quantum yield. Irradiation of the compound by X-rays generated a radioluminescence with the same emission spectrum as that obtained by UV-vis excitation. It proves the formation of the same excited triplet states regardless of the excitation source. By virtue of the described behavior, the compound is suggested as an efficient sensitizer of O2((1)Δg) upon X-ray excitation. The luminescence and radioluminescence properties were maintained upon embedding the compound in polystyrene films. In addition, polystyrene induced an enhancement of the radioluminescence intensity via energy transfer from the scintillating polymeric matrix. Sulfonated polystyrene nanofibers were used for the preparation of nanoparticles which form stable dispersions in water, while keeping intact the luminescence properties of the embedded compound over a long time period. Due to their small size and high oxygen diffusivity, these nanoparticles are suitable carriers of sensitizers of O2((1)Δg). The presented results define a new class of nanoscintillators with promising properties for X-ray inducible photodynamic therapy.

  7. Antibacterial nitric oxide- and singlet oxygen-releasing polystyrene nanoparticles responsive to light and temperature triggers

    Czech Academy of Sciences Publication Activity Database

    Dolanský, Jiří; Henke, P.; Malá, Z.; Žárská, L.; Kubát, Pavel; Mosinger, Jiří

    2018-01-01

    Roč. 10, č. 5 (2018), s. 2639-2648 ISSN 2040-3364 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : nanofiber materials * porphyrin photosensitizers * photophysical properties * reactive oxygen Subject RIV: CA - Inorganic Chemistry ; CF - Physical ; Theoretical Chemistry (UFCH-W) OBOR OECD: Inorganic and nuclear chemistry ; Physical chemistry (UFCH-W) Impact factor: 7.367, year: 2016

  8. Influence of gamma radiation and singlet oxygen on nucleic acid constituents

    International Nuclear Information System (INIS)

    Balland, Alain.

    1979-10-01

    The action of single oxygen on nucleosides proved to be extremely specific of deoxy-2' guanosine. The use of high performance liquid chromatography and spectrometric techniques (IR, mass and NMR) made it possible to isolate and characterise five main products of degradation. Ionizing radiations act mainly through radical species resulting from the radiolysis of water. The effects of the presence of DNA nucleosides in irradiated aqueous solutions of thymidine were investigated. It would appear, in these conditions, that the change in radio-sensitivity of thymidine in oxygenated solution can be explained essentially in terms of the competition of hydroxyl radicals. A study of the action of gamma rays on aqueous solutions of deoxy-2' guanilyl thymidine was carried out in the absence and presence of oxygen. The significant action of neutral radical species on the 'osidic' fragment explaining the break in the phosphodiester bond was noticed. The radio-induced modifications on the substrate were characterised indirectly by enzime hydrolysis (phosphodiesterasis). In an aerated aqueous solution, the monophosphate dinucleosides modified on the thymidine motive were identified by comparison with the substances obtained by synthesis. The characterisation of new substances and the study of synthetic ones required the use of NMR. Hence the configuration study of modified nucleosides was given much room [fr

  9. Characterization and singlet oxygen quenching capacity of spray-dried microcapsules of edible biopolymers containing antioxidant molecules.

    Science.gov (United States)

    Faria, Adelia F; Mignone, Ricardo A; Montenegro, Mariana A; Mercadante, Adriana Z; Borsarelli, Claudio D

    2010-07-14

    Microcapsules of gum arabic or maltodextrin 20DE containing antioxidant molecules (AOx), for example, carotenoids and tocopherol derivatives, were prepared by the spray-drying technique. The properties of these microcapsules were evaluated by several techniques, such as dynamic light scattering, scanning electronic microscopy, and steady-state and time-resolved fluorescence spectroscopy of microencapsulated pyrene. The quenching of photochemically generated singlet molecular oxygen ((1)O(2)) by the AOx in homogeneous solvents as well as in microcapsule solutions was evaluated using time-resolved phosphorescence detection of (1)O(2). The quenching rate constant of the process, k(Q)(AOx), was strongly dependent on the type of the AOx. These results are explained by compartmentalization effects of the AOx in the core of the microcapsules and the accessibility of (1)O(2). The contribution of the biopolymer as quencher of (1)O(2) was also investigated. The present results can be applied to the design of edible antioxidant microcapsules within the food and cosmetic industries.

  10. Polymeric micelles of zinc protoporphyrin for tumor targeted delivery based on EPR effect and singlet oxygen generation.

    Science.gov (United States)

    Iyer, Arun K; Greish, Khaled; Seki, Takahiro; Okazaki, Shoko; Fang, Jun; Takeshita, Keizo; Maeda, Hiroshi

    2007-01-01

    Polymeric micelles of zinc protoporphyrin (ZnPP) with water soluble biocompatible and amphiphilic polymer, polyethylene glycol (PEG) demonstrated unique characteristics to target tumor tissues selectively based on the enhanced permeability and retention (EPR) effect. The micellar macromolecular drug of ZnPP (SMA-ZnPP and PEG-ZnPP) previously showed notable anticancer activity as a consequence of selective tumor targeting ability and its potent HO-1 inhibitory potential, resulting in suppressed biliverdin/bilirubin production in tumors thereby leading to oxystress induced tumor cell killing. Furthermore, recent findings also showed that ZnPP efficiently generated reactive singlet oxygen under illumination of visible light, laser, or xenon light source, which could augment its oxystress induced cell killing abilities. In the present paper, we report the synergistic effects of light induced photosensitizing capabilities and HO-1 inhibitory potentials of these unique micelles when tested in vitro and in vivo on tumor models under localized, mild illumination conditions using a tungsten-xenon light source. The results indicate that these water soluble polymeric micelles of ZnPP portend to be promising candidates for targeted chemotherapy as well as photodynamic therapy against superficial tumors as well as solid tumors located at light penetrable depths.

  11. Influence of pulse-height discrimination threshold for photon counting on the accuracy of singlet oxygen luminescence measurement

    International Nuclear Information System (INIS)

    Lin, Huiyun; Chen, Defu; Wang, Min; Lin, Juqiang; Li, Buhong; Xie, Shusen

    2011-01-01

    Direct measurement of near-infrared (NIR) luminescence around 1270 nm is the golden standard of singlet oxygen ( 1 O 2 ) identification. In this study, the influence of pulse-height discrimination threshold on measurement accuracy of the 1 O 2 luminescence that is generated from the photoirradiation of meso-tetra (N-methyl-4-pyridyl) morphine tetra-tosylate (TMPyP) in aqueous solution was investigated by using our custom-developed detection system. Our results indicate that the discrimination threshold has a significant influence on the absolute 1 O 2 luminescence counts, and the optimal threshold for our detection system is found to be about − 41.2 mV for signal discrimination. After optimization, the derived triplet-state and 1 O 2 lifetimes of TMPyP in aqueous solution are found to be 1.73 ± 0.03 and 3.70 ± 0.04 µs, respectively, and the accuracy of measurement was further independently demonstrated using the laser flash photolysis technique

  12. Influence of pulse-height discrimination threshold for photon counting on the accuracy of singlet oxygen luminescence measurement

    Science.gov (United States)

    Lin, Huiyun; Chen, Defu; Wang, Min; Lin, Juqiang; Li, Buhong; Xie, Shusen

    2011-12-01

    Direct measurement of near-infrared (NIR) luminescence around 1270 nm is the golden standard of singlet oxygen (1O2) identification. In this study, the influence of pulse-height discrimination threshold on measurement accuracy of the 1O2 luminescence that is generated from the photoirradiation of meso-tetra (N-methyl-4-pyridyl) morphine tetra-tosylate (TMPyP) in aqueous solution was investigated by using our custom-developed detection system. Our results indicate that the discrimination threshold has a significant influence on the absolute 1O2 luminescence counts, and the optimal threshold for our detection system is found to be about - 41.2 mV for signal discrimination. After optimization, the derived triplet-state and 1O2 lifetimes of TMPyP in aqueous solution are found to be 1.73 ± 0.03 and 3.70 ± 0.04 µs, respectively, and the accuracy of measurement was further independently demonstrated using the laser flash photolysis technique.

  13. Involvement of Singlet Oxygen in 5-Aminolevulinic Acid-Induced Photodynamic Damage of Cucumber (Cucumis sativus L.) Chloroplasts 1

    Science.gov (United States)

    Chakraborty, Niranjan; Tripathy, Baishnab Charan

    1992-01-01

    Cucumber (Cucumis sativus L., cv Poinsette) plants were sprayed with 20 millimolar 5-aminolevulinic acid and then incubated in the dark for 14 hours. The intact chloroplasts were isolated from the above plants in the dark and were exposed to weak light (250 micromoles per square meter per second). Within 30 minutes, photosystem II activity was reduced by 50%. The singlet oxygen (1O2) scavengers, histidine and sodium azide (NaN3) significantly protected against the damage caused to photosystem II. The hydroxyl radical scavenger formate failed to protect the thylakoid membranes. The production of 1O2 monitored as N,N-dimethyl p-nitrosoaniline bleaching increased as a function of light exposure time of treated chloroplasts and was abolished by the 1O2 quencher, NaN3. Membrane lipid peroxidation monitored as malondialdehyde production was also significantly reduced when chloroplasts were illuminated in the presence of NaN3 and histidine. Protochlorophyllide was the most abundant pigment accumulated in intact chloroplasts isolated from 5-aminolevulinic acid-treated plants and was probably acting as type II photosensitizer. PMID:16668650

  14. Effects of pulse width and repetition rate of pulsed laser on kinetics and production of singlet oxygen luminescence

    Directory of Open Access Journals (Sweden)

    Defu Chen

    2016-11-01

    Full Text Available Pulsed and continuous-wave (CW lasers have been widely used as the light sources for photodynamic therapy (PDT treatment. Singlet oxygen (1O2 is known to be a major cytotoxic agent in type-II PDT and can be directly detected by its near-infrared luminescence at 1270nm. As compared to CW laser excitation, the effects of pulse width and repetition rate of pulsed laser on the kinetics and production of 1O2 luminescence were quantitatively studied during photosensitization of Rose Bengal. Significant difference in kinetics of 1O2 luminescence was found under the excitation with various pulse widths of nanosecond, microsecond and CW irradiation with power of 20mW. The peak intensity and duration of 1O2 production varied with the pulse widths for pulsed laser excitation, while the 1O2 was generated continuously and its production reached a steady state with CW excitation. However, no significant difference (P>0.05 in integral 1O2 production was observed. The results suggest that the PDT efficacy using pulsed laser may be identical to the CW laser with the same wavelength and the same average fluence rate below a threshold in solution.

  15. Correlation of in vivo tumor response and singlet oxygen luminescence detection in mTHPC-mediated photodynamic therapy

    Directory of Open Access Journals (Sweden)

    Brian C. Wilson

    2015-01-01

    Full Text Available Excited-state singlet oxygen (1O2, generated during photodynamic therapy (PDT, is believed to be the primary cytotoxic agent with a number of clinically approved photosensitizers. Its relative concentration in cells or tissues can be measured directly through its near-infrared (NIR luminescence emission, which has correlated well with in vitro cell and in vivo normal skin treatment responses. Here, its correlation with the response of tumor tissue in vivo is examined, using the photosensitizer meso-tetrahydroxyphenylchlorin (mTHPC in an animal model comprising luciferase- and green fluorescent protein (GFP-transduced gliosarcoma grown in a dorsal window chamber. The change in the bioluminescence signal, imaged pretreatment and at 2, 5 and 9 d post treatment, was used as a quantitative measure of the tumor response, which was classified in individual tumors as "non", "moderate" and "strong" in order to reduce the variance in the data. Plotting the bioluminescence-based response vs the 1O2 counts demonstrated clear correlation, indicating that 1O2 luminescence provides a valid dosimetric technique for PDT in tumor tissue.

  16. Ultrasound-assisted interaction between chlorin-e6 and human serum albumin: pH dependence, singlet oxygen production, and formulation effect

    Science.gov (United States)

    Mocanu, Mihaela N.; Yan, Fei

    2018-02-01

    The interaction between chlorin e6 (Ce6) and human serum albumin (HSA) in the presence and absence of ultrasound have been investigated by ultraviolet-visible absorption spectroscopy and fluorescence spectroscopy. Ce6 is found to bind strongly to HSA at or near physiological pH conditions, but the strength of the binding is significantly weakened at lower pHs. The intrinsic fluorescence of HSA is incrementally quenched with increasing concentration of Ce6, and the quenching is enhanced after exposure to high-frequency ultrasound. Our experimental results suggest that Ce6-induced sonodynamic oxidation of HSA is mainly mediated by singlet oxygen. The formulation of Ce6 by high molecular weight polyvinylpyrrolidone (PVP) increased its stability in aqueous solutions and its quantum yield of singlet oxygen under ultrasound irradiation.

  17. Thiocyanate potentiates antimicrobial photodynamic therapy: In situ generation of the sulfur trioxide radical anion by singlet oxygen

    Science.gov (United States)

    St Denis, Tyler G.; Vecchio, Daniela; Zadlo, Andrzej; Rineh, Ardeshir; Sadasivam, Magesh; Avci, Pinar; Huang, Liyi; Kozinska, Anna; Chandran, Rakkiyappan; Sarna, Tadeusz; Hamblin, Michael R.

    2013-01-01

    Antimicrobial photodynamic therapy (PDT) is used for the eradication of pathogenic microbial cells and involves the light excitation of dyes in the presence of O2, yielding reactive oxygen species including the hydroxyl radical (•OH) and singlet oxygen (1O2). In order to chemically enhance PDT by the formation of longer-lived radical species, we asked whether thiocyanate (SCN−) could potentiate the methylene blue (MB) and light-mediated killing of the gram-positive Staphylococcus aureus and the gram-negative Escherichia coli. SCN− enhanced PDT (10 μM MB, 5J/cm2 660 nm hv) killing in a concentration-dependent manner of S. aureus by 2.5 log10 to a maximum of 4.2 log10 at 10 mM (P < 0.001) and increased killing of E. coli by 3.6 log10 to a maximum of 5.0 log10 at 10 mM (P < 0.01). We determined that SCN− rapidly depleted O2 from an irradiated MB system, reacting exclusively with 1O2, without quenching the MB excited triplet state. SCN− reacted with 1O2, producing a sulfur trioxide radical anion (a sulfur-centered radical demonstrated by EPR spin trapping). We found that MB-PDT of SCN− in solution produced both sulfite and cyanide anions, and that addition of each of these salts separately enhanced MB-PDT killing of bacteria. We were unable to detect EPR signals of •OH, which, together with kinetic data, strongly suggests that MB, known to produce •OH and 1O2, may, under the conditions used, preferentially form 1O2. PMID:23969112

  18. Cross-talk between singlet oxygen- and hydrogen peroxide-dependent signaling of stress responses in Arabidopsis thaliana

    Science.gov (United States)

    Laloi, Christophe; Stachowiak, Monika; Pers-Kamczyc, Emilia; Warzych, Ewelina; Murgia, Irene; Apel, Klaus

    2007-01-01

    Upon a dark-to-light shift, the conditional fluorescent (flu) mutant of Arabidopsis releases singlet oxygen (1O2) within the plastid compartment. Distinct sets of nuclear genes are activated that are different from those induced by superoxide (O2•−) and/or hydrogen peroxide (H2O2), suggesting that different types of reactive oxygen species activate distinct signaling pathways. It is not known whether the pathways operate separately or interact with each other. We have addressed this problem by modulating noninvasively the level of H2O2 in plastids by means of a transgenic line that overexpresses the thylakoid-bound ascorbate peroxidase (tAPX). The overexpression of the H2O2-specific scavenger reduced strongly the activation of nuclear genes in plants treated with the herbicide paraquat that in the light leads to the enhanced generation of O2•− and H2O2. In the flu mutant overexpressing tAPX, the intensity of 1O2-mediated cell death and growth inhibition was increased when compared with the flu parental line. Also, the expression of most of the nuclear genes that were rapidly activated after the release of 1O2 was significantly higher in flu plants overexpressing tAPX, whereas in wild-type plants, overexpression of tAPX did not lead to visible stress responses and had only a very minor impact on nuclear gene expression. The results suggest that H2O2 antagonizes the 1O2-mediated signaling of stress responses as seen in the flu mutant. This cross-talk between H2O2- and 1O2-dependent signaling pathways might contribute to the overall stability and robustness of wild-type plants exposed to adverse environmental stress conditions. PMID:17197417

  19. Preliminary study on singlet oxygen production using CeF.sub.3./sub.:Tb.sup.3+./sup.@SiO.sub.2./sub.-PpIX.

    Czech Academy of Sciences Publication Activity Database

    Popovich, K.; Procházková, L.; Pelikánová, I.T.; Vlk, M.; Palkovský, M.; Jarý, Vítězslav; Nikl, Martin; Múčka, V.; Mihóková, Eva; Čuba, V.

    2016-01-01

    Roč. 90, Jul (2016), s. 325-328 ISSN 1350-4487. [International Conference on Luminescent Detectors and Transformers of Ionizing Radiation (LUMDETR). Tartu (Estonsko), 20.09.2015-25.09.2015] R&D Projects: GA ČR GA13-09876S; GA ČR GA13-28721S Institutional support: RVO:68378271 Keywords : singlet oxygen * cerium fluoride * photodynamic therapy * biofunctionalization * scintillator Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.442, year: 2016

  20. High-pressure gravity-independent singlet oxygen generator, laser nozzle, and iodine injection system for the chemical oxygen-iodine laser

    Science.gov (United States)

    Emanuel, George

    2004-09-01

    A novel approach is outlined for a singlet oxygen generator (SOG), a laser minimum length nozzle (MLN), and an iodine injector system for a chemical oxygen-iodine laser (COIL). A unified approach, referred to as a SOG/MLN/I2 system, is partly based on past experimental work. For instance, the SOG concept stems from sparger technology and a KSY fesibility experiment. A MLN with a curved sonic line is used for the laser nozzle, and slender struts are used for the injection, in the downstream direction, of iodine/helium vapor. The heated struts are located downstream of the nozzle's throat. The engineering logic behind the approach is discussed; it has a diversity of potential system benefits relative to current technology. These include a compact, scalable laser that can operate in space. The SOG operates at a significantly higher pressure with a high O2(1Δ) yield. In addition, basic hydrogen peroxide reconditioning is not required, a water vapor removal system is not required, and diluent may be unnecessary, although useful for pressure recovery. The impact on a COIL system in terms of power, efficiency, and pressure recovery is briefly assessed.

  1. BODIPY-doped silica nanoparticles with reduced dye leakage and enhanced singlet oxygen generation.

    Science.gov (United States)

    Wang, Zhuyuan; Hong, Xuehua; Zong, Shenfei; Tang, Changquan; Cui, Yiping; Zheng, Qingdong

    2015-07-27

    Photodynamic therapy (PDT) is a promising modality for cancer treatment. The essential element in PDT is the photosensitizer, which can be excited by light of a specific wavelength to generate cytotoxic oxygen species (ROS) capable of killing tumor cells. The effectiveness of PDT is limited in part by the low yield of ROS from existing photosensitizers and the unwanted side effects induced by the photosensitizers toward normal cells. Thus the design of nanoplatforms with enhanced PDT is highly desirable but remains challenging. Here, we developed a heavy atom (I) containing dipyrromethene boron difluoride (BODIPY) dye with a silylated functional group, which can be covalently incorporated into a silica matrix to form dye-doped nanoparticles. The incorporated heavy atoms can enhance the generation efficiency of ROS. Meanwhile, the covalently dye-encapsulated nanoparticles can significantly reduce dye leakage and subsequently reduce unwanted side effects. The nanoparticles were successfully taken up by various tumor cells and showed salient phototoxicity against these cells upon light irradiation, demonstrating promising applications in PDT. Moreover, the incorporated iodine atom can be replaced by a radiolabeled iodine atom (e.g., I-124, I-125). The resulting nanoparticles will be good contrast agents for positron emission tomography (PET) imaging with their PDT functionality retained.

  2. Marked improvement in photoinduced cell death by a new tris-heteroleptic complex with dual action: singlet oxygen sensitization and ligand dissociation.

    Science.gov (United States)

    Albani, Bryan A; Peña, Bruno; Leed, Nicholas A; de Paula, Nataly A B G; Pavani, Christiane; Baptista, Mauricio S; Dunbar, Kim R; Turro, Claudia

    2014-12-10

    The new tris-heteroleptic complex [Ru(bpy)(dppn)(CH3CN)2](2+) (3, bpy = 2,2'-bipyridine, dppn = benzo[i]dipyrido[3,2-a;2',3'-c]phenazine) was synthesized and characterized in an effort to generate a molecule capable of both singlet oxygen ((1)O2) production and ligand exchange upon irradiation. Such dual reactivity has the potential to be useful for increasing the efficacy of photochemotherapy drugs by acting via two different mechanisms simultaneously. The photochemical properties and photoinduced cytotoxicity of 3 were compared to those of [Ru(bpy)2(dppn)](2+) (1) and [Ru(bpy)2(CH3CN)2](2+) (2), since 1 sensitizes the production of (1)O2 and 2 undergoes ligand exchange of the monodentate CH3CN ligands with solvent when irradiated. The quantum yield of (1)O2 production was measured to be 0.72(2) for 3 in methanol, which is slightly lower than that of 1, Φ = 0.88(2), in the same solvent (λirr = 460 nm). Complex 3 also undergoes photoinduced ligand exchange when irradiated in H2O (λirr = 400 nm), but with a low quantum efficiency (action complex is more photoactive toward cells in spite of its low ligand exchange quantum yield.

  3. Experimental and theoretical studies of nuclear generation of ozone and its photolysis into singlet delta oxygen

    International Nuclear Information System (INIS)

    Elsayed-Ali, H.E.

    1985-01-01

    A series of measurements of O 3 yield in nuclear induced O 2 and O 2 -SF 6 discharges created by bombardment with energetic particles from the 10 B(n,α) 7 Li reaction are reported. Continuous irradiation at dose ratios of 10 15 -10 17 eV.cm -3 .s -1 and pulsed irradiation (approx.10 ms FWHM) at a peak dose rate of approx.10 20 eV.cm -3 .s -1 were conducted. At the lower dose rates, SF 6 addition generally increased the ozone yield, which at the high dose rates, SF 6 addition decreased the observed ozone concentration. A numerical model was developed and applied to experimental conditions. The steady-state ozone concentration was found to be limited by the reaction O 3 - + O 3 → 2O 2 + O 2 - . A simplified analytical model of steady-state conditions was used to predict model sensitivity to various parameters. In addition to dose rate effects, pressure and temperature effect on ozone production were discussed. The present study was extended to noble gas (He, Ne, and Ar)-O 2 and noble gas - O 2 -SF 6 mixtures. Without SF 6 , steady-state ozone concentrations were found to be about an order of magnitude lower than that observed for oxygen at similar dose rates. Addition of SF 6 was found to significantly increase the steady-state ozone concentration (3-6 times) in noble gas-O 2 mixtures. The developed models were amended to study noble gas-O 2 discharges. A detailed computer model of ultraviolet irradiation of O 3 -O 2 -noble gas mixtures was presented. Dependence of O 2 (a 1 Δ/sub g/) yield on various parameters was investigated. Conditions needed to create O 2 (a 1 Δ/sub g/) concentrations sufficient for pumping an atomic iodine laser were identified. The model was tested by applying it to date on quantum yield of ozone decomposition for various mixtures and by observation of the absolute O 2 (a 1 Δ/sub g/) concentration generated under various conditions

  4. Mitochondria Targetable Time-Gated Luminescence Probe for Singlet Oxygen Based on a β-Diketonate-Europium Complex.

    Science.gov (United States)

    Sun, Jingyan; Song, Bo; Ye, Zhiqiang; Yuan, Jingli

    2015-12-21

    Singlet oxygen ((1)O2) plays a key role in the photodynamic therapy (PDT) technique of neoplastic diseases. In this work, by using a 9,10-dimethyl-2-anthryl-containing β-diketone, 1,1,1,2,2-pentafluoro-5-(9',10'-dimethyl-2'-anthryl)-3,5-pentanedione (Hpfdap), as a (1)O2-recognition ligand, a novel β-diketonate-europium(III) complex that can act as a luminescence probe for (1)O2, [Eu(pfdap)3(tpy)] (tpy = 2,2',2″-terpyridine), has been designed and synthesized for the time-gated luminescence detection of (1)O2 in living cells. The complex is weakly luminescent due to the quenching effect of 9,10-dimethyl-2-anthryl groups. After reaction with (1)O2, accompanied by the formation of endoperoxides of 9,10-dimethyl-2-anthryl groups, the luminescence quenching disappears, so that the long-lived luminescence of the europium(III) complex is switched on. The complex showed highly selective luminescence response to (1)O2 with a remarkable luminescence enhancement. Combined with the time-gated luminescence imaging technique, the complex was successfully used as a luminescent probe for the monitoring of the time-dependent generation of (1)O2 in 5-aminolevulinic acid (a PDT drug) loaded HepG2 cells during the photodynamic process. In addition, by coloading the complex and a mitochondrial indicator, Mito-Tracker Green, into HepG2 cells, the specific localization of [Eu(pfdap)3(tpy)] molecules in mitochondria of HepG2 cells was demonstrated by confocal fluorescence imaging measurements.

  5. Ion-induced stacking of photosensitizer molecules can remarkably affect the luminescence detection of singlet oxygen in Candida albicans cells

    Science.gov (United States)

    Felgenträger, Ariane; Gonzales, Fernanda Pereira; Maisch, Tim; Bäumler, Wolfgang

    2013-04-01

    Singlet oxygen (O21) is an important reactive intermediate in photodynamic reactions, particularly in antimicrobial PDT (aPDT). The detection of O21 luminescence is frequently used to elucidate the role of O21 in various environments, particularly in microorganisms and human cells. When incubating the fungus, Candida albicans, with porphyrins XF73 (5,15-bis-[4-(3-Trimethylammonio-propyloxy)-phenyl]-porphyrin) or TMPyP (5,10,15,20-Tetrakis(1-methyl-4-pyridinio)-porphyrin tetra(p-toluenesulfonate)), the O21 luminescence signals were excellent for TMPyP. In case of XF73, the signals showed strange rise and decay times. Thus, O21 generation of XF73 was investigated and compared with TMPyP. Absorption spectroscopy of XF73 showed a change in absorption cross section when there was a change in the concentration from 1×10-6 M to 1×10-3 M indicating an aggregation process. The addition of phosphate buffered saline (PBS) substantially changed O21 luminescence in XF73 solution. Detailed experiments provided evidence that the PBS constituents NaCl and KCl caused the change of O21 luminescence. The results also indicate that Cl- ions may cause aggregation of XF73 molecules, which in turn enhances self-quenching of O21 via photosensitizer molecules. These results show that some ions, e.g., those present in cells in vitro or added by PBS, can considerably affect the detection and the interpretation of time-resolved luminescence signals of O21, particularly in in vitro and in vivo. These effects should be considered for any other photosensitizer used in photodynamic processes.

  6. Singlet oxygen generation in O2 flow excited by RF discharge: I. Homogeneous discharge mode: α-mode

    International Nuclear Information System (INIS)

    Braginskiy, O V; Vasilieva, A N; Klopovskiy, K S; Kovalev, A S; Lopaev, D V; Proshina, O V; Rakhimova, T V; Rakhimov, A T

    2005-01-01

    The production and transport dynamics of O 2 (a 1 Δ g ) and O 2 (b 1 Σ g + ) molecules as well as O( 3 P) atoms has been studied in an O 2 flow excited by a 13.56 MHz RF discharge in a quartz tube at pressures of 1-20 Torr. It has been shown that the densities of O 2 (a 1 Δ g ) and O( 3 P) are saturated with increasing energy input into the discharge. The maximum yield of singlet oxygen (SO) and the O 2 dissociation degree drops with pressure. It is demonstrated that depending on the energy input the RF discharge can exist in three modes: I-in the spatially homogeneous mode or α-mode; III-in the substantially inhomogeneous mode, when plasma jets are present outside the discharge; and II-in the transient mode between modes I and III. In this paper only the homogeneous mode of RF discharge in the O 2 flow is considered in detail. A self-consistent model of the α-mode is developed, that allows us to analyse elementary processes responsible for the production and loss of O 2 (a 1 Δ g ) and O 2 (b 1 Σ g + ) molecules as well as O( 3 P) atoms in detail. To verify both the kinetic scheme of the model and the conclusions, some experiments have been carried out at lower flow velocities and higher pressures (≥10 Torr), when the stationary densities of O 2 (a 1 Δ g ), O 2 (b 1 Σ g + ) and O( 3 P) in the discharge area were established not by the escape of particles but by the losses due to the volumetric and surface reactions. The O 2 (b 1 Σ g + ) density under these conditions is determined by the balance of O 2 (b 1 Σ g + ) production by both direct electron impact and electronic excitation transfer from metastable O( 1 D) atoms and deactivation by oxygen atoms and tube walls, including quenching by ozone in the afterglow. The O( 3 P) density is determined by the balance between the production through O 2 dissociation by electron impact and heterogeneous loss at the wall recombination. The stationary density of O 2 (a 1 Δ g ) is provided by the processes of O

  7. A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers

    Science.gov (United States)

    2016-08-24

    Phys. Chem. B 2015, 119, 7644−7650. (17) Zirzlmeier, J.; Lehnherr, D.; Coto, P. B.; Chernick, E. T.; Casillas, R.; Basel , B. S.; Thoss, M.; Tykwinski...Arago,́ J.; Serrano-Perez, J. J.; Ortí, E.; Loṕez Navarrete, J. T.; Takimiya, K.; Casanova, D.; Casado, J.; Goodson, T., III High Yield Ultrafast...theory of singlet exciton fission. III . Crystalline pentacene. J. Chem. Phys. 2014, 141, 074705. (32) Zeng, T.; Hoffmann, R.; Ananth, N. The Low-Lying

  8. Poly(D, L-lactide-co-glycolide) nanoparticles as delivery agents for photodynamic therapy: enhancing singlet oxygen release and photototoxicity by surface PEG coating.

    Science.gov (United States)

    Boix-Garriga, Ester; Acedo, Pilar; Casadó, Ana; Villanueva, Angeles; Stockert, Juan Carlos; Cañete, Magdalena; Mora, Margarita; Sagristá, Maria Lluïsa; Nonell, Santi

    2015-09-11

    Poly(D, L-lactide-co-glycolide) (PLGA) nanoparticles (NPs) are being considered as nanodelivery systems for photodynamic therapy. The physico-chemical and biological aspects of their use remain largely unknown. Herein we report the results of a study of PLGA NPs for the delivery of the model hydrophobic photosensitizer ZnTPP to HeLa cells. ZnTPP was encapsulated in PLGA with high efficiency and the NPs showed negative zeta potentials and diameters close to 110 nm. Poly(ethylene glycol) (PEG) coating, introduced to prevent opsonization and clearance by macrophages, decreased the size and zeta potential of the NPs by roughly a factor of two and improved their stability in the presence of serum proteins. Photophysical studies revealed two and three populations of ZnTPP and singlet oxygen in uncoated and PEGylated NPs, respectively. Singlet oxygen is confined within the NPs in bare PLGA while it is more easily released into the external medium after PEG coating, which contributes to a higher photocytotoxicity towards HeLa cells in vitro. PLGA NPs are internalized by endocytosis, deliver their cargo to lysosomes and induce cell death by apoptosis upon exposure to light. In conclusion, PLGA NPs coated with PEG show high potential as delivery systems for photodynamic applications.

  9. Investigation of the singlet delta oxygen and ozone yields from the pulsed radiolysis of oxygen and oxygen-noble gas mixtures

    International Nuclear Information System (INIS)

    Zediker, M.S.

    1984-01-01

    The experiments discussed herein were performed with a flowing gas apparatus coupled to the University of Illinois TRIGA reactor. The detectors (lambda = 1.27 μ 634 nm) were calibrated with a novel NO 2 titration scheme and the absorbed dose was estimated from the ozone concentrations measured in pure oxygen. The results of these experiments revealed an O 2 (a 1 Δ) production efficiency of 0.14% for direct nuclear pumping in an argon-oxygen mixture. Extensive modeling of the oxygen and argon-oxygen mixtures were benchmarked against these and other experiments. However, good agreement over a broad absorbed dose range was only possible if the O 4 + + O 4 - neutralization reaction was assumed to be nondissociative. In a second set of experiments with a nuclear sustained electrical discharge (low E/N), the O 2 (a 1 Δ) production efficiency was approx.0.40% for the electrical power densities examined. In addition, the O 2 (a 1 Δ) was observed to scale with the square root of the electrical power deposition but was independent of the oxygen concentration. A simple analytic model was developed which explains this behavior as a characteristic of an externally sustained discharge involving an electron attaching gas such as oxygen. The results of these experiments and the modeling of the chemical kinetics are discussed with an emphasis on optimizing the O 2 (a 1 Δ) and O 3 yields

  10. Singlet Fission

    Czech Academy of Sciences Publication Activity Database

    Smith, M. B.; Michl, Josef

    2010-01-01

    Roč. 110, č. 11 (2010), s. 6891-6936 ISSN 0009-2665 Grant - others:Department of Energy(US) DE- FG36 -08GO18017 Institutional research plan: CEZ:AV0Z40550506 Keywords : solar energy conversion * photovoltaics * singlet fission Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 33.033, year: 2010

  11. Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro

    KAUST Repository

    Filatov, Mikhail A.

    2017-04-14

    Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of the alkyl substituents in the BODIPY subunit defines the site of 1O2 addition. Novel bis- and tetraepoxides and bicyclic acetal products, arising from rearrangements of anthracene endoperoxides were isolated and characterized. 1O2 generation by BADs in living cells enables visualization of the dyads distribution, promising new imaging applications.

  12. Mechanisms of group A Streptococcus resistance to reactive oxygen species

    Science.gov (United States)

    Henningham, Anna; Döhrmann, Simon; Nizet, Victor; Cole, Jason N.

    2015-01-01

    Streptococcus pyogenes, also known as group A Streptococcus (GAS), is an exclusively human Gram-positive bacterial pathogen ranked among the ‘top 10’ causes of infection-related deaths worldwide. GAS commonly causes benign and self-limiting epithelial infections (pharyngitis and impetigo), and less frequent severe invasive diseases (bacteremia, toxic shock syndrome and necrotizing fasciitis). Annually, GAS causes 700 million infections, including 1.8 million invasive infections with a mortality rate of 25%. In order to establish an infection, GAS must counteract the oxidative stress conditions generated by the release of reactive oxygen species (ROS) at the infection site by host immune cells such as neutrophils and monocytes. ROS are the highly reactive and toxic byproducts of oxygen metabolism, including hydrogen peroxide (H2O2), superoxide anion (O2•−), hydroxyl radicals (OH•) and singlet oxygen (O2*), which can damage bacterial nucleic acids, proteins and cell membranes. This review summarizes the enzymatic and regulatory mechanisms utilized by GAS to thwart ROS and survive under conditions of oxidative stress. PMID:25670736

  13. Mechanisms of group A Streptococcus resistance to reactive oxygen species.

    Science.gov (United States)

    Henningham, Anna; Döhrmann, Simon; Nizet, Victor; Cole, Jason N

    2015-07-01

    Streptococcus pyogenes, also known as group A Streptococcus (GAS), is an exclusively human Gram-positive bacterial pathogen ranked among the 'top 10' causes of infection-related deaths worldwide. GAS commonly causes benign and self-limiting epithelial infections (pharyngitis and impetigo), and less frequent severe invasive diseases (bacteremia, toxic shock syndrome and necrotizing fasciitis). Annually, GAS causes 700 million infections, including 1.8 million invasive infections with a mortality rate of 25%. In order to establish an infection, GAS must counteract the oxidative stress conditions generated by the release of reactive oxygen species (ROS) at the infection site by host immune cells such as neutrophils and monocytes. ROS are the highly reactive and toxic byproducts of oxygen metabolism, including hydrogen peroxide (H2O2), superoxide anion (O2•(-)), hydroxyl radicals (OH•) and singlet oxygen (O2*), which can damage bacterial nucleic acids, proteins and cell membranes. This review summarizes the enzymatic and regulatory mechanisms utilized by GAS to thwart ROS and survive under conditions of oxidative stress. © FEMS 2015.

  14. Modulation of the Singlet Oxygen Generation from the Double Strand DNA-SYBR Green I Complex Mediated by T-Melamine-T Mismatch for Visual Detection of Melamine.

    Science.gov (United States)

    Hu, Hao; Zhang, Jinyi; Ding, Yu; Zhang, Xinfeng; Xu, Kailai; Hou, Xiandeng; Wu, Peng

    2017-05-02

    Singlet oxygen ( 1 O 2 ), generated via photosensitization, has been proved to oxidize chromogenic substrates with neither H 2 O 2 oxidation nor enzyme (horseradish peroxidase, HRP) catalysis. Of the various methods for modulation of the 1 O 2 generation, DNA-controlled photosensitization received great attention. Therefore, integration of the formation/deformation DNA structures with DNA-controlled photosensitization will be extremely appealing in visual biosensor developments. Here, the stable melamine-thymine complex was explored in combination with DNA-controlled photosensitization for visual detection of melamine. A T-rich single stand DNA was utilized as the recognition unit. Upon the formation of the T-M-T complex, double stand DNA was formed, which was ready for the binding of SYBR Green I and activated the photosensitization. Subsequent oxidation of TMB allowed visual detection of melamine in dairy products, with spike-recoveries ranging from 94% to 106%.

  15. C60 and Sc3N@C80(TMB-PPO derivatives as constituents of singlet oxygen generating, thiol-ene polymer nanocomposites

    Directory of Open Access Journals (Sweden)

    Ashli R. Toles

    2016-07-01

    Full Text Available Numerous functionalization methods have been employed to increase the solubility, and therefore, the processability of fullerenes in composite structures, and of these radical addition reactions continue to be an important methodology. C60 and Sc3N@C80 derivatives were prepared via radical addition of the photodecomposition products from the commercial photoinitiator TMB-PPO, yielding C60(TMB-PPO5 and Sc3N@C80(TMB-PPO3 as preferred soluble derivatives obtained in high yields. Characterization of the mixture of isomers using standard techniques suggests an overall 1PPO:6TMB ratio of addends, reflecting the increased reactivity of the carbon radical. Although, a higher percentage of PPO is observed in the Sc3N@C80(TMB-PPO3 population, perhaps due to reverse electronic requirements of the substrate. Visually dispersed thiol-ene nanocomposites with low extractables were prepared using two monomer compositions (PETMP:TTT and TMPMP:TMPDE with increasing fullerene derivative loading to probe network structure-property relationships. Thermal stability of the derivatives and the resulting networks decreased with increased functionality and at high fullerene loadings, respectively. TMPMP:TMPDE composite networks show well-dispersed derivatives via TEM imaging, and increasing Tg’s with fullerene loading, as expected for the incorporation of a more rigid network component. PETMP:TTT composites show phase separation in TEM, which is supported by the observed Tg’s. Singlet oxygen generation of the derivatives decreases with increased functionality; however, this is compensated for by the tremendous increase in solubility in organic solvents and miscibility with monomers. Most importantly, singlet oxygen generation from the composites increased with fullerene derivative loading, with good photostability of the networks.

  16. Calculation of singlet oxygen dose using explicit and implicit dose metrics during benzoporphyrin derivative monoacid ring A (BPD-MA)-PDT in vitro and correlation with MLL cell survival.

    Science.gov (United States)

    Weston, Mark A; Patterson, Michael S

    2011-01-01

    Photodynamic therapy (PDT) oxygen consumption, clonogenic cell survival, fluorescence photobleaching and photoproduct formation were investigated during benzoporphyrin derivative monoacid (BPD-MA)-PDT of MAT-LyLu cells in vitro. Cells were incubated with BPD-MA concentrations of 0.1, 0.5 or 2.5 μg mL(-1) for 2 h and then treated with 405 nm light under oxygenated and hypoxic conditions. Fluorescence spectra were acquired during treatment, and photobleaching and photoproduct generation were quantified using singular value decomposition of the spectra. Cell survival was measured at set times during the treatment using a colony-forming assay. The amount of oxygen consumed by PDT per photon absorbed decreased with BPD-MA intracellular concentration. Survival was correlated with the total amount of oxygen consumed by PDT per unit volume, which is assumed to be equivalent to the amount of singlet oxygen that reacted. A photobleaching-based singlet oxygen dose metric was also found to predict survival independent of intracellular BPD-MA concentration. The BPD-MA photoproduct was bleached during the treatment. Two singlet oxygen dose metrics based on photoproduct kinetics could not be correlated with cell survival over the full range of intracellular BPD-MA concentrations used. © 2011 The Authors. Photochemistry and Photobiology © 2011 The American Society of Photobiology.

  17. Molecular mechanisms of oxygen activation

    National Research Council Canada - National Science Library

    Hayaishi, Osamu

    1974-01-01

    ... OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER. ACADEMIC PRESS, INC. I l l Fifth Avenue, New York, New York 10003 United Kingdom ACADEMIC Edition PRESS, publis...

  18. Roles of singlet oxygen and triplet excited state of dissolved organic matter formed by different organic matters in bacteriophage MS2 inactivation

    KAUST Repository

    Rosado-Lausell, Sahid L.

    2013-09-01

    Inactivation of bacteriophage MS2 by reactive oxygen species (ROS) and triplet excited state of dissolved organic matter (3DOM*) produced by irradiation of natural and synthetic sensitizers with simulated sunlight of wavelengths greater than 320nm was investigated. Natural sensitizers included purified DOM isolates obtained from wastewater and river waters, and water samples collected from Singapore River, Stamford Canal, and Marina Bay Reservoir in Singapore. Linear correlations were found between MS2 inactivation rate constants (kobs) and the photo-induced reaction rate constants of 2,4,6-trimethylphenol (TMP), a probe compound shown to react mainly with 3DOM*. Linear correlations between MS2 kobs and singlet oxygen (1O2) concentrations were also found for both purified DOM isolates and natural water samples. These correlations, along with data from quenching experiments and experiments with synthetic sensitizers, Rose Bengal (RB), 3\\'-methoxyacetophenone (3\\'-MAP), and nitrite (NO2-), suggest that 1O2, 3DOM*, and hydroxyl radicals (•OH) could inactivate bacteriophage MS2. Linear correlations between MS2 kobs and Specific Ultraviolet Absorption determined at 254nm (SUVA254) were also found for both purified DOM isolates and natural samples. These results suggest the potential use of TMP as a chemical probe and SUVA254 as an indicator for virus inactivation in natural and purified DOM water samples. © 2013 Elsevier Ltd.

  19. Bovine Serum Albulmin Protein-Templated Silver Nanocluster (BSA-Ag13): An Effective Singlet Oxygen Generator for Photodynamic Cancer Therapy.

    Science.gov (United States)

    Yu, Yong; Geng, Junlong; Ong, Edward Yong Xi; Chellappan, Vijila; Tan, Yen Nee

    2016-10-01

    This paper reports a novel synthesis approach of bovine serum albumin (BSA) protein-templated ultrasmall (BSA-Ag 13 NC (i.e., 13 Ag atoms per cluster) is successfully synthesized for the first time by using NaOH-dissolved NaBH 4 solution as the controlling reducing agent. The ubiquitous size of BSA-Ag 13 NC results in unique behaviors of its photoexcited states as characterized by the ultrafast laser spectroscopy using time-correlated single photon counting and transient absorption techniques. In particular, triply excited states can be largely present in the excited BSA-Ag 13 NC and readily sensitized molecular oxygen to produce singlet oxygen ( 1 O 2 ) with a high quantum efficiency (≈1.26 using Rose Bengal as a standard). This value is much higher than its Au analogue (i.e., ≈0.07 for BSA-Au 25 NC) and the commonly available photosensitizers. Due to the good cellular uptake and inherent biocompatibility imparted by the surface protein, BSA-Ag 13 NC can be applied as an effective PDT agent in generating 1 O 2 to kill cancer cell as demonstrated in this study. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Singlet oxygen luminescence as an in vivo photodynamic therapy dose metric: validation in normal mouse skin with topical amino-levulinic acid

    Science.gov (United States)

    Niedre, M J; Yu, C S; Patterson, M S; Wilson, B C

    2005-01-01

    Although singlet oxygen (1O2) has long been proposed as the primary reactive oxygen species in photodynamic therapy (PDT), it has only recently been possible to detect it in biological systems by its luminescence at 1270 nm. Having previously demonstrated this in vitro and in vivo, we showed that cell survival was strongly correlated to the 1O2 luminescence in cell suspensions over a wide range of treatment parameters. Here, we extend this to test the hypothesis that the photobiological response in vivo is also correlated with 1O2 generation, independent of individual treatment parameters. The normal skin of SKH1-HR hairless mice was sensitised with 20% amino-levulinic acid-induced protoporophyrin IX and exposed to 5, 11, 22 or 50 J cm−2 of pulsed 523 nm light at 50 mW cm−2, or to 50 J cm−2 at 15 or 150 mW cm−2. 1O2 luminescence was measured during treatment and the photodynamic response of the skin was scored daily for 2 weeks after treatment. As observed by other authors, a strong irradiance dependence of the PDT effect was observed. However, in all cases the responses increased with the 1O2 luminescence, independent of the irradiance, demonstrating for the first time in vivo an unequivocal mechanistic link between 1O2 generation and photobiological response. PMID:15655542

  1. Interaction of singlet oxygen with bovine serum albumin and the role of the protein nano-compartmentalization

    Czech Academy of Sciences Publication Activity Database

    Gimenez, R.E.; Vargová, Veronika; Rey, V.; Turbay, M.B.E.; Abatedaga, I.; Vieyra, F.E.M.; Zanini, V.I.P.; Ortiz, J.H.M.; Katz, N. E.; Ostatná, Veronika; Borsarelli, C.D.

    2016-01-01

    Roč. 94, MAY2016 (2016), s. 99-109 ISSN 0891-5849 R&D Projects: GA ČR GBP206/12/G151 Institutional support: RVO:68081707 Keywords : oxidative stress * molecular-oxygen * amino-acids Subject RIV: BO - Biophysics Impact factor: 5.606, year: 2016

  2. Low Oxygen Response Mechanisms in Green Organisms

    Directory of Open Access Journals (Sweden)

    Pierdomenico Perata

    2013-02-01

    Full Text Available Low oxygen stress often occurs during the life of green organisms, mostly due to the environmental conditions affecting oxygen availability. Both plants and algae respond to low oxygen by resetting their metabolism. The shift from mitochondrial respiration to fermentation is the hallmark of anaerobic metabolism in most organisms. This involves a modified carbohydrate metabolism coupled with glycolysis and fermentation. For a coordinated response to low oxygen, plants exploit various molecular mechanisms to sense when oxygen is either absent or in limited amounts. In Arabidopsis thaliana, a direct oxygen sensing system has recently been discovered, where a conserved N-terminal motif on some ethylene responsive factors (ERFs, targets the fate of the protein under normoxia/hypoxia. In Oryza sativa, this same group of ERFs drives physiological and anatomical modifications that vary in relation to the genotype studied. The microalga Chlamydomonas reinhardtii responses to low oxygen seem to have evolved independently of higher plants, posing questions on how the fermentative metabolism is modulated. In this review, we summarize the most recent findings related to these topics, highlighting promising developments for the future.

  3. Enhanced red emission of 808 nm excited upconversion nanoparticles by optimizing the composition of shell for efficient generation of singlet oxygen

    Science.gov (United States)

    Liu, Jinxue; Zhang, Tingbin; Song, Xiaoyan; Xing, Jinfeng

    2018-01-01

    With the aim to enhance the upconversion luminescence (UCL) intensity, much attention was paid to reduce the energy-back transfer from Er3+ ions to Nd3+ ions by constructing various kinds of multilayer upconversion nanoparticles (UCNPs). However, the energy-back transfer was difficult to be completely eliminated. Also, the thick shell of multilayer UCNPs is not favourable for effective Förster resonance energy transfer (FRET) in photodynamic therapy (PDT) system. Herein, an effective and facile method was applied to prepare UCNPs by optimizing the composition to largely enhance the red emission (at 660 nm) for efficient generation of singlet oxygen (1O2). In detail, the concentrations of Nd3+ ions and Yb3+ ions doped in the sensitizing shell were systematically researched to balance the energy back-transfer and the light harvest ability. The optimal emission and a relatively high Red/Green (R/G) ratio of NaYF4:Yb,Er,Nd@NaYF4:Yb0.1Nd0.2 UCNPs were obtained simultaneously. Furthermore, the emission under 980 nm excitation demonstrated the energy back-transfer from Er3+ to Yb3+ ions was also notable which was largely ignored previously. Then, UCNPs were encapsulated into mesoporous silica shell, and the photosensitizer Chlorin e6 (Ce6) was covalently conjugated to form a non-leaking nanoplatform. The efficiency of 1O2 generation obviously increased with the enhanced emission of UCNPs.

  4. Reactivity differences of combined and free amino acids: quantifying the relationship between three-dimensional protein structure and singlet oxygen reaction rates.

    Science.gov (United States)

    Lundeen, Rachel A; McNeill, Kristopher

    2013-12-17

    It has long been appreciated that the photooxidation kinetics of amino acid (AA) residues in an intact protein differ from those of free AAs due to differences in the local steric microenvironment, such as its location in the three-dimensional structure. Yet there are only a few studies that have quantified the effect of protein structure on the photochemical reactivity of its residues. This is important for predicting phototransformation rates of AAs in aquatic environments where AAs in combined forms (e.g., oligopeptides and proteins) are more abundant than free AAs. In this work, the photochemical reactivity differences between free and combined AAs were assessed. Singlet oxygen ((1)O2) reaction kinetics of individual photooxidizable residues in the protein glyceraldehyde-3-phosphate dehydrogenase (GAPDH) were examined. The results suggest that the (1)O2 accessibility of residues in intact GAPDH has a profound effect on their photodegradation kinetics and for histidine residues can explain most of the variation in (1)O2 reactivity. Additionally, (1)O2-accessibile surface area values of residues calculated from protein crystal structure data are useful in predicting their reaction rates in GAPDH. This work illustrates a new approach to assess the differential photochemical reactivity of AA-based biomolecules in natural environments or engineered applications.

  5. Mechanical ventilation during extracorporeal membrane oxygenation

    OpenAIRE

    Schmidt, Matthieu; Pellegrino, Vincent; Combes, Alain; Scheinkestel, Carlos; Cooper, D Jamie; Hodgson, Carol

    2014-01-01

    The timing of extracorporeal membrane oxygenation (ECMO) initiation and its outcome in the management of respiratory and cardiac failure have received considerable attention, but very little attention has been given to mechanical ventilation during ECMO. Mechanical ventilation settings in non-ECMO studies have been shown to have an effect on survival and may also have contributed to a treatment effect in ECMO trials. Protective lung ventilation strategies established for non-ECMO-supported re...

  6. Singlet molecular oxygen generation by light-activated DHN-melanin of the fungal pathogen Mycosphaerella fijiensis in black Sigatoka disease of bananas.

    Directory of Open Access Journals (Sweden)

    Miguel J Beltrán-García

    Full Text Available In pathogenic fungi, melanin contributes to virulence, allowing tissue invasion and inactivation of the plant defence system, but has never been implicated as a factor for host cell death, or as a light-activated phytotoxin. Our research shows that melanin synthesized by the fungal banana pathogen Mycosphaerella fijiensis acts as a virulence factor through the photogeneration of singlet molecular oxygen O2 (1Δg. Using analytical tools, including elemental analysis, ultraviolet/infrared absorption spectrophometry and MALDI-TOF mass spectrometry analysis, we characterized both pigment content in mycelia and secreted to the culture media as 1,8-dihydroxynaphthalene (DHN-melanin type compound. This is sole melanin-type in M. fijiensis. Isolated melanins irradiated with a Nd:YAG laser at 532 nm produced monomol light emission at 1270 nm, confirming generation of O2 (1Δg, a highly reactive oxygen specie (ROS that causes cellular death by reacting with all cellular macromolecules. Intermediary polyketides accumulated in culture media by using tricyclazole and pyroquilon (two inhibitors of DHN-melanin synthesis were identified by ESI-HPLC-MS/MS. Additionally, irradiation at 532 nm of that mixture of compounds and whole melanized mycelium also generated O2 (1Δg. A pigmented-strain generated more O2 (1Δg than a strain with low melanin content. Banana leaves of cultivar Cavendish, naturally infected with different stages of black Sigatoka disease, were collected from field. Direct staining of the naturally infected leaf tissues showed the presence of melanin that was positively correlated to the disease stage. We also found hydrogen peroxide (H2O2 but we cannot distinguish the source. Our results suggest that O2 (1Δg photogenerated by DHN-melanin may be involved in the destructive effects of Mycosphaerella fijiensis on banana leaf tissues. Further studies are needed to fully evaluate contributions of melanin-mediated ROS to microbial pathogenesis.

  7. Singlet molecular oxygen generation by light-activated DHN-melanin of the fungal pathogen Mycosphaerella fijiensis in black Sigatoka disease of bananas.

    Science.gov (United States)

    Beltrán-García, Miguel J; Prado, Fernanda M; Oliveira, Marilene S; Ortiz-Mendoza, David; Scalfo, Alexsandra C; Pessoa, Adalberto; Medeiros, Marisa H G; White, James F; Di Mascio, Paolo

    2014-01-01

    In pathogenic fungi, melanin contributes to virulence, allowing tissue invasion and inactivation of the plant defence system, but has never been implicated as a factor for host cell death, or as a light-activated phytotoxin. Our research shows that melanin synthesized by the fungal banana pathogen Mycosphaerella fijiensis acts as a virulence factor through the photogeneration of singlet molecular oxygen O2 (1Δg). Using analytical tools, including elemental analysis, ultraviolet/infrared absorption spectrophometry and MALDI-TOF mass spectrometry analysis, we characterized both pigment content in mycelia and secreted to the culture media as 1,8-dihydroxynaphthalene (DHN)-melanin type compound. This is sole melanin-type in M. fijiensis. Isolated melanins irradiated with a Nd:YAG laser at 532 nm produced monomol light emission at 1270 nm, confirming generation of O2 (1Δg), a highly reactive oxygen specie (ROS) that causes cellular death by reacting with all cellular macromolecules. Intermediary polyketides accumulated in culture media by using tricyclazole and pyroquilon (two inhibitors of DHN-melanin synthesis) were identified by ESI-HPLC-MS/MS. Additionally, irradiation at 532 nm of that mixture of compounds and whole melanized mycelium also generated O2 (1Δg). A pigmented-strain generated more O2 (1Δg) than a strain with low melanin content. Banana leaves of cultivar Cavendish, naturally infected with different stages of black Sigatoka disease, were collected from field. Direct staining of the naturally infected leaf tissues showed the presence of melanin that was positively correlated to the disease stage. We also found hydrogen peroxide (H2O2) but we cannot distinguish the source. Our results suggest that O2 (1Δg) photogenerated by DHN-melanin may be involved in the destructive effects of Mycosphaerella fijiensis on banana leaf tissues. Further studies are needed to fully evaluate contributions of melanin-mediated ROS to microbial pathogenesis.

  8. Protective mechanisms against peptide and protein peroxides generated by singlet oxygen

    DEFF Research Database (Denmark)

    Morgan, Philip E; Dean, Roger T; Davies, Michael Jonathan

    2004-01-01

    or detoxify such peroxides. It is shown that catalase, horseradish peroxidase, and Cu/Zn superoxide dismutase do not react rapidly with these peroxides. Oxymyoglobin and oxyhemoglobin, but not the met (Fe3+) forms of these proteins, react with peptide but not protein, peroxides with oxidation of the heme iron...

  9. Threshold ionization mass spectrometry study of singlet molecular oxygen in the deposition of SnO2 by PACVD

    Science.gov (United States)

    Pulpytel, J.; Arefi-Khonsari, F.; Morscheidt, W.

    2005-05-01

    Threshold ionization mass spectrometry (TIMS) has been used to measure the excited molecular oxygen states O2 (1Δg) and O_{2 }(^{1}\\!\\Sigma _g^{+}) during plasma-assisted chemical vapour deposition of tin oxide (SnO2) thin films. The latter, composed of nanosized features, was deposited by feeding in a mixture of Ar, O2 and tetramethyltin (Sn(CH3)4 or TMT) in a capacitively coupled RF discharge reactor. Langmuir probe measurements were performed along with TIMS to measure the electron temperature and density. The correlations between these two diagnostic methods have been investigated. The observed densities of O2 (1Δg) and O_{2 }(^{1}\\!\\Sigma _g^{+}) in the γ mode of the discharge are maximum at a low electron temperature and high density. Furthermore, these results have been shown to be correlated to the trend of the electronic conductivity of the deposited SnO2 thin films.

  10. Singlet oxygen triggers chloroplast rupture and cell death in the zeaxanthin epoxidase defective mutant aba1 of Arabidopsis thaliana under high light stress.

    Science.gov (United States)

    Sánchez-Corrionero, Álvaro; Sánchez-Vicente, Inmaculada; González-Pérez, Sergio; Corrales, Ascensión; Krieger-Liszkay, Anja; Lorenzo, Óscar; Arellano, Juan B

    2017-09-01

    The two Arabidopsis thaliana mutants, aba1 and max4, were previously identified as sharing a number of co-regulated genes with both the flu mutant and Arabidopsis cell suspension cultures exposed to high light (HL). On this basis, we investigated whether aba1 and max4 were generating high amounts of singlet oxygen ( 1 O 2 ) and activating 1 O 2 -mediated cell death. Thylakoids of aba1 produced twice as much 1 O 2 as thylakoids of max4 and wild type (WT) plants when illuminated with strong red light. 1 O 2 was measured using the spin probe 2,2,6,6-tetramethyl-4-piperidone hydrochloride. 77-K chlorophyll fluorescence emission spectra of thylakoids revealed lower aggregation of the light harvesting complex II in aba1. This was rationalized as a loss of connectivity between photosystem II (PSII) units and as the main cause for the high yield of 1 O 2 generation in aba1. Up-regulation of the 1 O 2 responsive gene AAA-ATPase was only observed with statistical significant in aba1 under HL. Two early jasmonate (JA)-responsive genes, JAZ1 and JAZ5, encoding for two repressor proteins involved in the negative feedback regulation of JA signalling, were not up-regulated to the WT plant levels. Chloroplast aggregation followed by chloroplast rupture and eventual cell death was observed by confocal imaging of the fluorescence emission of leaf cells of transgenic aba1 plants expressing the chimeric fusion protein SSU-GFP. Cell death was not associated with direct 1 O 2 cytotoxicity in aba1, but rather with a delayed stress response. In contrast, max4 did not show evidence of 1 O 2 -mediated cell death. In conclusion, aba1 may serve as an alternative model to other 1 O 2 -overproducing mutants of Arabidopsis for investigating 1 O 2 -mediated cell death. Copyright © 2017 Elsevier GmbH. All rights reserved.

  11. Singlet-triplet annihilation in single LHCII complexes.

    Science.gov (United States)

    Gruber, J Michael; Chmeliov, Jevgenij; Krüger, Tjaart P J; Valkunas, Leonas; van Grondelle, Rienk

    2015-08-14

    In light harvesting complex II (LHCII) of higher plants and green algae, carotenoids (Cars) have an important function to quench chlorophyll (Chl) triplet states and therefore avoid the production of harmful singlet oxygen. The resulting Car triplet states lead to a non-linear self-quenching mechanism called singlet-triplet (S-T) annihilation that strongly depends on the excitation density. In this work we investigated the fluorescence decay kinetics of single immobilized LHCIIs at room temperature and found a two-exponential decay with a slow (3.5 ns) and a fast (35 ps) component. The relative amplitude fraction of the fast component increases with increasing excitation intensity, and the resulting decrease in the fluorescence quantum yield suggests annihilation effects. Modulation of the excitation pattern by means of an acousto-optic modulator (AOM) furthermore allowed us to resolve the time-dependent accumulation and decay rate (∼7 μs) of the quenching species. Inspired by singlet-singlet (S-S) annihilation studies, we developed a stochastic model and then successfully applied it to describe and explain all the experimentally observed steady-state and time-dependent kinetics. That allowed us to distinctively identify the quenching mechanism as S-T annihilation. Quantitative fitting resulted in a conclusive set of parameters validating our interpretation of the experimental results. The obtained stochastic model can be generalized to describe S-T annihilation in small molecular aggregates where the equilibration time of excitations is much faster than the annihilation-free singlet excited state lifetime.

  12. Mechanical ventilation during extracorporeal membrane oxygenation.

    Science.gov (United States)

    Schmidt, Matthieu; Pellegrino, Vincent; Combes, Alain; Scheinkestel, Carlos; Cooper, D Jamie; Hodgson, Carol

    2014-01-21

    The timing of extracorporeal membrane oxygenation (ECMO) initiation and its outcome in the management of respiratory and cardiac failure have received considerable attention, but very little attention has been given to mechanical ventilation during ECMO. Mechanical ventilation settings in non-ECMO studies have been shown to have an effect on survival and may also have contributed to a treatment effect in ECMO trials. Protective lung ventilation strategies established for non-ECMO-supported respiratory failure patients may not be optimal for more severe forms of respiratory failure requiring ECMO support. The influence of positive end-expiratory pressure on the reduction of the left ventricular compliance may be a matter of concern for patients receiving ECMO support for cardiac failure. The objectives of this review were to describe potential mechanisms for lung injury during ECMO for respiratory or cardiac failure, to assess the possible benefits from the use of ultra-protective lung ventilation strategies and to review published guidelines and expert opinions available on mechanical ventilation-specific management of patients requiring ECMO, including mode and ventilator settings. Articles were identified through a detailed search of PubMed, Ovid, Cochrane databases and Google Scholar. Additional references were retrieved from the selected studies. Growing evidence suggests that mechanical ventilation settings are important in ECMO patients to minimize further lung damage and improve outcomes. An ultra-protective ventilation strategy may be optimal for mechanical ventilation during ECMO for respiratory failure. The effects of airway pressure on right and left ventricular afterload should be considered during venoarterial ECMO support of cardiac failure. Future studies are needed to better understand the potential impact of invasive mechanical ventilation modes and settings on outcomes.

  13. Influence of an intermolecular charge-transfer state on excited-state relaxation dynamics: solvent effect on the methylnaphthalene-oxygen system and its significance for singlet oxygen production.

    Science.gov (United States)

    Jensen, Poul-Gudmund; Arnbjerg, Jacob; Tolbod, Lars Poulsen; Toftegaard, Rasmus; Ogilby, Peter R

    2009-09-17

    The extent to which an intermolecular charge-transfer (CT) state can influence excited-state relaxation dynamics is examined for the system wherein 1-methylnaphthalene (MN) interacts with molecular oxygen. The MN-O2 system is ideally suited for such a study because excited states can be independently accessed by (i) irradiation into the discrete MN-O2 CT absorption band, (ii) direct irradiation of MN, and (iii) the photosensitized production of triplet state MN. Changing the solvent in which the MN-O2 system is dissolved influences the MN-dependent photoinduced production of singlet oxygen, O2(a1Delta(g)), which, in turn, yields information about fundamental concepts of state mixing. Results of experiments conducted in the polar solvent acetonitrile differ substantially from those obtained from the nonpolar solvent cyclohexane. The data reflect differences in the energy and behavior of the solvent-equilibrated MN-O2 CT state, CT(SE), and the extent to which this state couples to other states of the MN-O2 system. In particular, the data are consistent with a model where both the MN triplet state and the MN-O2 CT(SE) state are immediate precursors of O2(a1Delta(g)). Although the work reported herein is of direct and practical significance for the wide variety of systems in which O2(a1Delta(g)) can be produced upon irradiation, it also serves as an accessible model for a study of general issues pertinent to state mixing and the solvent-dependent dynamics of CT-mediated excited-state relaxation.

  14. Mechanisms of oxygen radiosensitization in CHO cells

    International Nuclear Information System (INIS)

    Whillans, D.W.

    1981-01-01

    A model is presented for repair and fixation pathways when CHO cells are irradiated in the presence of O 2 . This analysis predicts that an increase in the repair path such as has been postulated for addition of a radioprotective sulfhydryl should increase OER/sub max/ in porportion to k prime, the new repair rate constant and also increase K with k prime. Any radiosensitizer which mimics the action of O 2 simply increases k prime 2 , so that the OER/sub max/ decreases at 1/k prime 2 but K increases as k prime 2 . These predictions have been tested in mammalian CHO cells making use of a Clark-type oxygen probe with defined conditions to ensure that O 2 is not depleted by radiation or cellular consumption, and so O 2 levels are known with accuracy. In a complementary study, the technique of rapid-mixing was used to measure the rate of development of O 2 sensitization in these same cells. By a variation of this rapid-mixing approach, the rate of diffusion into these cells has also been measured independently. Neither the dependence of OER on O 2 concentration nor the development of radiosensitivity with time of incubation in O 2 gives evidence in CHO cells for two components of sensitization indicative of two sites or two mechanisms of action, as seen in some V79 sublines. 13 references, 4 figures

  15. A prototype of an electric-discharge gas flow oxygen−iodine laser: I. Modeling of the processes of singlet oxygen generation in a transverse cryogenic slab RF discharge

    International Nuclear Information System (INIS)

    Vagin, N. P.; Ionin, A. A.; Kochetov, I. V.; Napartovich, A. P.; Sinitsyn, D. V.; Yuryshev, N. N.

    2017-01-01

    The existing kinetic model describing self-sustained and electroionization discharges in mixtures enriched with singlet oxygen has been modified to calculate the characteristics of a flow RF discharge in molecular oxygen and its mixtures with helium. The simulations were performed in the gas plug-flow approximation, i.e., the evolution of the plasma components during their motion along the channel was represented as their evolution in time. The calculations were carried out for the O 2 : He = 1: 0, 1: 1, 1: 2, and 1: 3 mixtures at an oxygen partial pressure of 7.5 Torr. It is shown that, under these conditions, volumetric gas heating in a discharge in pure molecular oxygen prevails over gas cooling via heat conduction even at an electrode temperature as low as ~100 K. When molecular oxygen is diluted with helium, the behavior of the gas temperature changes substantially: heat removal begins to prevail over volumetric gas heating, and the gas temperature at the outlet of the discharge zone drops to ~220–230 K at room gas temperature at the inlet, which is very important in the context of achieving the generation threshold in an electric-discharge oxygen−iodine laser based on a slab cryogenic RF discharge.

  16. Hypoxia switches episodic breathing to singlet breathing in red-eared slider turtles (Trachemys scripta) via a tropisetron-sensitive mechanism

    OpenAIRE

    Johnson, Stephen M.; Krisp, Ashley R.; Bartman, Michelle E.

    2014-01-01

    Hypoxia-induced changes in the chelonian breathing pattern are poorly understood. Thus, breathing was measured in freely swimming adult red-eared slider turtles breathing air prior to breathing nitrogen for 4 h. Ventilation increased 10-fold within 10 min due to increased breath frequency and tidal volume. Breaths/episode decreased by ~50% within after 1 h of hypoxia while the number of singlet breaths increased from 3.1 ± 1.6 singlets/h to a maximum of 66.1 ± 23.5 singlets/h. Expiratory and ...

  17. Kinetics and mechanisms of some atomic oxygen reactions

    Science.gov (United States)

    Cvetanovic, R. J.

    1987-01-01

    Mechanisms and kinetics of some reactions of the ground state of oxygen atoms, O(3P), are briefly summarized. Attention is given to reactions of oxygen atoms with several different types of organic and inorganic compounds such as alkanes, alkenes, alkynes, aromatics, and some oxygen, nitrogen, halogen and sulfur derivatives of these compounds. References to some recent compilations and critical evaluations of reaction rate constants are given.

  18. Mechanism of pulse discharge production of iodine atoms from CF3I molecules for a chemical oxygen-iodine laser

    International Nuclear Information System (INIS)

    Kochetov, I V; Napartovich, A P; Vagin, N P; Yuryshev, N N

    2009-01-01

    The pulsed chemical oxygen-iodine laser (COIL) development is aimed at many new applications. Pulsed electric discharge is most effective in turning COIL operation into the pulse mode by instant production of iodine atoms. A numerical model is developed for simulations of the pulsed COIL initiated by an electric discharge. The model comprises a system of kinetic equations for neutral and charged species, electric circuit equation, gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are found by solving the electron Boltzmann equation, which is re-calculated in a course of computations when plasma parameters changed. The processes accounted for in the Boltzmann equation include excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron-ion recombination, electron-electron collisions, second-kind collisions and stepwise excitation of molecules. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. Results of numerical simulations are compared with experimental laser pulse waveforms. It is concluded that there is satisfactory agreement between theory and the experiment. The prevailing mechanism of iodine atom formation from the CF 3 I donor in a very complex kinetic system of the COIL medium under pulse discharge conditions, based on their detailed numerical modelling and by comparing these results both with experimental results of other authors and their own experiments, is established. The dominant iodine atom production mechanism for conditions under study is the electron-impact dissociation of CF 3 I molecules. It was proved that in the conditions of the experiment the secondary chemical reactions with O atoms play an insignificant role.

  19. Hypoxia switches episodic breathing to singlet breathing in red-eared slider turtles (Trachemys scripta) via a tropisetron-sensitive mechanism.

    Science.gov (United States)

    Johnson, Stephen M; Krisp, Ashley R; Bartman, Michelle E

    2015-02-01

    Hypoxia-induced changes in the chelonian breathing pattern are poorly understood. Thus, breathing was measured in freely swimming adult red-eared slider turtles breathing air prior to breathing nitrogen for 4h. Ventilation increased 10-fold within 10min due to increased breath frequency and tidal volume. Breaths/episode decreased by ∼50% within after 1h of hypoxia while the number of singlet breaths increased from 3.1±1.6singlets/h to a maximum of 66.1±23.5singlets/h. Expiratory and inspiratory duration increased during hypoxia. For doublet and triplet breaths, expiratory duration increased during the first breath only, while inspiratory duration increased for all breaths. Tropisetron (5-HT3 receptor antagonist, 5mg/kg) administration prior to hypoxia attenuated the hypoxia-induced increase in singlet breath frequency. Along with results from previous in vitro studies, this study suggests that 5-HT3 receptor activation may be required for the hypoxia-induced increase in singlet breathing pattern in red-eared slider turtles. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Hypoxia switches episodic breathing to singlet breathing in red-eared slider turtles (Trachemys scripta) via a tropisetron-sensitive mechanism

    Science.gov (United States)

    Johnson, Stephen M.; Krisp, Ashley R.; Bartman, Michelle E.

    2015-01-01

    Hypoxia-induced changes in the chelonian breathing pattern are poorly understood. Thus, breathing was measured in freely swimming adult red-eared slider turtles breathing air prior to breathing nitrogen for 4 h. Ventilation increased 10-fold within 10 min due to increased breath frequency and tidal volume. Breaths/episode decreased by ~50% within after 1 h of hypoxia while the number of singlet breaths increased from 3.1 ± 1.6 singlets/h to a maximum of 66.1 ± 23.5 singlets/h. Expiratory and inspiratory duration increased during hypoxia. For doublet and triplet breaths, expiratory duration increased during the first breath only, while inspiratory duration increased for all breaths. Tropisetron (5-HT3 receptor antagonist, 5 mg/kg) administration prior to hypoxia attenuated the hypoxia-induced increase in singlet breath frequency. Along with results from previous in vitro studies, this study suggests that 5-HT3 receptor activation may be required for the hypoxia-induced increase in singlet breathing pattern in red-eared slider turtles. PMID:25543027

  1. Optimizing Oxygenation in the Mechanically Ventilated Patient: Nursing Practice Implications.

    Science.gov (United States)

    Barton, Glenn; Vanderspank-Wright, Brandi; Shea, Jacqueline

    2016-12-01

    Critical care nurses constitute front-line care provision for patients in the intensive care unit (ICU). Hypoxemic respiratory compromise/failure is a primary reason that patients require ICU admission and mechanical ventilation. Critical care nurses must possess advanced knowledge, skill, and judgment when caring for these patients to ensure that interventions aimed at optimizing oxygenation are both effective and safe. This article discusses fundamental aspects of respiratory physiology and clinical indices used to describe oxygenation status. Key nursing interventions including patient assessment, positioning, pharmacology, and managing hemodynamic parameters are discussed, emphasizing their effects toward mitigating ventilation-perfusion mismatch and optimizing oxygenation. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Safety of hyperbaric oxygen therapy in mechanically ventilated patients.

    Science.gov (United States)

    Bessereau, Jacques; Aboab, Jérôme; Hullin, Thomas; Huon-Bessereau, Anne; Bourgeois, Jean-Luc; Brun, Pierre-Marie; Chevret, Sylvie; Annane, Djillali

    2017-01-01

    To evaluate the epidemiology of patients who require mechanical ventilation during hyperbaric oxygen therapy. One-hundred-fifty patients who required mechanical ventilation during hyperbaric oxygen therapy were prospectively studied during a 6-year period in a French university hyperbaric centre. We analysed the indication of hyperbaric oxygen therapy, agent used for sedation, presence of a chest tube, need for vasopressor agents and tolerance and appearance of side effects. Finally, we compared the outcomes of patients according to the presence or absence of acute respiratory distress syndrome (ARDS). Eleven children and 139 adult patients were included (n = 150) in the study. In both populations, carbon monoxide poisoning (51%) and iatrogenic gas embolism (33%) were the two main causes of intubation and mechanical ventilation. The combination of midazolam and sufentanil was used in 85 (67%) patients. All of the patients were given a bolus of a neuromuscular blocker during the hyperbaric session, despite the presence of ARDS in 35 patients. Patient-ventilator asynchrony was the most frequent side effect in 6 (5%) patients and was often the consequence of suboptimal sedation. Mortality was higher in the group with ARDS (23%). Carbon monoxide poisoning and iatrogenic gas embolism are the two main diseases of the patients who required mechanical ventilation during hyperbaric oxygen therapy in this study. Mechanical ventilation is a safe method for patients during hyperbaric oxygen therapy. Sedation needs to be perfected to avoid patient-ventilator asynchrony.

  3. Effective photo-enhancement of cellular activity of fluorophore-octaarginine antisense PNA conjugates correlates with singlet oxygen formation, endosomal escape and chromophore lipophilicity

    DEFF Research Database (Denmark)

    Yarani, Reza; Shiraishi, Takehiko; Nielsen, Peter E.

    2018-01-01

    Photochemical internalization (PCI) is a cellular drug delivery method based on the generation of light-induced reactive oxygen species (ROS) causing damage to the endosomal membrane and thereby resulting in drug release to the cytoplasm. In our study a series of antisense fluorophore octaarginine...

  4. Influence of singlet oxygen (1O2) generated by a lipophilic photosensitizer (Pyropheophorbide-a, PPa) on membrane and firing properties of cultured hippocampus neurons

    DEFF Research Database (Denmark)

    Breitenbach, Thomas; Ogilby, Peter Remsen; Lambert, John D. C.

    2008-01-01

    During Photodynamic Therapy (PDT) of cancer, cells are killed by 1O2, which is generated in a photosensitized process. A photosensitizer (PS) is applied to the tissue and irradiated with light to form an exited molecule. This generates 1O2 from ground state oxygen, which then induce processes...

  5. Novel foamy origin for singlet fermion masses

    Science.gov (United States)

    Ellis, John; Mavromatos, Nick E.; Nanopoulos, Dimitri V.

    2017-10-01

    We show how masses for singlet fermions can be generated by interactions with a D-particle model of space-time foam inspired by brane theory. It has been shown previously by one of the authors (N. E. M.) that such interactions may generate dynamically small masses for charged fermions via the recoils of D-particle defects interacting with photons. In this work we consider the direct interactions of D-particle with uncharged singlet fermions such as right-handed neutrinos. Quantum fluctuations of the lattice of D-particles have massless vector (spin-one) excitations that are analogues of phonons. These mediate forces with the singlet fermions, generating large dynamical masses that may be communicated to light neutrinos via the seesaw mechanism.

  6. Singlet Oxygen Production and Biological Activity of Hexanuclear Chalcocyanide Rhenium Cluster Complexes [{Re(6)Q(8)}(CN)(6)](4-) (Q = S, Se, Te)

    Czech Academy of Sciences Publication Activity Database

    Solovieva, A.O.; Kirakci, Kaplan; Ivanov, A.; Kubát, Pavel; Pozmogova, T.N.; Miroshnichenko, S.M.; Vorontsova, E.V.; Chechushkov, A.V.; Trifonova, K.E.; Fufaeva, M.S.; Kretov, E.I.; Mironov, Y.V.; Poveshchenko, A.F.; Lang, Kamil; Shestopalov, M.A.

    2017-01-01

    Roč. 56, č. 21 (2017), s. 13491-13499 ISSN 0020-1669 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : photophysical properties * silica nanoparticles * molecular-oxygen * iodide cluster * luminescence Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) OBOR OECD: Inorganic and nuclear chemistry; Physical chemistry (UFCH-W) Impact factor: 4.857, year: 2016

  7. Small CAB-like proteins prevent formation of singlet oxygen in the damaged photosystem II complex of the cyanobacterium Synechocystis sp PCC 6803

    Czech Academy of Sciences Publication Activity Database

    Sinha, R. K.; Komenda, Josef; Knoppová, Jana; Sedlářová, M.; Pospíšil, P.

    2012-01-01

    Roč. 35, č. 4 (2012), s. 806-818 ISSN 0140-7791 R&D Projects: GA MŠk(CZ) ED2.1.00/03.0110; GA ČR(CZ) GAP501/11/0377 Institutional research plan: CEZ:AV0Z50200510 Keywords : oxidative stress * photoinhibition * reactive oxygen species Subject RIV: EE - Microbiology, Virology Impact factor: 5.135, year: 2012

  8. Synthesis, singlet-oxygen photogeneration, two-photon absorption, photo-induced DNA cleavage and cytotoxic properties of an amphiphilic β-Schiff-base linked Ru(II) polypyridyl–porphyrin conjugate

    International Nuclear Information System (INIS)

    Ke, Hanzhong; Ma, Wanpeng; Wang, Hongda; Cheng, Guoe; Yuan, Han; Wong, Wai-Kwok; Kwong, Daniel W.J.; Tam, Hoi-Lam; Cheah, Kok-Wai; Chan, Chi-Fai; Wong, Ka-Leung

    2014-01-01

    A novel porphyrin–polypyridyl ruthenium(II) conjugate (TPP–Ru), in which the ruthenium(II) polypyridyl moiety is linked to the β-position of the tetraphenylporphyrin via a Schiff base linkage, has been synthesized and characterized by 1 H NMR, HRMS and UV–visible spectroscopy. The relative singlet oxygen quantum yield and two-photon absorption cross-section of this conjugate, together with its photo-induced DNA cleavage and cytotoxic activities were measured. The results show that the amphiphilic ruthenium(II) polypyridyl–porphyrin conjugate is an effective DNA photocleavage agent, with potential application in one- and two-photon absorption anti-cancer photodynamic therapy. - Highlights: • New porphyrin–ruthenium(II) polypyridyl complexes (TTP–Ru) have been synthesized. • The TTP–Ru shows substantial two-photon absorption cross-section (σ 2 =391 GM). • The TTP–Ru exhibits a substantial 1 O 2 quantum yield (0.64±0.13). • The TTP–Ru exhibits a strong DNA cleavage activity upon photo-excitation. • The TTP–Ru is available for in vitro imaging and as a photodynamic therapy agent

  9. Synthesis, singlet-oxygen photogeneration, two-photon absorption, photo-induced DNA cleavage and cytotoxic properties of an amphiphilic β-Schiff-base linked Ru(II) polypyridyl–porphyrin conjugate

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Hanzhong, E-mail: kehanz@163.com [Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan, Hubei 430074 (China); Ma, Wanpeng; Wang, Hongda; Cheng, Guoe [Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan, Hubei 430074 (China); Yuan, Han [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Wong, Wai-Kwok, E-mail: wkwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Institute of Advanced Materials, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Kwong, Daniel W.J. [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Tam, Hoi-Lam; Cheah, Kok-Wai [Department of Physics, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Institute of Advanced Materials, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China); Chan, Chi-Fai; Wong, Ka-Leung [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong SAR (China)

    2014-10-15

    A novel porphyrin–polypyridyl ruthenium(II) conjugate (TPP–Ru), in which the ruthenium(II) polypyridyl moiety is linked to the β-position of the tetraphenylporphyrin via a Schiff base linkage, has been synthesized and characterized by {sup 1}H NMR, HRMS and UV–visible spectroscopy. The relative singlet oxygen quantum yield and two-photon absorption cross-section of this conjugate, together with its photo-induced DNA cleavage and cytotoxic activities were measured. The results show that the amphiphilic ruthenium(II) polypyridyl–porphyrin conjugate is an effective DNA photocleavage agent, with potential application in one- and two-photon absorption anti-cancer photodynamic therapy. - Highlights: • New porphyrin–ruthenium(II) polypyridyl complexes (TTP–Ru) have been synthesized. • The TTP–Ru shows substantial two-photon absorption cross-section (σ{sub 2}=391 GM). • The TTP–Ru exhibits a substantial {sup 1}O{sub 2} quantum yield (0.64±0.13). • The TTP–Ru exhibits a strong DNA cleavage activity upon photo-excitation. • The TTP–Ru is available for in vitro imaging and as a photodynamic therapy agent.

  10. New Hypothesis for SOFC Ceramic Oxygen Electrode Mechanisms

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg; Chatzichristodoulou, Christodoulos; Graves, Christopher R.

    2016-01-01

    A new hypothesis for the electrochemical reaction mechanism in solid oxide cell ceramic oxygen electrodes is proposed based on literature including our own results. The hypothesis postulates that the observed thin layers of SrO-La2O3 on top of ceramic perovskite and other Ruddlesden-Popper...

  11. Effect of Mechanical Alloying Atmospheres and Oxygen Concentration on Mechanical Properties of ODS Ferritic Steels

    International Nuclear Information System (INIS)

    Noh, Sanghoon; Choi, Byoungkwon; Han, Changhee; Kim, Kibaik; Kang, Sukhoon; Chun, Youngbum; Kim, Taekyu

    2013-01-01

    Finely dispersed nano-oxide particles with a high number density in the homogeneous grain matrix are essential to achieve superior mechanical properties at high temperatures, and these unique microstructures can be obtained through the mechanical alloying (MA) and hot consolidation process. The microstructure and mechanical property of ODS steel significantly depends on its powder property and the purity after the MA process. These contents should be carefully controlled to improve the mechanical property at elevated temperature. In particular, appropriate the control of oxygen concentration improves the mechanical property of ODS steel at high temperature. An effective method is to control the mechanical alloying atmosphere by high purity inert gas. In the present study, the effects of mechanical alloying atmospheres and oxygen concentration on the mechanical property of ODS steel were investigated. ODS ferritic alloys were fabricated in various atmospheres, and the HIP process was used to investigate the effects of MA atmospheres and oxygen concentration on the microstructure and mechanical property. ODS ferritic alloys milled in an Ar-H 2 mixture, and He is effective to reduce the excess oxygen concentration. The YH 2 addition made an extremely reduced oxygen concentration by the internal oxygen reduction reaction and resulted in a homogeneous microstructure and superior creep strength

  12. Singlet Ground State Magnetism:

    DEFF Research Database (Denmark)

    Loidl, A.; Knorr, K.; Kjems, Jørgen

    1979-01-01

    The magneticGamma 1 –Gamma 4 exciton of the singlet ground state system TbP has been studied by inelastic neutron scattering above the antiferromagnetic ordering temperature. Considerable dispersion and a pronounced splitting was found in the [100] and [110] directions. Both the band width...... and the splitting increased rapidly as the transition temperature was approached in accordance with the predictions of the RPA-theory. The dispersion is analysed in terms of a phenomenological model using interactions up to the fourth nearest neighbour....

  13. Oxygen etching mechanism in carbon-nitrogen (CNx) domelike nanostructures

    International Nuclear Information System (INIS)

    Acuna, J. J. S.; Figueroa, C. A.; Kleinke, M. U.; Alvarez, F.; Biggemann, D.

    2008-01-01

    We report a comprehensive study involving the ion beam oxygen etching purification mechanism of domelike carbon nanostructures containing nitrogen. The CN x nanodomes were prepared on Si substrate containing nanometric nickel islands catalyzed by ion beam sputtering of a carbon target and assisting the deposition by a second nitrogen ion gun. After preparation, the samples were irradiated in situ by a low energy ion beam oxygen source and its effects on the nanostructures were studied by x-ray photoelectron spectroscopy in an attached ultrahigh vacuum chamber, i.e., without atmospheric contamination. The influence of the etching process on the morphology of the samples and structures was studied by atomic force microscopy and field emission gun-secondary electron microscopy, respectively. Also, the nanodomes were observed by high resolution transmission electron microscopy. The oxygen atoms preferentially bond to carbon atoms by forming terminal carbonyl groups in the most reactive parts of the nanostructures. After the irradiation, the remaining nanostructures are grouped around two well-defined size distributions. Subsequent annealing eliminates volatile oxygen compounds retained at the surface. The oxygen ions mainly react with nitrogen atoms located in pyridinelike structures

  14. Singlets of fermionic gauge symmetries

    NARCIS (Netherlands)

    Bergshoeff, E.A.; Kallosh, R.E.; Rahmanov, M.A.

    1989-01-01

    We investigate under which conditions singlets of fermionic gauge symmetries which are "square roots of gravity" can exist. Their existence is non-trivial because there are no fields neutral in gravity. We tabulate several examples of singlets of global and local supersymmetry and κ-symmetry and

  15. Gaugino Mass without Singlets

    CERN Document Server

    Giudice, Gian Francesco; Murayama, H; Rattazzi, Riccardo; Giudice, Gian F.; Luty, Markus A.; Murayama, Hitoshi; Rattazzi, Riccardo

    1998-01-01

    In models with dynamical supersymmetry breaking in the hidden sector, the gaugino masses in the observable sector have been believed to be extremely suppressed (below 1 keV), unless there is a gauge singlet in the hidden sector with specific couplings to the observable sector gauge multiplets. We point out that there is a pure supergravity contribution to gaugino masses at the quantum level arising from the superconformal anomaly. Our results are valid to all orders in perturbation theory and are related to the `exact' beta functions for soft terms. There is also an anomaly contribution to the A terms proportional to the beta function of the corresponding Yukawa coupling. The gaugino masses are proportional to the corresponding gauge beta functions, and so do not satisfy the usual GUT relations.

  16. Search for Singlet Fission Chromophores

    Energy Technology Data Exchange (ETDEWEB)

    Havlas, Z.; Akdag, A.; Smith, M. B.; Dron, P.; Johnson, J. C.; Nozik, A. J.; Michl, J.

    2012-01-01

    Singlet fission, in which a singlet excited chromophore shares its energy with a ground-state neighbor and both end up in their triplet states, is of potential interest for solar cells. Only a handful of compounds, mostly alternant hydrocarbons, are known to perform efficiently. In view of the large number of conditions that a successful candidate for a practical cell has to meet, it appears desirable to extend the present list of high performers to additional classes of compounds. We have (i) identified design rules for new singlet fission chromophores and for their coupling to covalent dimers, (ii) synthesized them, and (iii) evaluated their performance as neat solids or covalent dimers.

  17. Redox mechanism of reactive oxygen species in exercise

    Directory of Open Access Journals (Sweden)

    Feng He

    2016-11-01

    Full Text Available It is well known that regular exercise benefits health. However, unaccustomed and/or exhaustive exercise can generate excessive reactive oxygen species (ROS, leading to oxidative stress-related tissue damage and impaired muscle contractility. ROS are produced in both aerobic and anaerobic exercise. Although mitochondria, NADPH oxidases and xanthine oxidase have all been identified as contributors to ROS production, the exact redox mechanisms underlying exercise-induced oxidative stress remain elusive. Interestingly, moderate exposure to ROS is necessary to induce the body’s adaptive responses such as the activation of antioxidant defense mechanisms. Dietary antioxidant manipulation can also reduce ROS levels and muscle fatigue, as well as enhance exercise recovery. To elucidate the complex role of ROS in exercise, this article updates on new findings of ROS origins within skeletal muscles associated with various types of exercises such as endurance, sprint and mountain climbing, corresponding antioxidant defense systems as well as dietary manipulation against damage caused by ROS.

  18. Quantification of reactive oxygen species for photodynamic therapy

    Science.gov (United States)

    Tan, Zou; Zhang, Jinde; Lin, Lisheng; Li, Buhong

    2016-10-01

    Photodynamic therapy (PDT) is an effective therapeutic modality that uses a light source to activate light-sensitive photosensitizers to treat both oncologic and nononcological indications. Photosensitizers are excited to the long-lived triplet state, and they react with biomolecules via type I or II mechanism resulted in cell death and tumor necrosis. Free radicals and radical ions are formed by electron transfer reactions (type I), which rapidly react with oxygen leading to the production of reactive oxygen species (ROS), including superoxide ions, hydroxyl radicals and hydrogen peroxide. Singlet molecular oxygen is produced in a Type II reaction, in which the excited singlet state of the photosensitizer generated upon photon absorption by the ground-state photosensitizer molecule undergoes intersystem crossing to a long-lived triplet state. In this talk, the fundmental mechanisms and detection techniques for ROS generation in PDT will be introduced. In particular, the quantification of singlet oxygen generation for pre-clinical application will be highlighted, which plays an essential role in the establishment of robust singlet oxygen-mediated PDT dosimetry.

  19. An evaluation of the liquid oxygen mechanical impact test

    Science.gov (United States)

    Moffett, Gary E.; Schmidt, Naomi E.; Pedley, Michael D.; Linley, Larry J.

    1989-01-01

    This study was conducted to evaluate the repeatability of the ambient LO2 mechanical impact test used by NASA to screen materials for oxygen service (NHB 8060.1B Test 12 Part 1, which is based on the ASTM method). Four materials were tested: Teflon, Vespel SP-21, Viton A, and nylon 6/6. Each test material was subjected to several series of tests that were conducted at different impact energy levels. The results show that the variability from series to series in the reaction threshold energy level is within the precision statement of the ASTM method. However, this precision is considerably broader than the reaction threshold implied by the NHB 8060.1B test criteria.

  20. Mechanisms of polymer degradation using an oxygen plasma generator

    Science.gov (United States)

    Colony, Joe A.; Sanford, Edward L.

    1987-01-01

    An RF oxygen plasma generator was used to produce polymer degradation which appears to be similar to that which has been observed in low Earth orbit. Mechanisms of this type of degradation were studied by collecting the reaction products in a cryogenic trap and identifying the molecular species using infrared, mass spectral, and X-ray diffraction techniques. No structurally dependent species were found from Kapton, Teflon, or Saran polymers. However, very reactive free radical entities are produced during the polymer degradation, as well as carbon dioxide and water. Reactions of the free radicals with the glass reaction vessel, with copper metal in the cold trap, and with a triphenyl phosphate scavenger in the cold trap, demonstrated the reactivity of the primary products.

  1. Mechanisms of nanotoxicity: generation of reactive oxygen species.

    Science.gov (United States)

    Fu, Peter P; Xia, Qingsu; Hwang, Huey-Min; Ray, Paresh C; Yu, Hongtao

    2014-03-01

    Nanotechnology is a rapidly developing field in the 21(st) century, and the commercial use of nanomaterials for novel applications is increasing exponentially. To date, the scientific basis for the cytotoxicity and genotoxicity of most manufactured nanomaterials are not understood. The mechanisms underlying the toxicity of nanomaterials have recently been studied intensively. An important mechanism of nanotoxicity is the generation of reactive oxygen species (ROS). Overproduction of ROS can induce oxidative stress, resulting in cells failing to maintain normal physiological redox-regulated functions. This in turn leads to DNA damage, unregulated cell signaling, change in cell motility, cytotoxicity, apoptosis, and cancer initiation. There are critical determinants that can affect the generation of ROS. These critical determinants, discussed briefly here, include: size, shape, particle surface, surface positive charges, surface-containing groups, particle dissolution, metal ion release from nanometals and nanometal oxides, UV light activation, aggregation, mode of interaction with cells, inflammation, and pH of the medium. Copyright © 2014. Published by Elsevier B.V.

  2. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Klier, Kamil; Herman, Richard G

    2005-11-30

    This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brnsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with

  3. The antileishmanial activity of novel oxygenated chalcones and their mechanism of action

    DEFF Research Database (Denmark)

    Zhai, L; Chen, M; Blom, J

    1999-01-01

    and the mechanism of action of a group of new oxygenated chalcones. The tested oxygenated chalcones inhibited the in-vitro growth of Leishmania major promastigotes and Leishmania donovani amastigotes. Treatment of hamsters infected with L. donovani with intraperitoneal administration of two oxygenated chalcones...

  4. Pulmonary function after prolonged mechanical ventilation with high concentrations of oxygen.

    OpenAIRE

    Gillbe, C E; Salt, J C; Branthwaite, M A

    1980-01-01

    The mortality and morbidity resulting from mechanical ventilation with high concentrations of inspired oxygen has been investigated in two groups of patients. Ninety-one patients requiring mechanical ventilation for pulmonary disease included six (group 1) in whom death was attributed directly to respiratory failure but only three in whom oxygen toxicity might have been relevant. Review of the clinical and postmortem findings suggests that oxygen was probably not a contributory factor in two ...

  5. Assessment of ventilation inhomogeneity during mechanical ventilation using a rapid-response oxygen sensor-based oxygen washout method

    NARCIS (Netherlands)

    Bikker, Ido G.; Holland, Wim; Specht, Patricia; Ince, Can; Gommers, Diederik

    2014-01-01

    Ventilatory inhomogeneity indexes in critically ill mechanically ventilated patients could be of importance to optimize ventilator settings in order to reduce additional lung injury. The present study compared six inhomogeneity indexes calculated from the oxygen washout curves provided by the rapid

  6. Mechanical reliability of geometrically imperfect tubular oxygen transport membranes

    DEFF Research Database (Denmark)

    Kwok, Kawai; Frandsen, Henrik Lund; Søgaard, Martin

    2014-01-01

    operation. This paper investigates numerically the failure risk of tubular oxygen transport membranes under industrial operating conditions using finite element modeling and Weibull strength analysis. The effects of component manufacturing defects on fracture probability are elucidated by explicit modeling...... of imperfections in the tubular membrane geometry. A supported membrane made of dense and porous Zr-doped-BSCF is studied as an illustrative example. It is shown that stresses induced by oxygen stoichiometry gradients relax over time due to creep and external pressure is the dominating source of stress in the long...... quality (in terms of specification of tolerable deviation from perfect tubular shape) that allows fail-safe operation are deduced....

  7. Supersymmetric singlet majorons and cosmology

    International Nuclear Information System (INIS)

    Chun, E.J.; Kim, H.B.; Lukas, A.

    1994-02-01

    We examine cosmological constraints on the lepton number breaking scale in super-symmetric singlet majoron models. Special attention is drawn to the model dependence arising from the particular choice of a certain majoron extension and a cosmological scenario. We find that the bounds on the symmetry breaking scale can vary substantially. Large values of this scale can be allowed if the decoupling temperature of majoron and majorino exceeds the reheating temperature of inflation. In the opposite case an upper bound depending on the majoron model can be obtained which, however, is unlikely to be much larger than 10 10 GeV. (author). 13 refs, 2 figs

  8. Mechanisms of oxygen permeation through plastic films and barrier coatings

    Science.gov (United States)

    Wilski, Stefan; Wipperfürth, Jens; Jaritz, Montgomery; Kirchheim, Dennis; Mitschker, Felix; Awakowicz, Peter; Dahlmann, Rainer; Hopmann, Christian

    2017-10-01

    Oxygen and water vapour permeation through plastic films in food packaging or other applications with high demands on permeation are prevented by inorganic barrier films. Most of the permeation occurs through small defects (PET) are investigated and the mass transport through the polymer is simulated in a 3D approach. Calculations of single defects showed that there is no linear correlation between the defect area and the resulting permeability. The influence of adjacent defects in different distances was observed and led to flow reduction functions depending on the defect spacing and defect area. A critical defect spacing where no interaction between defects occurs was found and compared to other findings. According to the superposition principle, the permeability of single defects was added up and compared to experimentally determined oxygen permeation. The results showed the same trend of decreasing permeability with decreasing defect densities.

  9. Dynamic mechanisms of cardiac oxygenation during brief ischemia and reperfusion

    International Nuclear Information System (INIS)

    Parsons, W.J.; Rembert, J.C.; Bauman, R.P.; Greenfield, J.C. Jr.; Piantadosi, C.A.

    1990-01-01

    Myocardial oxygenation may be altered markedly by changes in tissue blood flow. During brief ischemia and reperfusion produced by transient occlusion of the left anterior descending artery in 10 open-chest dogs, changes in the oxygenation of tissue hemoglobin (Hb) plus myoglobin (Mb) and the oxidation-reduction (redox) state of mitochondrial cytochrome aa3 were monitored continuously using near-infrared spectroscopy. The nondestructive optical technique indicated that coronary occlusion produced an abrupt drop in tissue oxygen stores (tHb02 + Mb02), tissue blood volume (tBV), and the oxidation level of cytochrome aa3. Changes in the cytochrome oxidation state were related inversely to transmural collateral blood flow within the ischemic region (r = 0.77) measured with radiolabeled microspheres. Furthermore, there was a direct relationship (r = 0.91) between collateral blood flow and the tissue level of desaturated Hb and Mb (tHb + Mb). Reperfusion after 2 min of ischemia led to a synchronous overshoot of baseline in coronary flow and tBV followed by supranormal increases in tHb + Mb02 and the oxidation level of cytochrome aa3. The tHb + Mb level increased transiently during reperfusion. This response correlated inversely with collateral flow during ischemia (r = 0.91). Accordingly, the time required to reach peak tHb + Mb levels was shortest in dogs with high collateral flows (r = 0.75). Thus collateral blood flow partially sustains myocardial oxygenation during coronary artery occlusion and influences tissue reoxygenation early during reperfusion

  10. Endogenous mechanisms of reactive oxygen species (ROS generation

    Directory of Open Access Journals (Sweden)

    Agata Sarniak

    2016-11-01

    Full Text Available The main cellular source of reactive oxygen species (ROS is mitochondrial respiratory chain and active NADPH responsible for “respiratory burst” of phagocytes. Whatsmore ROS are produced in endoplasmic reticulum, peroxisomes, with the participation of xanthine and endothelial oxidase and during autoxidation process of small molecules. Mitochondrial respiratory chain is the main cellular source of ROS. It is considered that in aerobic organisms ROS are mainly formed during normal oxygen metabolism, as byproducts of oxidative phosphorylation, during the synthesis of ATP. The intermembranous phagocyte enzyme – activated NADPH oxidase, responsible for the “respiratory burst” of phagocytes, which is another source of ROS, plays an important role in defense of organism against infections.The aim of this article is to resume actuall knowledge about structure and function of the mitochondrial electron transport chain in which ROS are the byproducts and about NADPH oxidase as well as the function of each of its components in the “respiratory burst” of phagocytes.

  11. Active oxygen generation as a possible mechanism of selenium toxicity.

    Science.gov (United States)

    Seko, Y; Imura, N

    1997-09-01

    Selenium plays an important role in scavenging active oxygen (AO) species as an essential constituent of glutathione peroxidase. On the other hand, several reports proposed a possible induction of toxic AO by selenium compounds in vitro. However, some of these experiments including ours, were revealed to conclude on the basis of experimental artifacts, and to have problems in the interpretation of data. Methods or principles so far used for the detection of AO species generated by selenium compound were measurement of chemiluminescence from lucigenin or luminol by AO species, the spectrophotometric analysis of reduction of ferricytochrome c or nitroblue tetrazolium (NBT) by superoxide anion (O2-), electron spin resonance (ESR) spectra using dimethylpyrroline oxide (DMPO) as a spin trapping agent, the deoxyribose decomposition by hydroxyl radical (HO.), the salicylate hydroxylation by HO., and the strand breakage of DNA by AO. Many of these methods together with their principles seem to have some defects which prevent clear conclusion as stated below. (i) Lucigenin was found to mediate the formation of O2- in the presence of selenite and reduced glutathione (GSH). Therefore, lucigenin is not a suitable reagent. (ii) Luminol may also mediate O2- generation in the presence of HO.. (iii) ferricytochrome c can be reduced to ferrocytochrome c in the mixture of selenite and GSH in the absence of oxygen. Moreover, the spectrophotometric method is interfered by turbidity of elemental selenium formed under some conditions in the reaction mixture containing selenite and GSH. (iv) NBT is also reduced by selenium compounds in the absence of O2. (v) ESR signals of AO species were obtained in the reaction mixture containing selenite and GSH, or in the solution of hydrogen selenide in the presence of O2. However, selenide decomposed spin adduct of DMPO with HO. (DMPO-OH). Therefore, the intensity of the signals is not quantitative. (vi) CuZn-SOD is not necessarily a good tool to

  12. Colour singlets in perturbative QCD

    International Nuclear Information System (INIS)

    Bassetto, A.

    1979-01-01

    In the axial gauge and at the leading log level, a definite and consistent picture seems to emerge of a parton decay into states in which many partons are found just before confinement should take place. They are grouped into colourless clusters in a number sufficient to exhaust the ''final'' state, still possessing a finite average mass. This result is peculiar of QCD, in particular of its non-abelian nature. Large transverse momenta or more generally average invariant quantities of partons are mainly due to the multiplicities involved in the branching processes. If eventually confinement would convert these clusters into hadrons (and this is of course the main issue which has still to be proven) without a large rearrangement of the colour lines, the picture we have found for colour singlets could apply to the real hadronic world. (author)

  13. Singlet and triplet instability theorems

    Energy Technology Data Exchange (ETDEWEB)

    Yamada, Tomonori; Hirata, So, E-mail: sohirata@illinois.edu [Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801 (United States); CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan)

    2015-09-21

    A useful definition of orbital degeneracy—form-degeneracy—is introduced, which is distinct from the usual energy-degeneracy: Two canonical spatial orbitals are form-degenerate when the energy expectation value in the restricted Hartree–Fock (RHF) wave function is unaltered upon a two-electron excitation from one of these orbitals to the other. Form-degenerate orbitals tend to have isomorphic electron densities and occur in the highest-occupied and lowest-unoccupied molecular orbitals (HOMOs and LUMOs) of strongly correlated systems. Here, we present a mathematical proof of the existence of a triplet instability in a real or complex RHF wave function of a finite system in the space of real or complex unrestricted Hartree–Fock wave functions when HOMO and LUMO are energy- or form-degenerate. We also show that a singlet instability always exists in a real RHF wave function of a finite system in the space of complex RHF wave functions, when HOMO and LUMO are form-degenerate, but have nonidentical electron densities, or are energy-degenerate. These theorems provide Hartree–Fock-theory-based explanations of Hund’s rule, a singlet instability in Jahn–Teller systems, biradicaloid electronic structures, and a triplet instability during some covalent bond breaking. They also suggest (but not guarantee) the spontaneous formation of a spin density wave (SDW) in a metallic solid. The stability theory underlying these theorems extended to a continuous orbital-energy spectrum proves the existence of an oscillating (nonspiral) SDW instability in one- and three-dimensional homogeneous electron gases, but only at low densities or for strong interactions.

  14. Photochemical hydrogen-deuterium exchange reaction of tryptophan: the role in nonradiative decay of singlet tryptophan

    International Nuclear Information System (INIS)

    Saito, I.; Sugiyama, H.; Yamamoto, A.; Muramatsu, S.; Matsuura, T.

    1984-01-01

    The mechanism of nonradiative decay of singlet excited tryptophan (Trp) in aqueous solution was investigated by a highly selective photosubstitution of the C-4 hydrogen of Trp with deuterium of solvent D 2 O. It was concluded that intramolecular proton transfer from the α-ammonia group giving rise to formation of a protonated species plays an important role in the nonradiative decay of singlet Trp at neutral pH. 11 references, 1 figure

  15. Mechanism of oxygen detoxification by the surprisingly oxygen-tolerant hyperthermophilic archaeon, Pyrococcus furiosus

    Science.gov (United States)

    Thorgersen, Michael P.; Stirrett, Karen; Scott, Robert A.; Adams, Michael W. W.

    2012-01-01

    The anaerobic archaeon Pyrococcus furiosus grows by fermenting carbohydrates producing H2, CO2, and acetate. We show here that it is surprisingly tolerant to oxygen, growing well in the presence of 8% (vol/vol) O2. Although cell growth and acetate production were not significantly affected by O2, H2 production was reduced by 50% (using 8% O2). The amount of H2 produced decreased in a linear manner with increasing concentrations of O2 over the range 2–12% (vol/vol), and for each mole of O2 consumed, the amount of H2 produced decreased by approximately 2 mol. The recycling of H2 by the two cytoplasmic hydrogenases appeared not to play a role in O2 resistance because a mutant strain lacking both enzymes was not more sensitive to O2 than the parent strain. Decreased H2 production was also not due to inactivation of the H2-producing, ferredoxin-dependent membrane-bound hydrogenase because its activity was unaffected by O2 exposure. Electrons from carbohydrate oxidation must therefore be diverted to relieve O2 stress at the level of reduced ferredoxin before H2 production. Deletion strains lacking superoxide reductase (SOR) and putative flavodiiron protein A showed increased sensitivity to O2, indicating that these enzymes play primary roles in resisting O2. However, a mutant strain lacking the proposed electron donor to SOR, rubredoxin, was unaffected in response to O2. Hence, electrons from sugar oxidation normally used to produce H2 are diverted to O2 detoxification by SOR and putative flavodiiron protein A, but the electron flow pathway from ferredoxin does not necessarily involve rubredoxin.| PMID:23093671

  16. Molecular and biochemical mechanisms in teratogenesis involving reactive oxygen species

    International Nuclear Information System (INIS)

    Wells, Peter G.; Bhuller, Yadvinder; Chen, Connie S.; Jeng, Winnie; Kasapinovic, Sonja; Kennedy, Julia C.; Kim, Perry M.; Laposa, Rebecca R.; McCallum, Gordon P.; Nicol, Christopher J.; Parman, Toufan; Wiley, Michael J.; Wong, Andrea W.

    2005-01-01

    Developmental pathologies may result from endogenous or xenobiotic-enhanced formation of reactive oxygen species (ROS), which oxidatively damage cellular macromolecules and/or alter signal transduction. This minireview focuses upon several model drugs (phenytoin, thalidomide, methamphetamine), environmental chemicals (benzo[a]pyrene) and gamma irradiation to examine this hypothesis in vivo and in embryo culture using mouse, rat and rabbit models. Embryonic prostaglandin H synthases (PHSs) and lipoxygenases bioactivate xenobiotics to free radical intermediates that initiate ROS formation, resulting in oxidation of proteins, lipids and DNA. Oxidative DNA damage and embryopathies are reduced in PHS knockout mice, and in mice treated with PHS inhibitors, antioxidative enzymes, antioxidants and free radical trapping agents. Thalidomide causes embryonic DNA oxidation in susceptible (rabbit) but not resistant (mouse) species. Embryopathies are increased in mutant mice deficient in the antioxidative enzyme glucose-6-phosphate dehydrogenase (G6PD), or by glutathione (GSH) depletion, or inhibition of GSH peroxidase or GSH reductase. Inducible nitric oxide synthase knockout mice are partially protected. Inhibition of Ras or NF-kB pathways reduces embryopathies, implicating ROS-mediated signal transduction. Atm and p53 knockout mice deficient in DNA damage response/repair are more susceptible to xenobiotic or radiation embryopathies, suggesting a teratological role for DNA damage, consistent with enhanced susceptibility to methamphetamine in ogg1 knockout mice with deficient repair of oxidative DNA damage. Even endogenous embryonic oxidative stress carries a risk, since untreated G6PD- or ATM-deficient mice have increased embryopathies. Thus, embryonic processes regulating the balance of ROS formation, oxidative DNA damage and repair, and ROS-mediated signal transduction may be important determinants of teratological risk

  17. Helium-oxygen reduces the production of carbon dioxide during weaning from mechanical ventilation

    Directory of Open Access Journals (Sweden)

    Flynn Gordon

    2010-08-01

    Full Text Available Abstract Background Prolonged weaning from mechanical ventilation has a major impact on ICU bed occupancy and patient outcome, and has significant cost implications. There is evidence in patients around the period of extubation that helium-oxygen leads to a reduction in the work of breathing. Therefore breathing helium-oxygen during weaning may be a useful adjunct to facilitate weaning. We hypothesised that breathing helium-oxygen would reduce carbon dioxide production during the weaning phase of mechanical ventilation. Materials/patients and methods We performed a prospective randomised controlled single blinded cross-over trial on 19 adult intensive care patients without significant airways disease who fulfilled criteria for weaning with CPAP. Patients were randomised to helium-oxygen and air-oxygen delivered during a 2 hour period of CPAP ventilation. Carbon dioxide production (VCO2 was measured using a near patient main stream infrared carbon dioxide sensor and fixed orifice pneumotachograph. Results Compared to air-oxygen, helium-oxygen significantly decreased VCO2 production at the end of the 2 hour period of CPAP ventilation; there was a mean difference in CO2 production of 48.9 ml/min (95% CI 18.7-79.2 p = 0.003 between the groups. There were no significant differences in other respiratory and haemodynamic parameters. Conclusion This study shows that breathing a helium-oxygen mixture during weaning reduces carbon dioxide production. This physiological study supports the need for a clinical trial of helium-oxygen mixture during the weaning phase of mechanical ventilation with duration of weaning as the primary outcome. Trial registration ISRCTN56470948

  18. Assessment of ventilation inhomogeneity during mechanical ventilation using a rapid-response oxygen sensor-based oxygen washout method.

    Science.gov (United States)

    Bikker, Ido G; Holland, Wim; Specht, Patricia; Ince, Can; Gommers, Diederik

    2014-12-01

    Ventilatory inhomogeneity indexes in critically ill mechanically ventilated patients could be of importance to optimize ventilator settings in order to reduce additional lung injury. The present study compared six inhomogeneity indexes calculated from the oxygen washout curves provided by the rapid oxygen sensor of the LUFU end-expiratory lung volume measurement system. Inhomogeneity was tested in a porcine model before and after induction of acute lung injury (ALI) at four different levels of positive end-expiratory pressure (PEEP; 15, 10, 5 and 0 cm H2O). The following indexes were assessed: lung clearance index (LCI), mixing ratio, Becklake index, multiple breath alveolar mixing inefficiency, moment ratio and pulmonary clearance delay. LCI, mixing ratio, Becklake index and moment ratio were comparable with previous reported values and showed acceptable variation coefficients at baseline with and without ALI. Moment ratio had the highest precision, as calculated by the variation coefficients. LCI, Becklake index and moment ratio showed comparable increases in inhomogeneity during decremental PEEP steps before and after ALI. The advantage of the method we introduce is the combined measurement of end-expiratory lung volume (EELV) and inhomogeneity of lung ventilation with the LUFU fast-response medical-grade oxygen sensor, without the need for external tracer gases. This can be combined with conventional breathing systems. The moment ratio and LCI index appeared to be the most favourable for integration with oxygen washout curves as judged by high precision and agreement with previous reported findings. Studies are under way to evaluate the indexes in critically ill patients.

  19. Mechanisms of photosensititization by furocoumarins

    International Nuclear Information System (INIS)

    Grossweiner, L.I.

    1982-01-01

    Furocoumarins photosensitize biomolecules to UVA by way of Type I (sensitizer-substrate) and Type II (sensitizer-oxygen) mechanisms. The Type I reactions with DNA are mediated by ground state complexes. Covalent monoadducts of the furocoumarin with pyrimidines are formed in the first photochemical step. A fraction of the monoadducts of difunctional furocoumarins are converted to interstrand cross-links in a second photochemical step, as controlled by the type of monoadduct site and the spectral distribution of the radiation. Certain furocoumarins generate singlet molecular oxygen by energy transfer from the furocoumarin triplet state. The photosensitized inactivation of enzymes involves a Type II mechanism mediated by singlet oxygen. Singlet oxygen reacts with 8-methoxypsoralen to form long-lived products, which have been implicated in the formation of covalent photoconjugates with serum albumin and other proteins and peroxidation of unsaturated lipids. The available information about furocoumarin photosensitized inactivation of microorganisms indicates that DNA monoadducts are removed by an efficient excision repair process and DNA cross-links are removed by a more complex, error-prone process, both of which are under genetic control. The significantly higher sensitivity of microorganisms to difunctional furocoumarins has been identified with the formation of cross-links. Both monoadducts and cross-links induce mutations in microorganisms, with a strong dependence on the specific furocoumarin structure, the strain, and the type of mutation. 62 references, 5 tables

  20. Mechanism of p47phox-induced increase of reactive oxygen species in peripheral blood mononuclear cells from premature infants on oxygen therapy.

    Science.gov (United States)

    Zhang, Lingping; Dong, Wenbin; Li, Qingping; Kang, Lan; Zhang, Lianyu; Lu, Youying; Zhai, Xuesong

    2016-11-01

    This study aimed to explore the mechanism of p47phox-induced increase of reactive oxygen species (ROS) in peripheral blood mononuclear cells (PBMCs) from premature infants after oxygen therapy, and determine a new target for oxidative stress injury alleviation in clinical setting. First, ROS levels as well as p47phox translocation and expression in PBMC samples were evaluated after treatment of premature infants with different concentrations of oxygen. Then, changes of all various parameters were detected after in vitro treatment of PBMCs with diphenyleneiodonium (DPI), apocynin, and high oxygen levels. In premature infants, ROS levels increased significantly after treatment with oxygen, in a concentration-dependent manner (p oxygen concentrations; p47phox translocation, and expression increased as well (p oxygen increases p47phox translocationand expression, which in turn induce ROS production. DPI and apocynin have the opposite effects.

  1. Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

    KAUST Repository

    Wang, Zhandong

    2017-11-28

    Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500–600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound’s molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

  2. MEKANISME DAN KINETIKA QUENCHING OKSIGEN SINGLET DARI SENYAWA FENOLIK DAUN CENGKEH TERHADAP FOTOKSIDASI YANG DISENSITASI OLEH ERITROSIN

    Directory of Open Access Journals (Sweden)

    Edi Suryanto

    2012-02-01

    isolate phenolic compound of clove leaves and to study the mechanism and kinetic of singlet oxygen quenching. Clove leaves was extracted by steam distillation using water for 6 hours. Crude clove leaves oil was purifi ed by distillation under reduced pressure. Isolated fractions were determined its structure by infrared (IR, nuclear magnetic resonance (1H-NMR, and mass spectrometry (MS techniques. The effects of 0, 500, 1000 and 1500 ppm isolated compound on the photooxidation of linoleic acid (0,03M containing 15 ppm erythrosine in ethanol were studied by measuring peroxide value of the oil. The quenching mechanism and kinetics of eugenol were studied by the steady-state kinetic method. Samples of 0; 0,06 x 10-4; 0,12 x 10-4; 0,24 x 10-4 dan 0,48x 10-4 mM eugenol prepared in water contained 0; 17,05 x10-4; 34,10 x 10-4; 68,19 x 10-4 and 136,39 x 10-4 mM of erythrosine stored under fl uorescent light (4000 lux at room temperature for 15 hours. The result indicated that eugenol content of clove oil, F1, F2, F3 and F4 were 49.68; 54.32; 87.16 and 73.65%, respectively. The structure of F3 was identifi ed by IR spectrometry which shows strong absorption at 3448 cm-1 indicating hydroxyl group from the phenolic compound and the 1H NMR spectra showed that the number of proton ring was 3 hydrogen while the mass spectrometry showed the molecular ion peak at m/e = 164 as base peak and the absence of peak at (M-41+ as the indicator of eugenol. The result showed that eugenol had antiphotooxidation activity on erythrosine sensitized photooxidation of oil. The mechanism of singlet oxygen quenching on erythrosine photodegradation showed that eugenol only quenched singlet oxygen. The total quenching rate constant of eugenol was 4,42 x 108/M/s. Keywords: Clove leave, eugenol, quencher, erythrosine, singlet oxygen

  3. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

    2010-01-01

    We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

  4. Uncondensed Graphitic Carbon Nitride on Reduced Graphene Oxide for Oxygen Sensing via a Photoredox Mechanism.

    Science.gov (United States)

    Ellis, James E; Sorescu, Dan C; Burkert, Seth C; White, David L; Star, Alexander

    2017-08-16

    Melon, a polymeric, uncondensed graphitic carbon nitride with a two-dimensional structure, has been coupled with reduced graphene oxide (rGO) to create an oxygen chemiresistor sensor that is active under UV photoactivation. Oxygen gas is an important sensor target in a variety of areas including industrial safety, combustion process monitoring, as well as environmental and biomedical fields. Because of the intimate electrical interface formed between melon and rGO, charge transfer of photoexcited electrons occurs between the two materials when under UV (λ = 365 nm) irradiation. A photoredox mechanism wherein oxygen is reduced on the rGO surface provides the basis for sensing oxygen gas in the concentration range 300-100 000 ppm. The sensor response was found to be logarithmically proportional to oxygen gas concentration. DFT calculations of a melon-oxidized graphene composite found that slight protonation of melon leads to charge accumulation on the rGO layer and a corresponding charge depletion on the melon layer. This work provides an example of a metal-free system for solid-gas interface sensing via a photoredox mechanism.

  5. Reaction mechanism of oxygen atoms with unsaturated hydrocarbons by the crossed molecular beams method

    Energy Technology Data Exchange (ETDEWEB)

    Buss, R.J.; Baseman, R.J.; Guozhong, H.; Lee, Y.T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  6. Reaction Mechanism of Oxygen Atoms with Unsaturated Hydrocarbons by the Crossed-Molecular-Beams Method

    Science.gov (United States)

    Buss, R. J.; Baseman, R. J.; Guozhong, H.; Lee, Y. T.

    1982-04-01

    From a series of studies of the reaction of oxygen atoms with unsaturated hydrocarbons using the crossed molecular beam method, the dominant reaction mechanisms were found to be the simple substitution reactions with oxygen atoms replacing H, Cl, Br atom or alkyl groups. Complication due to secondary reaction was avoided by carrying out experiments under single collisions and observing primary products directly. Primary products were identified by measuring the angular and velocity distributions of products at all the mass numbers which could be detected by the mass spectrometer, and from comparison of these distributions, applying the requirement of energy and momentum conservation.

  7. Oxygen plasma treatments of jute fibers in improving the mechanical properties of jute/HDPE composites

    International Nuclear Information System (INIS)

    Sever, K.; Erden, S.; Guelec, H.A.; Seki, Y.; Sarikanat, M.

    2011-01-01

    Highlights: → To improve mechanical properties of jute/HDPE composites, jute fabric was subjected to oxygen plasma treatment. → LF and RF plasma systems at different plasma powers were used for treatment. → In LF system, interlaminar shear strength, tensile and flexure strengths showed a tendency to increase at plasma powers of 30 and 60 W. - Abstract: The surfaces of jute fabrics have been oxygen plasma treated using low frequency (LF) and radio frequency (RF) plasma systems at different plasma powers (30, 60, and 90 W) for 15 min to improve the mechanical properties of jute fiber/HDPE (high density polyethylene) composites. The effect of oxygen plasma treatment on the functional groups of jute fibers was examined by X-ray photoelectron spectroscopy (XPS) analysis. Effects of oxygen plasma treatments on the mechanical properties of jute fiber/HDPE composites were investigated by means of tensile, flexure, and short-beam shear tests. Surface morphology of the fractured surfaces of composites was observed by using scanning electron microscopy (SEM). When RF plasma system was used, the interlaminar shear strength (ILSS) values of the composites increased with increasing plasma power. Similarly, in LF plasma system, ILSS values showed a tendency to increase at plasma powers of 30 and 60 W. However, increasing of plasma power to 90 W decreased the ILSS value of jute/HDPE composite. Also, tensile and flexure strengths of the composites showed similar trends.

  8. Study of Al-Si Alloy Oxygen Saturation on Its Microstructure and Mechanical Properties.

    Science.gov (United States)

    Finkelstein, Arkady; Schaefer, Arseny; Chikova, Оlga; Borodianskiy, Konstantin

    2017-07-11

    One of the main goals of modern materials research is obtaining different microstructures and studying their influence on the mechanical properties of metals; aluminum alloys are particularly of interest due to their advanced performance. Traditionally, their required properties are obtained by alloying process, modification, or physical influence during solidification. The present work describes a saturation of the overheated AlSi₇Fe₁ casting alloy by oxides using oxygen blowing approach in overheated alloy. Changes in metals' microstructural and mechanical properties are also described in the work. An Al 10 SiFe intermetallic complex compound was obtained as a preferable component to Al₂O₃ precipitation on it, and its morphology was investigated by scanning electron microscopy. The mechanical properties of the alloy after the oxygen blowing treatment are discussed in this work.

  9. Production and Consumption of Reactive Oxygen Species by Fullerenes

    Science.gov (United States)

    Reactive oxygen species (ROS) are one of the most important intermediates in chemical, photochemical, and biological processes. To understand the environmental exposure and toxicity of fullerenes better, the production and consumption of ROS (singlet oxygen, superoxide, hydrogen ...

  10. Effects of Extrinsic and Intrinsic Proton Activity on The Mechanism of Oxygen Reduction in Ionic Liquids

    Science.gov (United States)

    Zeller, Robert August

    Mechanisms for oxygen reduction are proposed for three distinct cases covering two ionic liquids of fundamentally different archetypes and almost thirty orders of magnitude of proton activity. Proton activity is treated both extrinsically by varying the concentration and intrinsically by selecting proton donors with a wide range of aqueous pKa values. The mechanism of oxygen reduction in ionic liquids is introduced by way of the protic ionic liquid (pIL) triethylammonium triflate (TEATf) which shares some similarities with aqueous acid solutions. Oxygen reduction in TEATf begins as the one electron rate limited step to form superoxide, O2 *-, which is then rapidly protonated by the pIL cation forming the perhydroxyl radical, HO2*. The perhydroxyl radical is further reduced to peroxidate (HO2-) and hydrogen peroxide in proportions in accordance with their pKa. The reaction does not proceed beyond this point due to the adsorption of the conjugate base triethylammine interfering with the disproportionation of hydrogen peroxide. This work demonstrates that this mechanism is consistent across Pt, Au, Pd, and Ag electrodes. Two related sets of experiments were performed in the inherently aprotic ionic liquid 1-butyl-2,3-dimethylimidazolium triflate (C4dMImTf). The first involved the titration of acidic species of varying aqueous pKa into the IL while monitoring the extent of oxygen reduction as a function of pKa and potential on Pt and glassy carbon (GC) electrodes. These experiments confirmed the greater propensity of Pt to reduce oxygen by its immediate and abrupt transition from one electron reduction to four electron reduction, while oxygen reduction on GC gradually approaches four electron reduction as the potentials were driven more cathodic. The potential at which oxygen reduction initiates shows general agreement with the Nernst equation and the acid's tabulated aqueous pKa value, however at the extremely acidic end, a small deviation is observed. The second set

  11. Oxygen transport in perovskite-type solid oxide fuel cell materials: insights from quantum mechanics.

    Science.gov (United States)

    Muñoz-García, Ana B; Ritzmann, Andrew M; Pavone, Michele; Keith, John A; Carter, Emily A

    2014-11-18

    CONSPECTUS: Global advances in industrialization are precipitating increasingly rapid consumption of fossil fuel resources and heightened levels of atmospheric CO2. World sustainability requires viable sources of renewable energy and its efficient use. First-principles quantum mechanics (QM) studies can help guide developments in energy technologies by characterizing complex material properties and predicting reaction mechanisms at the atomic scale. QM can provide unbiased, qualitative guidelines for experimentally tailoring materials for energy applications. This Account primarily reviews our recent QM studies of electrode materials for solid oxide fuel cells (SOFCs), a promising technology for clean, efficient power generation. SOFCs presently must operate at very high temperatures to allow transport of oxygen ions and electrons through solid-state electrolytes and electrodes. High temperatures, however, engender slow startup times and accelerate material degradation. SOFC technologies need cathode and anode materials that function well at lower temperatures, which have been realized with mixed ion-electron conductor (MIEC) materials. Unfortunately, the complexity of MIECs has inhibited the rational tailoring of improved SOFC materials. Here, we gather theoretically obtained insights into oxygen ion conductivity in two classes of perovskite-type materials for SOFC applications: the conventional La1-xSrxMO3 family (M = Cr, Mn, Fe, Co) and the new, promising class of Sr2Fe2-xMoxO6 materials. Using density functional theory + U (DFT+U) with U-J values obtained from ab initio theory, we have characterized the accompanying electronic structures for the two processes that govern ionic diffusion in these materials: (i) oxygen vacancy formation and (ii) vacancy-mediated oxygen migration. We show how the corresponding macroscopic oxygen diffusion coefficient can be accurately obtained in terms of microscopic quantities calculated with first-principles QM. We find that the

  12. Color-singlet instantaneous potential in the coulomb gauge QCD

    International Nuclear Information System (INIS)

    Nakagawa, Yoshiyuki; Toki, Hiroshi; Nakamura, Atsushi; Saito, Takuya

    2007-01-01

    We study the Coulomb gauge confinement mechanism in the quenched lattice QCD simulations. It is found that the color-Coulomb instantaneous potential in the color-singlet channel between two quarks grows linearly at large distances; namely, the color-Coulomb interaction is a source of color confinement. However, the linearity of this potential remains even in the quark-gluon plasma phase. We discuss the relation between this thermal Coulomb-string tension and a magnetic scaling introduced as an infrared cutoff of the thermal QCD theory. (author)

  13. Non-diagonal processes of singlet and ordinary quark production

    International Nuclear Information System (INIS)

    Bejlin, V.A.; Vereshkov, G.M.; Kuksa, V.I.

    1995-01-01

    Non-diagonal processes of singlet and ordinary quark production are analyzed in the model where the down singlet quark mixes with the ordinary ones. The possibility of experimental selection of h-quark effects is demonstrated

  14. Targeted oxidation of Torpedo californica acetylcholinesterase by singlet oxygen: identification of N-formylkynurenine tryptophan derivatives within the active-site gorge of its complex with the photosensitizer methylene blue.

    Science.gov (United States)

    Triquigneaux, Mathilde M; Ehrenshaft, Marilyn; Roth, Esther; Silman, Israel; Ashani, Yakov; Mason, Ronald P; Weiner, Lev; Deterding, Leesa J

    2012-11-15

    The principal role of AChE (acetylcholinesterase) is termination of impulse transmission at cholinergic synapses by rapid hydrolysis of the neurotransmitter acetylcholine. The active site of AChE is near the bottom of a long and narrow gorge lined with aromatic residues. It contains a CAS (catalytic 'anionic' subsite) and a second PAS (peripheral 'anionic' site), the gorge mouth, both of which bind acetylcholine via π-cation interactions, primarily with two conserved tryptophan residues. It was shown previously that generation of (1)O(2) by illumination of MB (Methylene Blue) causes irreversible inactivation of TcAChE (Torpedo californica AChE), and suggested that photo-oxidation of tryptophan residues might be responsible. In the present study, structural modification of the TcAChE tryptophan residues induced by MB-sensitized oxidation was investigated using anti-N-formylkynurenine antibodies and MS. From these analyses, we determined that N-formylkynurenine derivatives were specifically produced from Trp(84) and Trp(279), present at the CAS and PAS respectively. Peptides containing these two oxidized tryptophan residues were not detected when the competitive inhibitors, edrophonium and propidium (which should displace MB from the gorge) were present during illumination, in agreement with their efficient protection against the MB-induced photo-inactivation. Thus the bound MB elicited selective action of (1)O(2) on the tryptophan residues facing on to the water-filled active-site gorge. The findings of the present study thus demonstrate the localized action and high specificity of MB-sensitized photo-oxidation of TcAChE, as well as the value of this enzyme as a model system for studying the mechanism of action and specificity of photosensitizing agents.

  15. Targeted oxidation of Torpedo californica acetylcholinesterase by singlet oxygen: Identification of N-formylkynurenine tryptophan derivatives within the active-site gorge of its complex with the photosensitizer methylene blue

    Science.gov (United States)

    Triquigneaux, Mathilde M.; Ehrenshaft, Marilyn; Roth, Esther; Silman, Israel; Ashani, Yakov; Mason, Ronald P.; Weiner, Lev; Deterding, Leesa J.

    2013-01-01

    Synopsis The principal role of acetylcholinesterase (AChE) is termination of impulse transmission at cholinergic synapses by rapid hydrolysis of the neurotransmitter acetylcholine. The active site of AChE is near the bottom of a long and narrow gorge lined with aromatic residues. It contains a catalytic ‘anionic’ subsite (CAS) and a second peripheral ‘anionic’ site (PAS), the gorge mouth, both of which bind acetylcholine via π-cation interactions, primarily with two conserved tryptophans (Trps). It was earlier shown that generation of 1O2 by illumination of methylene blue (MB) causes irreversible inactivation of Torpedo californica AChE (TcAChE), and suggested that photo-oxidation of Trps might be responsible. In the present study, structural modification of the TcAChE Trps induced by MB-sensitized oxidation was investigated using anti-N-formylkynurenine antibodies and mass spectrometry. From these analyses, we determined that N-formylkynurenine derivatives were specifically produced from Trp 84 and Trp 279 – present at the CAS and PAS, respectively. Peptides containing these two oxidized Trp residues were not detected when the competitive inhibitors, edrophonium and propidium (which should displace MB from the gorge) were present during illumination, in agreement with their efficient protection against the MB-induced photo-inactivation. Thus, the bound MB elicited selective action of 1O2 on Trp residues facing onto the water-filled active-site gorge. Our findings thus demonstrate the localized action and high specificity of MB-sensitized photo-oxidation of TcAChE, as well as the value of this enzyme as a model system for studying the mechanism of action and specificity of photosensitizing agents. PMID:22888904

  16. Mechanisms underlying reductant-induced reactive oxygen species formation by anticancer copper(II) compounds

    OpenAIRE

    Kowol, Christian R.; Heffeter, Petra; Miklos, Walter; Gille, Lars; Trondl, Robert; Cappellacci, Loredana; Berger, Walter; Keppler, Bernhard K.

    2011-01-01

    Intracellular generation of reactive oxygen species (ROS) via thiol-mediated reduction of copper(II) to copper(I) has been assumed as the major mechanism underlying the anticancer activity of copper(II) complexes. The aim of this study was to compare the anticancer potential of copper(II) complexes of Triapine (3-amino-pyridine-2-carboxaldehyde thiosemicarbazone; currently in phase II clinical trials) and its terminally dimethylated derivative with that of 2-formylpyridine thiosemicarbazone a...

  17. Recycling and imaging of nuclear singlet hyperpolarization

    DEFF Research Database (Denmark)

    Pileio, Giuseppe; Bowen, Sean; Laustsen, Christoffer

    2013-01-01

    observation of the same batch of polarized nuclei over a period of 30 min and more. We report a recycling protocol in which the enhanced nuclear polarization achieved by dissolution-DNP is observed with full intensity and then returned to singlet order. MRI experiments may be run on a portion of the available...

  18. Alginate Biosynthesis in Azotobacter vinelandii: Overview of Molecular Mechanisms in Connection with the Oxygen Availability

    Directory of Open Access Journals (Sweden)

    Ivette Pacheco-Leyva

    2016-01-01

    Full Text Available The Gram-negative bacterium Azotobacter vinelandii can synthetize the biopolymer alginate that has material properties appropriate for plenty of applications in industry as well as in medicine. In order to settle the foundation for improving alginate production without compromising its quality, a better understanding of the polymer biosynthesis and the mechanism of regulation during fermentation processes is necessary. This knowledge is crucial for the development of novel production strategies. Here, we highlight the key aspects of alginate biosynthesis that can lead to producing an alginate with specific material properties with particular focus on the role of oxygen availability linked with the molecular mechanisms involved in the alginate production.

  19. Conservative versus Liberal Oxygenation Targets for Mechanically Ventilated Patients. A Pilot Multicenter Randomized Controlled Trial.

    Science.gov (United States)

    Panwar, Rakshit; Hardie, Miranda; Bellomo, Rinaldo; Barrot, Loïc; Eastwood, Glenn M; Young, Paul J; Capellier, Gilles; Harrigan, Peter W J; Bailey, Michael

    2016-01-01

    There are no randomized controlled trials comparing different oxygenation targets for intensive care unit (ICU) patients. To determine whether a conservative oxygenation strategy is a feasible alternative to a liberal oxygenation strategy among ICU patients requiring invasive mechanical ventilation (IMV). At four multidisciplinary ICUs, 103 adult patients deemed likely to require IMV for greater than or equal to 24 hours were randomly allocated to either a conservative oxygenation strategy with target oxygen saturation as measured by pulse oximetry (SpO2) of 88-92% (n = 52) or a liberal oxygenation strategy with target SpO2 of greater than or equal to 96% (n = 51). The mean area under the curve and 95% confidence interval (CI) for SpO2 (93.4% [92.9-93.9%] vs. 97% [96.5-97.5%]), SaO2 (93.5% [93.1-94%] vs. 96.8% [96.3-97.3%]), PaO2 (70 [68-73] mm Hg vs. 92 [89-96] mm Hg), and FiO2 (0.26 [0.25-0.28] vs. 0.36 [0.34-0.39) in the conservative versus liberal oxygenation arm were significantly different (P liberal arm was 1% versus 0.3% (P = 0.03), and percentage time spent with SpO2 greater than 98% in conservative versus liberal arm was 4% versus 22% (P < 0.001). The adjusted hazard ratio for 90-day mortality in the conservative arm was 0.77 (95% CI, 0.40-1.50; P = 0.44) overall and 0.49 (95% CI, 0.20-1.17; P = 0.10) in the prespecified subgroup of patients with a baseline PaO2/FiO2 less than 300. Our study supports the feasibility of a conservative oxygenation strategy in patients receiving IMV. Larger randomized controlled trials of this intervention appear justified. Clinical trial registered with Australian New Zealand Clinical Trials Registry (ACTRN 12613000505707).

  20. Time-resolved CIDEP study of the photogenerated camphorquinone radical anion: a case of dual singlet and triplet precursors

    Energy Technology Data Exchange (ETDEWEB)

    Depew, M.C.; Wan, J.K.S.

    1986-12-04

    Photoreduction of camphorquinone in 2-propanol produced electron spin polarized camphorquinone radical anions. The time-resolved electron spin resonance spectra of the spin-polarized radical anions provided the first evidence of dual singlet and triplet precursors in the CIDEP phenomenon. With the results from fluorescence quenching experiments, the time dependence of the CIDEP spectra can be accounted for qualitatively by the changes of the relative contributions to the polarization among the singlet pair, F and triplet pairs, and the triplet mechanisms.

  1. Reactive species formed on proteins exposed to singlet oxygen

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan

    2004-01-01

    hydroperoxides, which can be reduced to the corresponding alcohols; other products arising from radical intermediates can also be generated, particularly in the presence of UV light and metal ions. With His side-chains, poorly characterised peroxides are also formed. Reaction with Met and Cys has been proposed...... to occur via zwitterionic peroxy intermediates. Peroxides are also generated on isolated proteins, and protein within intact cells, via(1)O(2)-mediated reactions. The peroxides formed on Trp, Tyr, and His peptides, as well as on proteins, have been shown to induce damage to other targets, with molecular...... oxidation of thiol residues an important reaction. This can result in the inactivation of cellular enzymes and the oxidation of other biological targets. Protein cross-linking and aggregation can also be induced by reactive species formed on photo-oxidised proteins, though the nature of the species...

  2. Virucidal Nanofiber Textiles Based on Photosensitized Production of Singlet Oxygen

    Science.gov (United States)

    Lhotáková, Yveta; Plíštil, Lukáš; Morávková, Alena; Kubát, Pavel; Lang, Kamil; Forstová, Jitka; Mosinger, Jiří

    2012-01-01

    Novel biomaterials based on hydrophilic polycaprolactone and polyurethane (Tecophilic®) nanofibers with an encapsulated 5,10,5,20-tetraphenylporphyrin photosensitizer were prepared by electrospinning. The doped nanofiber textiles efficiently photo-generate O2(1Δg), which oxidize external chemical and biological substrates/targets. Strong photo-virucidal effects toward non-enveloped polyomaviruses and enveloped baculoviruses were observed on the surface of these textiles. The photo-virucidal effect was confirmed by a decrease in virus infectivity. In contrast, no virucidal effect was detected in the absence of light and/or the encapsulated photosensitizer. PMID:23139839

  3. Virucidal Nanofiber Textiles Based on Photosensitized Production of Singlet Oxygen

    Czech Academy of Sciences Publication Activity Database

    Lhotáková, Y.; Plištil, L.; Morávková, A.; Kubát, Pavel; Lang, Kamil; Forstová, J.; Mosinger, J.

    2012-01-01

    Roč. 7, č. 11 (2012), e49226 E-ISSN 1932-6203 R&D Projects: GA ČR GAP208/10/1678 Institutional support: RVO:61388955 ; RVO:61388980 Keywords : photosynthesis * biomaterials * nanofiber textiles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.730, year: 2012

  4. Bioinspired composites from cross-linked galactoglucomannan and microfibrillated cellulose: Thermal, mechanical and oxygen barrier properties.

    Science.gov (United States)

    Oinonen, Petri; Krawczyk, Holger; Ek, Monica; Henriksson, Gunnar; Moriana, Rosana

    2016-01-20

    In this study, new wood-inspired films were developed from microfibrillated cellulose and galactoglucomannan-lignin networks isolated from chemothermomechanical pulping side streams and cross-linked using laccase enzymes. To the best of our knowledge, this is the first time that cross-linked galactoglucomannan-lignin networks have been used for the potential development of composite films inspired by woody-cell wall formation. Their capability as polymeric matrices was assessed based on thermal, structural, mechanical and oxygen permeability analyses. The addition of different amounts of microfibrillated cellulose as a reinforcing agent and glycerol as a plasticizer on the film performances was evaluated. In general, an increase in microfibrillated cellulose resulted in a film with better thermal, mechanical and oxygen barrier performance. However, the presence of glycerol decreased the thermal stability, stiffness and oxygen barrier properties of the films but improved their elongation. Therefore, depending on the application, the film properties can be tailored by adjusting the amounts of reinforcing agent and plasticizer in the film formulation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Photophysical characterization and time-resolved spectroscopy of a anthradithiophene dimer: exploring the role of conformation in singlet fission

    KAUST Repository

    Dean, Jacob C.

    2017-08-18

    Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of >5000 cm−1. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result

  6. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO2 surface: The case of terminal oxygen atom exchange

    Science.gov (United States)

    Kevorkyants, Ruslan; Sboev, Mikhail. N.; Chizhov, Yuri V.

    2017-05-01

    Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between 16O18O and terminal oxygen atom of a defect TiO2 surface, which is modeled by amorphous Ti8O16 nanocluster in excited S1 electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O3- chemisorption species match well EPR data on O2 adsorption on UV-irradiated nanocrystalline TiO2. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction's mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VOx/TiO2 reported earlier.

  7. Examination of the mechanism of phenanthrenequinone toxicity to Vibrio fischeri: evidence for a reactive oxygen species-mediated toxicity mechanism.

    Science.gov (United States)

    Wang, Wenxi; Nykamp, Julie; Huang, Xiao-Dong; Gerhardt, Karen; Dixon, D George; Greenberg, Bruce M

    2009-08-01

    Phenanthrenequinone (PHQ) is a photoproduct of phenanthrene, one of the most prevalent polycyclic aromatic hydrocarbons in the environment. Phenanthrenequinone is a compound of substantial interest, because its toxicity can be much greater than its parent chemical to aquatic organisms. The toxicity mechanisms of PHQ to the luminescent marine bacterium Vibrio fischeri were examined in the present study. Phenanthrenequinone can redox cycle in bacterial cells and transfer electrons to O2, enhancing the production of superoxide (O*2-), hydrogen peroxide (H2O2), and other reactive oxygen species (ROS). Exposure of cells to PHQ increased activity of superoxide dismutase (SOD), which detoxifies the ROS superoxide. Concentrations of PHQ that induced the production of H2O2 and other ROS, as well as the elevated levels of Fe-SOD, were correlated with its toxicity as measured by luminescence. Furthermore, toxicity of PHQ to V. fischeri was lowered under the anaerobic conditions, suggesting that the absence of oxygen, which would limit the production of ROS, alleviated toxicity of PHQ. Thus, a ROS-mediated toxicity mechanism of PHQ is highly implicated by in the present study.

  8. Case report: an infant with congenital junctional ectopic tachycardia requiring extracorporeal mechanical oxygenation.

    Science.gov (United States)

    Darst, Jeffrey R; Kaufman, Jon

    2007-10-01

    A case report of an infant with hemodynamic compromise and impending collapse due to congenital junctional ectopic tachycardia. Medical therapy was maximized and he required the rapid initiation of extracorporeal life support, in order to achieve hemodynamic stability. This case report briefly reviews the presentation and treatment options for congenital junctional ectopic tachycardia, as well as the indications for initiation of mechanical support for this potentially lethal condition. Congenital junctional ectopic tachycardia is a rare though often fatal arrhythmia of the newborn or infant. Medical treatment options may be limited, or may require time to attain efficacy. Despite aggressive escalation of antiarrhythmic therapy, mechanical support in the form of extracorporeal mechanical oxygenation is a viable option, until the arrhythmia is well controlled and the myocardium recovers function.

  9. Transport and noise properties of a normal metal-superconductor-normal metal junction with mixed singlet and chiral triplet pairings

    Science.gov (United States)

    Paul, Ganesh C.; Dutta, Paramita; Saha, Arijit

    2017-01-01

    We study transport and zero frequency shot noise properties of a normal metal-superconductor-normal metal (NSN) junction, with the superconductor having mixed singlet and chiral triplet pairings. We show that in the subgapped regime when the chiral triplet pairing amplitude dominates over that of the singlet, a resonance phenomena emerges out at zero energy where all the quantum mechanical scattering probabilities acquire a value of 0.25. At the resonance, crossed Andreev reflection mediating through such junction, acquires a zero energy peak. This reflects as a zero energy peak in the conductance as well depending on the doping concentration. We also investigate shot noise for this system and show that shot noise cross-correlation is negative in the subgapped regime when the triplet pairing dominates over the singlet one. The latter is in sharp contrast to the positive shot noise obtained when the singlet pairing is the dominating one.

  10. In situ monitoring of the deformation mechanisms in titanium with different oxygen contents

    Energy Technology Data Exchange (ETDEWEB)

    Barkia, B. [Laboratoire de Mécanique des Solides, UMR 7649, CNRS, École Polytechnique, Palaiseau (France); Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182, CNRS/UPEC, Thiais (France); Doquet, V. [Laboratoire de Mécanique des Solides, UMR 7649, CNRS, École Polytechnique, Palaiseau (France); Couzinié, J.P., E-mail: couzinie@icmpe.cnrs.fr [Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182, CNRS/UPEC, Thiais (France); Guillot, I. [Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182, CNRS/UPEC, Thiais (France); Héripré, E. [Laboratoire de Mécanique des Solides, UMR 7649, CNRS, École Polytechnique, Palaiseau (France)

    2015-06-11

    The deformation mechanisms of two titanium batches with different oxygen contents were monitored during tensile tests performed along the rolling and transverse directions under an optical or scanning electron microscope, after EBSD mappings of grain orientations. Whereas the contribution of mechanical twinning was very limited, grain boundary sliding, sometimes leading to intergranular decohesion, as well as kink bands formation were observed. Based on the identification of the primary slip traces in a significant number of grains, the critical resolved shear stresses (CRSSs) for prismatic, basal and π{sub 1}〈a〉 were estimated. Transmission electron microscopy was used to identify unambiguously dislocations of π{sub 1}〈c+a〉 systems and to estimate the corresponding CRSS. The difference in oxygen content between T40 and T60 was found to modify the magnitude of the CRSSs, but to leave their relative values nearly unchanged. The evolutions in the work hardening rate were correlated with the active deformation mechanisms.

  11. Singlet Glueballs In Klebanov-Strassler Theory

    Science.gov (United States)

    Gordeli, Ivan

    In this thesis we complete the singlet glueball sector analysis of the N = 1 super-symmetric Klebanov-Strassler gauge theory. Employing the string theory holographic approach we come up with a prediction of the spectrum of lightest glueballs in SU(N) N = 1 supersymmetric Yang-Mills theory at large N. Interestingly the spectrum of some of the glueballs is consistent with the lattice results for QCD glueballs.

  12. Magnetic properties of singlet ground state systems

    International Nuclear Information System (INIS)

    Diederix, K.M.

    1979-01-01

    Experiments are described determining the properties of a magnetic system consisting of a singlet ground state. Cu(NO 3 ) 2 .2 1/2H 2 O has been studied which is a system of S = 1/2 alternating antiferromagnetic Heisenberg chains. The static properties, spin lattice relaxation time and field-induced antiferromagnetically ordered state measurements are presented. Susceptibility and magnetic cooling measurements of other compounds are summarised. (Auth.)

  13. The effect of neuromuscular blockade on oxygen consumption in sedated and mechanically ventilated pediatric patients after cardiac surgery.

    NARCIS (Netherlands)

    Lemson, J.; Driessen, J.J.; Hoeven, J.G. van der

    2008-01-01

    OBJECTIVE: To measure the effect of intense neuromuscular blockade (NMB) on oxygen consumption (VO(2)) in deeply sedated and mechanically ventilated children on the first day after complex congenital cardiac surgery. DESIGN: Prospective clinical interventional study. SETTING: Pediatric intensive

  14. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

    2017-05-01

    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  15. Mechanical impact tests of materials in oxygen effects of contamination. [Teflon, stainless steel, and aluminum

    Science.gov (United States)

    Ordin, P. M.

    1980-01-01

    The effect of contaminants on the mechanical impact sensitivity of Teflon, stainless steel, and aluminum in a high-pressure oxygen environment was investigated. Uncontaminated Teflon did not ignite under the test conditions. The liquid contaminants - cutting oil, motor lubricating oil, and toolmaker dye - caused Teflon to ignite. Raising the temperature lowered the impact energy required for ignition. Stainless steel was insensitive to ignition under the test conditions with the contaminants used. Aluminum appeared to react without contaminants under certain test conditions; however, contamination with cutting oil, motor lubricating oil, and toolmakers dye increased the sensitivity of aluminum to mechanical impact. The grit contaminants silicon dioxide and copper powder did not conclusively affect the sensitivity of aluminum.

  16. Investigation on the oxygen transport mechanisms in the Sarcheshmeh waste rock dumps

    Directory of Open Access Journals (Sweden)

    Saeed Yousefi

    2015-04-01

    Full Text Available Introduction Pyrite oxidation and acid mine drainage (AMD are the serious environmental problems associated with the mining activities in sulphide ores. The rate of pyrite oxidation is governed by the availability of oxygen (Borden, 2003. Therefore, the identifying oxygen supplying mechanism is one of the most important issues related to the environmental assessment of waste rock dumps (Cathles and Apps, 1975; Jaynes et al., 1984; Davis and Ritchie, 1986. Although comprehensive researches were performed on the mathematical description of oxygen transport processes using the numerical modeling (Morin et al., 1988; Blowes et al., 1991; Wunderly et al., 1986; Elberling et al., 1994; Jannesar Malakooti et al., 2014, so far, the interactions between these processes and geochemical and mineralogical characteristics has not been studied especially in waste rock dumps. Therefore the main objective of this study is to identify the evidences for knowing the oxygen transport mechanisms in the waste dumps and also, its role in intensity of pyrite oxidation. It is expected that such these structural studies could be useful for better understanding of dominant processes in numerical modeling and also providing environmental management strategies in the study area and other sites by similar characteristics. Materials and Methods In this study, thirty solid samples were collected from six excavated trenches in the waste rock dumps No. 19 and 31 of the Sarcheshmeh porphyry copper mine. Collected samples were studied using several methods such as XRD, ASTM-D2492, paste pH and grain size distribution. The results obtained from these methods were used with the field observations in order to characterize some detail information about oxygen supplying mechanisms for oxidation reactions in the waste rock dumps. Result The main minerals found by the XRD analysis were quartz and muscovite which were present in all samples. Pyrite, orthose, albite, and chlorite were also

  17. Mechanical control of magnetism in oxygen deficient perovskite SrTiO3.

    Science.gov (United States)

    Zhang, Yajun; Wang, Jie; Sahoo, M P K; Shimada, Takahiro; Kitamura, Takayuki

    2015-10-28

    Mechanical control of magnetism in perovskite oxides is an important and promising approach in spintronics. Based on the first-principles calculations, we demonstrate that a negative pressure leads to a great enhancement of magnetic moment in deficient SrTiO3 with oxygen vacancies, whereas a positive pressure results in the gradual disappearance of magnetism. Spin charge density, Bader charge analysis and electronic density of states successfully elucidate the origin and underlying physics of the enhancement and disappearance of magnetism. It is found that the split electronic states of dz(2), dyz and dzx in the 3d orbitals of Ti atoms remarkably contribute to the occupancy of majority spin states under negative pressure, which induces a large magnetic moment. Under positive pressure, however, the equal occupancy of both majority and minority t2g and eg states leads to the disappearance of magnetization. In addition, both negative and positive pressures can largely lower the vacancy formation enthalpy, suggesting that the oxygen vacancy is preferable with pressure. Our findings may provide a mechanism to achieve the pressure control of magnetization in nonmagnetic perovskite oxides.

  18. A Simple Mechanism for Fractionating Oxygen Isotopes in the Solar Nebula

    Science.gov (United States)

    Nuth, Joseph A., III; Johnson, N. M.

    2009-01-01

    Lightning in the Solar Nebula is caused by the tribo-electric charging of dust grains carried by massive turbulent flows and driven by the accretion energy in the disk: it has long been one agent assumed responsible for the formation of chondrules. The degree to which charge separation can occur is dependent upon a number of factors, including the concentration of radioactive sources and the total level of ionization in the nebula, and these factors determine the maximum energy likely to be released by a single bolt. While chondrule formation requires a massive discharge, even a small lightning bolt can vaporize grains in the ionized discharge channel. Experimental studies have shown that silica, iron silicate and iron oxide grains formed from a high voltage discharge in hydrogen rich gas containing some oxygen produces solids that are enriched in O-17 and O-18 relative to the composition of the starting gas. Vaporization of silicates produces SiO, metal and free oxygen atoms in each discharge and these species will immediately begin to recondense from the hot plasma. Freshly condensed grains are incrementally enriched in heavy oxygen while the gas is enriched in O-16. Repeated evaporation and condensation of silicates in continuously occurring lightning discharges will monotonically increase the fractionation of oxygen isotopes between the O-17 and O-18 rich dust and the O-16 rich gas. The first mass independently fractionated refractory oxide particles were produced in the lab following the condensation of a flowing gas mixture containing variable amounts of hydrogen, silane, pentacarbonyl iron and oxygen that passed through a high voltage discharge powered by a Tesla coil. While the exact chemical pathway is still uncertain, the most probable reaction mechanisms involve oxidation of the growing refractory clusters by O3, OH or O atoms. This model has some interesting consequences for chemical processes in the early solar nebula. Chemical fractionation of

  19. Probing color-singlet exchange at D0

    International Nuclear Information System (INIS)

    Abbott, B.; Abolins, M.; Acharya, B.S.

    1997-07-01

    We present latest preliminary results on hard color-singlet exchange in proton-antiproton collisions. The fraction of dijet events produced via color-singlet exchange is measured as a function of jet transverse energy, dijet pseudorapidity separation, and proton-antiproton center-of-mass energy. These results are qualitatively consistent with a color-singlet fraction that increases with increasing quark-initiated processes

  20. Reaction pathways and mechanisms of photodegradation of pesticides.

    Science.gov (United States)

    Burrows, H D; Canle L, M; Santaballa, J A; Steenken, S

    2002-06-01

    The photodegradation of pesticides is reviewed, with particular reference to the studies that describe the mechanisms of the processes involved, the nature of reactive intermediates and final products. Potential use of photochemical processes in advanced oxidation methods for water treatment is also discussed. Processes considered include direct photolysis leading to homolysis or heterolysis of the pesticide, photosensitized photodegradation by singlet oxygen and a variety of metal complexes, photolysis in heterogeneous media and degradation by reaction with intermediates generated by photolytic or radiolytic means.

  1. Reaction pathways and mechanisms of photodegradation of pesticides

    OpenAIRE

    Burrows, H. D.; Canle L, M.; Santaballa, J. A.; Steenken, S.

    2002-01-01

    The photodegradation of pesticides is reviewed, with particular reference to the studies that describe the mechanisms of the processes involved, the nature of reactive intermediates and final products. Potential use of photochemical processes in advanced oxidation methods for water treatment is also discussed. Processes considered include direct photolysis leading to homolysis or heterolysis of the pesticide, photosensitized photodegradation by singlet oxygen and a variety of metal complexes,...

  2. Significant enhancement of the selectivity of propylene epoxidation for propylene oxide: a molecular oxygen mechanism.

    Science.gov (United States)

    Dai, Yimeng; Chen, Zongjia; Guo, Yanglong; Lu, Guanzhong; Zhao, Yifang; Wang, Haifeng; Hu, P

    2017-09-20

    As an attractive and environmentally friendly process for propylene oxide (PO) production, direct epoxidation of propylene (DEP) with molecular oxygen catalyzed by metal-based catalysts such as Ag and Cu has drawn much attention, but remains one of the biggest challenges in chemistry. In this work, the crucial competitive reactions of propylene α-H stripping (AHS) versus the oxametallacycle formation (OMMP formation) using adsorbed atomic oxygen (O*) or adsorbed molecular oxygen (O 2 *) as an oxidant are extensively compared on IB group metal surfaces (Cu, Ag and Au) with varied electronic and structural effects in order to explore the possibility to enhance the PO selectivity by virtue of first-principles calculations. The determining factor for the PO selectivity is quantitatively revealed: it is found that with atomic O*, the AHS pathway was preferred, indicating the reason for low PO selectivity with current catalysts. By contrast, the undissociated molecular O 2 * species is found to prefer to electrophilically attack the C[double bond, length as m-dash]C double bond of propylene and form a special oxametallacycle intermediate (OOMMP) rather than nucleophilically abstracting the α-H. This OOMMP can readily cleave the O-O bond and transform into OMMP. These results demonstrate that the presence of undissociated O 2 * can efficiently promote the PO selectivity. Furthermore, the merit of such a molecular O 2 * mechanism can be rationalized by our quantitative barrier decomposition analyses, which reveal that the lower hydrogen affinity (ΔE H ) of the O 2 * species dominantly contributes to the limited AHS reaction, and boosts the OMMP selectivity. Therefore, ΔE H can be applied as a selectivity descriptor. An efficient strategy to promote PO formation is presented. The insight obtained could pave the way for further development of catalysts for propylene epoxidation.

  3. Temperature Dependence of the Oxygen Reduction Mechanism in Nonaqueous Li–O 2 Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Bin [Energy; Xu, Wu [Energy; Zheng, Jianming [Energy; Yan, Pengfei [Environmental; Walter, Eric D. [Environmental; Isern, Nancy [Environmental; Bowden, Mark E. [Environmental; Engelhard, Mark H. [Environmental; Kim, Sun Tai [Energy; Department; Read, Jeffrey [Power; Adams, Brian D. [Energy; Li, Xiaolin [Energy; Cho, Jaephil [Department; Wang, Chongmin [Environmental; Zhang, Ji-Guang [Energy

    2017-10-11

    The temperature dependence of the oxygen reduction mechanism in Li-O2 batteries was investigated using carbon nanotube-based air electrodes and 1,2-dimethoxyethane-based electrolyte within a temperature range of 20C to 40C. It is found that the discharge capacity of the Li-O2 batteries decreases from 7,492 mAh g-1 at 40C to 2,930 mAh g-1 at 0C. However, a sharp increase in capacity was found when the temperature was further decreased and a very high capacity of 17,716 mAh g-1 was observed at 20C at a current density of 0.1 mA cm-2. When the temperature increases from 20C to 40C, the morphologies of the Li2O2 formed varied from ultra-small spherical particles to small flakes and then to large flake-stacked toroids. The lifetime of superoxide and the solution pathway play a dominate role on the battery capacity in the temperature range of -20C to 0C, but the electrochemical kinetics of oxygen reduction and the surface pathway dominate the discharge behavior in the temperature range of 0C to 40C. These findings provide fundamental understanding on the temperature dependence of oxygen reduction process in a Li-O2 battery and will enable a more rational design of Li-O2 batteries.

  4. Induction of radiation resistance and radio-protective mechanism. On the reactive oxygen and free radical

    Energy Technology Data Exchange (ETDEWEB)

    Yukawa, Osami [National Inst. of Radiological Sciences, Chiba (Japan). Research Center for Radiation Safety

    2003-03-01

    Radical scavenging system for reactive oxygen species (ROS) leading to radio-protection is reviewed on findings in animals, tissues and cells. Protection against oxygen toxicity in evolution can be seen in anaerobes' superoxide dismutase (SOD) over 3500 million years ago. ROS is generated endogenously and also by radiation. However, the intracellular sites of the generated ROS are different depending on its cause. The protection is done through enzymes like SOD, peroxidase, catalase, glutathione-related enzymes and through substances like GSH, {alpha}-tocopherol, ascorbic acid etc. Induction of ROS scavenging substances related with radio-resistance includes the responses to the low dose radiation (5-50 cGy) in those enzymes described above; to middle to high dose radiation (1-30 Gy) in a similar and in other unknown mechanisms; to exposure of ROS like H{sub 2}O{sub 2} at low concentration; and to antioxidant treatment. The cross-resistance between radiation and drugs suggests necessity of this induction. (N.I.)

  5. Carbon substituting for oxygen in silicates: A novel mechanism for carbon incorporation in the deep Earth

    Science.gov (United States)

    Armentrout, M. M.; Tavakoli, A.; Ionescu, E.; Mera, G.; Riedel, R.; Navrotsky, A.

    2013-12-01

    Traditionally, carbon in the deep Earth has been thought of in terms of either carbonate at high oxygen fugacities or graphite or diamond under more reducing conditions. However, material science studies of amorphous Si-O-C polymer derived ceramics have demonstrated that carbon can be accommodated as an anion substituting for oxygen in mixed silica tetrahedra. Furthermore these structures are energetically favorable relative to a mixture of crystalline silica, silicon carbide, and graphite by ten or more kJ/g.atom. Thermodynamic stability suggests that these nano-structured composites are a potentially important storage mechanism for carbon under moderately reducing conditions. Here we expand the scope of the previous work by examining the compositional effect of geologically relevant cations (calcium and magnesium) on the thermodynamic stability, nanostructure, and ability to accommodate carbon of these composites. Silicon oxy-carbides doped with magnesium, magnesium and calcium or undoped resisted crystallization at 1100 C under inert atmosphere. 29Si NMR of the samples shows a similar distribution of silicon between end-member and mixed sites (Table 1). Results are presented from studies utilizing NMR, high temperature solution calorimetry, and microprobe. Table 1. Percentages of Si species in each material as determined by 29Si NMR.

  6. Induction of radiation resistance and radio-protective mechanism. On the reactive oxygen and free radical

    International Nuclear Information System (INIS)

    Yukawa, Osami

    2003-01-01

    Radical scavenging system for reactive oxygen species (ROS) leading to radio-protection is reviewed on findings in animals, tissues and cells. Protection against oxygen toxicity in evolution can be seen in anaerobes' superoxide dismutase (SOD) over 3500 million years ago. ROS is generated endogenously and also by radiation. However, the intracellular sites of the generated ROS are different depending on its cause. The protection is done through enzymes like SOD, peroxidase, catalase, glutathione-related enzymes and through substances like GSH, α-tocopherol, ascorbic acid etc. Induction of ROS scavenging substances related with radio-resistance includes the responses to the low dose radiation (5-50 cGy) in those enzymes described above; to middle to high dose radiation (1-30 Gy) in a similar and in other unknown mechanisms; to exposure of ROS like H 2 O 2 at low concentration; and to antioxidant treatment. The cross-resistance between radiation and drugs suggests necessity of this induction. (N.I.)

  7. Mechanism of action of oxygen ozone therapy in the treatment of disc herniation and low back pain.

    Science.gov (United States)

    Borrelli, Emma

    2011-01-01

    In the low back syndrome the pain has a multifactorial origin and ozone can surprisingly display a number of beneficial effects ranging from the inhibition of inflammation, correction of ischemia and venous stasis, and finally inducing a reflex therapy effect by stimulating anti-nociceptor analgesic mechanisms. The intradiscal and intramuscular injection of oxygen-ozone is a successful approach comparable to other minimally invasive procedures, but the elucidation of the mechanisms of action remains elusive. This communication shortly reports the mechanisms of action of oxygen ozone therapy at the level of intervertebral disc and paravertebral muscles.

  8. Mechanism of artemisinin phytotoxicity action: induction of reactive oxygen species and cell death in lettuce seedlings.

    Science.gov (United States)

    Yan, Zhi-Qiang; Wang, Dan-Dan; Ding, Lan; Cui, Hai-Yan; Jin, Hui; Yang, Xiao-Yan; Yang, Jian-She; Qin, Bo

    2015-03-01

    Artemisinin has been recognized as an allelochemical that inhibits growth of several plant species. However, its mode of action is not well clarified. In this study, the mechanism of artemisinin phytotoxicity on lettuce seedlings was investigated. Root and shoot elongation of lettuce seedlings were inhibited by artemisinin in a concentration-dependent manner. The compound effectively arrested cell division and caused loss of cell viability in root tips of lettuce. Overproduction of reactive oxygen species (ROS) was induced by artemisinin. Lipid peroxidation, proline overproduction and reduction of chlorophyll content in lettuce seedlings were found after treatments. These results suggested that artemisinin could induce ROS overproduction, which caused membrane lipids peroxidation and cell death, and impacted mitosis and physiological processes, resulting in growth inhibition of receptor plants. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  9. Mechanical Ventilation during Extracorporeal Membrane Oxygenation in Patients with Acute Severe Respiratory Failure

    Directory of Open Access Journals (Sweden)

    Zhongheng Zhang

    2017-01-01

    Full Text Available Conventionally, a substantial number of patients with acute respiratory failure require mechanical ventilation (MV to avert catastrophe of hypoxemia and hypercapnia. However, mechanical ventilation per se can cause lung injury, accelerating the disease progression. Extracorporeal membrane oxygenation (ECMO provides an alternative to rescue patients with severe respiratory failure that conventional mechanical ventilation fails to maintain adequate gas exchange. The physiology behind ECMO and its interaction with MV were reviewed. Next, we discussed the timing of ECMO initiation based on the risks and benefits of ECMO. During the running of ECMO, the protective ventilation strategy can be employed without worrying about catastrophic hypoxemia and carbon dioxide retention. There is a large body of evidence showing that protective ventilation with low tidal volume, high positive end-expiratory pressure, and prone positioning can provide benefits on mortality outcome. More recently, there is an increasing popularity on the use of awake and spontaneous breathing for patients undergoing ECMO, which is thought to be beneficial in terms of rehabilitation.

  10. Mechanical Ventilation during Extracorporeal Membrane Oxygenation in Patients with Acute Severe Respiratory Failure.

    Science.gov (United States)

    Zhang, Zhongheng; Gu, Wan-Jie; Chen, Kun; Ni, Hongying

    2017-01-01

    Conventionally, a substantial number of patients with acute respiratory failure require mechanical ventilation (MV) to avert catastrophe of hypoxemia and hypercapnia. However, mechanical ventilation per se can cause lung injury, accelerating the disease progression. Extracorporeal membrane oxygenation (ECMO) provides an alternative to rescue patients with severe respiratory failure that conventional mechanical ventilation fails to maintain adequate gas exchange. The physiology behind ECMO and its interaction with MV were reviewed. Next, we discussed the timing of ECMO initiation based on the risks and benefits of ECMO. During the running of ECMO, the protective ventilation strategy can be employed without worrying about catastrophic hypoxemia and carbon dioxide retention. There is a large body of evidence showing that protective ventilation with low tidal volume, high positive end-expiratory pressure, and prone positioning can provide benefits on mortality outcome. More recently, there is an increasing popularity on the use of awake and spontaneous breathing for patients undergoing ECMO, which is thought to be beneficial in terms of rehabilitation.

  11. Dynamic zero modes of Dirac fermions and competing singlet phases of antiferromagnetic order

    Science.gov (United States)

    Goswami, Pallab; Si, Qimiao

    2017-06-01

    In quantum spin systems, singlet phases often develop in the vicinity of an antiferromagnetic order. Typical settings for such problems arise when itinerant fermions are also present. In this paper, we develop a theoretical framework for addressing such competing orders in an itinerant system, described by Dirac fermions strongly coupled to an O(3) nonlinear sigma model. We focus on two spatial dimensions, where upon disordering the antiferromagnetic order by quantum fluctuations the singular tunneling events also known as (anti)hedgehogs can nucleate competing singlet orders in the paramagnetic phase. In the presence of an isolated hedgehog configuration of the nonlinear sigma model field, we show that the fermion determinant vanishes as the dynamic Euclidean Dirac operator supports fermion zero modes of definite chirality. This provides a topological mechanism for suppressing the tunneling events. Using the methodology of quantum chromodynamics, we evaluate the fermion determinant in the close proximity of magnetic quantum phase transition, when the antiferromagnetic order-parameter field can be described by a dilute gas of hedgehogs and antihedgehogs. We show how the precise nature of emergent singlet order is determined by the overlap between dynamic fermion zero modes of opposite chirality, localized on the hedgehogs and antihedgehogs. For a Kondo-Heisenberg model on the honeycomb lattice, we demonstrate the competition between spin Peierls order and Kondo singlet formation, thereby elucidating its global phase diagram. We also discuss other physical problems that can be addressed within this general framework.

  12. Dissociation kinetics of iodine in oxygen-containing electrical discharge plasmas

    International Nuclear Information System (INIS)

    Zakharov, A.I.; Klopovskii, K.S.; Rakhimova, T.V.; Samorodov, V.A.

    1993-01-01

    Studies of the kinetics of gaseous media containing oxygen and iodine molecules have been stimulated to a substantial degree by the search for ways of improving iodine-oxygen lasers and by the need for information on loss processes for atmospheric ozone. Results are presented from an experimental study and numerical simulations of the kinetics of the dissociation of iodine in self-sustained volume discharges in high-pressure O 2 :Ar:I 2 mixtures. It is shown that the well-studied mechanism for dissociation based on excitation of iodine molecules in successive collisions with singlet oxygen and excited iodine atoms is supplanted by a substantially different mechanism involving the creation and loss of 10 radicals when the densities of atomic oxygen and ozone are high enough. It is also shown that iodine fractions as low as ∼10 -3 in the mixture lead to rapid loss of ozone molecules while less than 18% of the discharge energy is expended in the production of singlet oxygen

  13. Stability of singlet and triplet trions in carbon nanotubes

    International Nuclear Information System (INIS)

    Ronnow, Troels F.; Pedersen, Thomas G.; Cornean, Horia D.

    2009-01-01

    We investigate singlet and triplet trion states in semiconducting carbon nanotubes using a one-dimensional model. It is concluded that singlet trion states in bind up to 13.6% stronger than exciton states, and that they lower the optical transition energy with up to 50% of the tight binding band gap energy.

  14. Stability of singlet and triplet trions in carbon nanotubes

    DEFF Research Database (Denmark)

    Rønnow, Troels Frimodt; Pedersen, Thomas Garm; Cornean, Horia

    2009-01-01

    We investigate singlet and triplet trion states in semiconducting carbon nanotubes using a one-dimensional model. It is concluded that singlet trion states in bind up to 13.5% stronger than exciton states, and that they lower the optical transition energy with up to 50% of the tight binding band...

  15. An Intelligent Optical Dissolved Oxygen Measurement Method Based on a Fluorescent Quenching Mechanism

    Directory of Open Access Journals (Sweden)

    Fengmei Li

    2015-12-01

    Full Text Available Dissolved oxygen (DO is a key factor that influences the healthy growth of fishes in aquaculture. The DO content changes with the aquatic environment and should therefore be monitored online. However, traditional measurement methods, such as iodometry and other chemical analysis methods, are not suitable for online monitoring. The Clark method is not stable enough for extended periods of monitoring. To solve these problems, this paper proposes an intelligent DO measurement method based on the fluorescence quenching mechanism. The measurement system is composed of fluorescent quenching detection, signal conditioning, intelligent processing, and power supply modules. The optical probe adopts the fluorescent quenching mechanism to detect the DO content and solves the problem, whereas traditional chemical methods are easily influenced by the environment. The optical probe contains a thermistor and dual excitation sources to isolate visible parasitic light and execute a compensation strategy. The intelligent processing module adopts the IEEE 1451.2 standard and realizes intelligent compensation. Experimental results show that the optical measurement method is stable, accurate, and suitable for online DO monitoring in aquaculture applications.

  16. An Intelligent Optical Dissolved Oxygen Measurement Method Based on a Fluorescent Quenching Mechanism.

    Science.gov (United States)

    Li, Fengmei; Wei, Yaoguang; Chen, Yingyi; Li, Daoliang; Zhang, Xu

    2015-12-09

    Dissolved oxygen (DO) is a key factor that influences the healthy growth of fishes in aquaculture. The DO content changes with the aquatic environment and should therefore be monitored online. However, traditional measurement methods, such as iodometry and other chemical analysis methods, are not suitable for online monitoring. The Clark method is not stable enough for extended periods of monitoring. To solve these problems, this paper proposes an intelligent DO measurement method based on the fluorescence quenching mechanism. The measurement system is composed of fluorescent quenching detection, signal conditioning, intelligent processing, and power supply modules. The optical probe adopts the fluorescent quenching mechanism to detect the DO content and solves the problem, whereas traditional chemical methods are easily influenced by the environment. The optical probe contains a thermistor and dual excitation sources to isolate visible parasitic light and execute a compensation strategy. The intelligent processing module adopts the IEEE 1451.2 standard and realizes intelligent compensation. Experimental results show that the optical measurement method is stable, accurate, and suitable for online DO monitoring in aquaculture applications.

  17. A quantum protective mechanism in photosynthesis

    Science.gov (United States)

    Marais, Adriana; Sinayskiy, Ilya; Petruccione, Francesco; van Grondelle, Rienk

    2015-03-01

    Since the emergence of oxygenic photosynthesis, living systems have developed protective mechanisms against reactive oxygen species. During charge separation in photosynthetic reaction centres, triplet states can react with molecular oxygen generating destructive singlet oxygen. The triplet product yield in bacteria is observed to be reduced by weak magnetic fields. Reaction centres from plants' photosystem II share many features with bacterial reaction centres, including a high-spin iron whose function has remained obscure. To explain observations that the magnetic field effect is reduced by the iron, we propose that its fast-relaxing spin plays a protective role in photosynthesis by generating an effective magnetic field. We consider a simple model of the system, derive an analytical expression for the effective magnetic field and analyse the resulting triplet yield reduction. The protective mechanism is robust for realistic parameter ranges, constituting a clear example of a quantum effect playing a macroscopic role vital for life.

  18. Effect of fluid balance on alveolar-arterial oxygen gradient in mechanically ventilated patients.

    Science.gov (United States)

    Aliyali, Masoud; Sharifpour, Ali; Tavakoli, Abdolrasol

    2011-01-01

    Fluid balance affects outcome in critically ill patients. We studied the effect of fluid balance on oxygen exchange by assessing alveolar-arterial oxygen gradient (PA-a O2) in mechanically ventilated patients. Our primary objective was to evaluate the difference in PA-aO2 and the secondary goal was to evaluate the differences in age and mortality rate. This retrospective observational study was performed on patients who were admitted to medical and surgical ICUs of Sari Imam Hospital, Mazandaran University of Medical Sciences, from 2003 to 2009. Daily fluid balance was calculated by input minus output. Thirty patients with continuous positive fluid balance (PFB) and 30 subjects with continuous negative fluid balance (NFB) during 4 consecutive days were enrolled in this study. PA-a O2 was calculated in these two groups. The mean (±SD) age was 48.9±21.2 yrs. in PFB group (19 males and 11 females) and 37.1±15.7 yrs. in NFB group (25 males and 5 females) which showed a statistically significant difference in age between the two groups (p = 0.017). The 24h, 48h, and 96h fluid balances were 1226(cc)±881, 1311(cc)±751, and 957(cc)±661 in PFB group and -1122(cc)±692, -920(cc)±394, and -1164(cc)±695 in NFB group, respectively. The mean differences (±SD) of PA-a O2 in 24h, 48h, and 96h versus the same value in the admission day were 11.3±39.2, 1.69±51.1, and -1.50±64 in PFB subjects and -21.8±60.8, -27.8±84.9, and -19.3±68.7 in NFB patients. The difference was statistically significant only in the first day of admission (p = 0.015). However, no difference was detected in overall mean oxygen gradient during 96h among the two groups. Mortality rate was significantly higher in PFB patients (P < 0.0001). Positive fluid balance had no significant effect on PA-a O2 but can be used as a predictor of mortality.

  19. EFFECT OF OXYGEN INHALATION ON MICROEMBOLIC SIGNALS IN PATIENTS WITH MECHANICAL AORTIC VALVE

    Directory of Open Access Journals (Sweden)

    K. Ghandehari Z. Izadimoud

    2005-06-01

    Full Text Available Microembolic signals (MES are frequently observed in transcranial ‎Doppler (TCD recordings of patients with mechanical heart valve (MHV. If gaseous bubbles are the underlying cause, number of MES produced by MHV could be reduced with oxygen ‎inhalation. From September 2003 to September ‎2004, a consecutive series of 14 patients ‎with St Jude aortic valve visited in the cardiology clinic were referred to ‎neurosonology unit, Valie Asr Hospital, Khorasan. TCD monitoring of MES was performed with an ultrasound device and a 2 MHz probe. The MES counts were recorded during 30 ‎minutes breathing room air and thereafter 30 minutes breathing through a facial mask ‎with reservoir bag (6 liter O2 per minute. The criteria of MES detection were ‎characteristic chirping sound, unidirectional signal, random appearance within cardiac ‎cycle and intensity increase ≥ 3dB above background. The MES counts in two periods ‎of monitoring were compared with paired t test and significance was declared at P ‎< 0.05. Twelve patients (8 females and 4 males were investigated. Oxygen ventilation ‎caused a significant decrease of MES counts in the patients in comparison to breathing ‎room air (P = 0.001. It seems that MES in patients with MHV are mainly gaseous bubbles ‎caused by blood agitation with MHV. The quantity of MES in patients with MHV is ‎not related to the risk of thromboembolic complications in these patients.

  20. Magnetism of singlet - singlet ions interacting with an electron gas: application to PrAl2

    International Nuclear Information System (INIS)

    Palermo, L.

    1986-01-01

    Various magnetic quantities are investigated for a system consisting of singlet-singlet ions interacting with an electron gas. In obtaining the magnetic state equations, the molecular field approximation is used. At T=0, an onset magnetic order condition in function of crystal field and exchange parameters and eletronic density of states at Fermi level is derived. A parametric study of the model is performed numerically. Main results are shown on diagrams. From the experimental data existent in the literature for magnetisation, susceptibility and magnetic specific heat of the PrAl 2 , a fitting with the model predictions is obtained using the following parameters: exchange interaction: 611meV; crystal field parameters: 2,5 meV; band with: 10 eV (of a rectangular density of states with 0,8 el/atom). (author) [pt

  1. Complex singlet extension of the standard model

    International Nuclear Information System (INIS)

    Barger, V.; Langacker, P.; McCaskey, M.; Ramsey-Musolf, M.; Shaughnessy, G.

    2009-01-01

    We analyze a simple extension of the standard model (SM) obtained by adding a complex singlet to the scalar sector (cxSM). We show that the cxSM can contain one or two viable cold dark matter candidates and analyze the conditions on the parameters of the scalar potential that yield the observed relic density. When the cxSM potential contains a global U(1) symmetry that is both softly and spontaneously broken, it contains both a viable dark matter candidate and the ingredients necessary for a strong first order electroweak phase transition as needed for electroweak baryogenesis. We also study the implications of the model for discovery of a Higgs boson at the Large Hadron Collider

  2. Oxygen Ion Conduction in Oxide Materials: Selected Examples and Basic Mechanisms

    Directory of Open Access Journals (Sweden)

    Traqueia, L. S. M.

    2006-06-01

    Full Text Available Oxygen ion conductors with most symmetrical structures such as fluorite- and perovskite-related phases, rely on the mobility of oxygen vacancies. High-performance electrolytes, namely with the apatite type structure, recently developed, show dominant interstitial transport. In order to assess basic composition-conductivity relationships in a fluorite-derived C-type cubic structure with high tolerance to different types of oxygen defects, a series of Y2O3-based materials were studied by impedance spectroscopy in air in the range 700-1000oC. Yttria doped with CaO exhibits reasonably high ionic conduction via the vacancy mechanism. Samples doped with ZrO2 and HfO2 possess oxygen interstitials as dominant defects, but show poor ionic conductivity when compared to Ca-doped materials. These tendencies, known for other fluorite-related phases such as pyrochlores, are opposite to those observed for apatite- and K2NiF4-type structures. Comparison of ionic conductivity levels in various oxide materials suggests that fast interstitial migration may be expected for complex multicomponent materials where the ion transport occurs in lattice fragments with high bond ionicity. Furthermore, conduction-affecting stereological parameters, to a great extent, depend on the relaxation of covalent fragments.

    Los conductores iónicos de oxígeno con estructuras más simétricas como fluorita y perovsquita dependen de la movilidad de las vacantes de oxígeno. Se han desarrollado recientemente electrolitos con elevadas prestaciones, los llamados de estructura tipo apatito, que muestran transporte intersticial dominante. Con el objeto de establecer las relaciones básicas entre composición y conductividad en una estructura cúbica tipo-C derivada de la fluorita con alta tolerancia a diferentes defectos de oxígeno, se han estudiado materiales basados en Y2O3 por espectroscopía de impedancia en el rango de temperaturas entre 700 y 1000ºC. La ytria dopada con Ca

  3. Is π-Stacking Prone To Accelerate Singlet-Singlet Energy Transfers?

    Science.gov (United States)

    Gao, Di; Aly, Shawkat M; Karsenti, Paul-Ludovic; Harvey, Pierre D

    2018-03-23

    π-Stacking is the most common structural feature that dictates the optical and electronic properties of chromophores in the solid state. Herein, a unidirectional singlet-singlet energy-transfer dyad has been designed to test the effect of π-stacking of zinc(II) porphyrin, [Zn 2 ], as a slipped dimer acceptor using a BODIPY unit, [bod], as the donor, bridged by the linker C 6 H 4 C≡CC 6 H 4 . The rate of singlet energy transfer, k ET (S 1 ), at 298 K ( k ET (S 1 ) = 4.5 × 10 10 s -1 ) extracted through the change in fluorescence lifetime, τ F , of [bod] in the presence (27.1 ps) and the absence of [Zn 2 ] (4.61 ns) from Streak camera measurements, and the rise time of the acceptor signal in femtosecond transient absorption spectra (22.0 ps), is faster than most literature cases where no π-stacking effect exists (i.e., monoporphyrin units). At 77 K, the τ F of [bod] increases to 45.3 ps, indicating that k ET (S 1 ) decreases by 2-fold (2.2 × 10 10 s -1 ), a value similar to most values reported in the literature, thus suggesting that the higher value at 298 K is thermally promoted at a higher temperature.

  4. Thermal and mechanical behaviour of oxygen carrier materials for chemical looping combustion in a packed bed reactor

    International Nuclear Information System (INIS)

    Jacobs, M.; Van Noyen, J.; Larring, Y.; Mccann, M.; Pishahang, M.; Amini, S.; Ortiz, M.; Galluci, F.; Sint-Annaland, M.V.; Tournigant, D.; Louradour, E.; Snijkers, F.

    2015-01-01

    Highlights: • Ilmenite-based oxygen carriers were developed for packed-bed chemical looping. • Addition of Mn 2 O 3 increased mechanical strength and microstructure of the carriers. • Oxygen carriers were able to withstand creep and thermal cycling up to 1200 °C. • Ilmenite-based granules are a promising shape for packed-bed reactor conditions. - Abstract: Chemical looping combustion (CLC) is a promising carbon capture technology where cyclic reduction and oxidation of a metallic oxide, which acts as a solid oxygen carrier, takes place. With this system, direct contact between air and fuel can be avoided, and so, a concentrated CO 2 stream is generated after condensation of the water in the exit gas stream. An interesting reactor system for CLC is a packed bed reactor as it can have a higher efficiency compared to a fluidized bed concept, but it requires other types of oxygen carrier particles. The particles must be larger to avoid a large pressure drop in the reactor and they must be mechanically strong to withstand the severe reactor conditions. Therefore, oxygen carriers in the shape of granules and based on the mineral ilmenite were subjected to thermal cycling and creep tests. The mechanical strength of the granules before and after testing was investigated by crush tests. In addition, the microstructure of these oxygen particles was studied to understand the relationship between the physical properties and the mechanical performance. It was found that the granules are a promising shape for a packed bed reactor as no severe degradation in strength was noticed upon thermal cycling and creep testing. Especially, the addition of Mn 2 O 3 to the ilmenite, which leads to the formation of an iron–manganese oxide, seems to results in stronger granules than the other ilmenite-based granules.

  5. Tuning of redox regulatory mechanisms, reactive oxygen species and redox homeostasis under salinity stress

    Directory of Open Access Journals (Sweden)

    Hossain eSazzad

    2016-05-01

    Full Text Available Soil salinity is a crucial environmental constraint which limits biomass production at many sites on a global scale. Saline growth conditions cause osmotic and ionic imbalances, oxidative stress and perturb metabolism, e.g. the photosynthetic electron flow. The plant ability to tolerate salinity is determined by multiple biochemical and physiological mechanisms protecting cell functions, in particular by regulating proper water relations and maintaining ion homeostasis. Redox homeostasis is a fundamental cell property. Its regulation includes control of reactive oxygen species (ROS generation, sensing deviation from and readjustment of the cellular redox state. All these redox related functions have been recognized as decisive factors in salinity acclimation and adaptation. This review focuses on the core response of plants to overcome the challenges of salinity stress through regulation of ROS generation and detoxification systems and to maintain redox homeostasis. Emphasis is given to the role of NADH oxidase (RBOH, alternative oxidase (AOX, the plastid terminal oxidase (PTOX and the malate valve with the malate dehydrogenase isoforms under salt stress. Overwhelming evidence assigns an essential auxiliary function of ROS and redox homeostasis to salinity acclimation of plants.

  6. Mechanisms underlying reductant-induced reactive oxygen species formation by anticancer copper(II) compounds.

    Science.gov (United States)

    Kowol, Christian R; Heffeter, Petra; Miklos, Walter; Gille, Lars; Trondl, Robert; Cappellacci, Loredana; Berger, Walter; Keppler, Bernhard K

    2012-03-01

    Intracellular generation of reactive oxygen species (ROS) via thiol-mediated reduction of copper(II) to copper(I) has been assumed as the major mechanism underlying the anticancer activity of copper(II) complexes. The aim of this study was to compare the anticancer potential of copper(II) complexes of Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone; currently in phase II clinical trials) and its terminally dimethylated derivative with that of 2-formylpyridine thiosemicarbazone and that of 2,2'-bipyridyl-6-carbothioamide. Experiments on generation of oxidative stress and the influence of biologically relevant reductants (glutathione, ascorbic acid) on the anticancer activity of the copper complexes revealed that reductant-dependent redox cycling occurred mainly outside the cells, leading to generation and dismutation of superoxide radicals resulting in cytotoxic amounts of H(2)O(2). However, without extracellular reductants only weak intracellular ROS generation was observed at IC(50) levels, suggesting that cellular thiols are not involved in copper-complex-induced oxidative stress. Taken together, thiol-induced intracellular ROS generation might contribute to the anticancer activity of copper thiosemicarbazone complexes but is not the determining factor.

  7. The relationship between two different mechanical cost functions and muscle oxygen consumption.

    Science.gov (United States)

    Praagman, M; Chadwick, E K J; van der Helm, F C T; Veeger, H E J

    2006-01-01

    Inverse-dynamic models often use cost functions to solve the load-sharing problem. Although it is often assumed that energy is minimised, most cost functions are based on mechanically related measures like muscle force or stress. The aim of this study was to analyse the relationships of two cost functions with experimentally determined data on muscle energy consumption. Four subjects performed isometric contractions generating combinations of elbow flexion/extension and pro/supination moments. Muscle oxygen consumption (VO2) of the m. biceps breve, m. biceps longum, m. brachioradialis and m. triceps laterale was measured with near infrared spectroscopy. Both cost functions were implemented into an existing inverse-dynamic shoulder and elbow model and the individual cost values per muscle were calculated, normalised and subsequently compared to experimental VO2 values. The minimum stress cost function led to a good correspondence between VO2 and cost for the m. triceps laterale but for the flexor muscles cost was significantly lower. A newly proposed energy-related cost function showed, however, a far better correspondence. The inclusion of a linear term and muscle mass in the new criterion led model results to correspond better to experimental results. The energy-related cost function appeared to be a better measure for muscle energy consumption than the stress cost function and led to more realistic predictions of muscle activation.

  8. Mechanisms Underlying Interferon-γ-Induced Priming of Microglial Reactive Oxygen Species Production.

    Directory of Open Access Journals (Sweden)

    Nicholas G Spencer

    Full Text Available Microglial priming and enhanced reactivity to secondary insults cause substantial neuronal damage and are hallmarks of brain aging, traumatic brain injury and neurodegenerative diseases. It is, thus, of particular interest to identify mechanisms involved in microglial priming. Here, we demonstrate that priming of microglia with interferon-γ (IFN γ substantially enhanced production of reactive oxygen species (ROS following stimulation of microglia with ATP. Priming of microglial ROS production was substantially reduced by inhibition of p38 MAPK activity with SB203580, by increases in intracellular glutathione levels with N-Acetyl-L-cysteine, by blockade of NADPH oxidase subunit NOX2 activity with gp91ds-tat or by inhibition of nitric oxide production with L-NAME. Together, our data indicate that priming of microglial ROS production involves reduction of intracellular glutathione levels, upregulation of NADPH oxidase subunit NOX2 and increases in nitric oxide production, and suggest that these simultaneously occurring processes result in enhanced production of neurotoxic peroxynitrite. Furthermore, IFNγ-induced priming of microglial ROS production was reduced upon blockade of Kir2.1 inward rectifier K+ channels with ML133. Inhibitory effects of ML133 on microglial priming were mediated via regulation of intracellular glutathione levels and nitric oxide production. These data suggest that microglial Kir2.1 channels may represent novel therapeutic targets to inhibit excessive ROS production by primed microglia in brain pathology.

  9. Thermal bridgehead double inversion of the 6-methylene-and 6-ethylidene-2-methylbicyclo[3.1.0] hexanes and related materials. Rotational kinetic deuterium isotope effects and the mechanism of the thermal interconversion of cis- and trans-2,3-dimethylmethylenecyclopropanes via orthogonal and planar trimethylenemethane singlet biradicals

    International Nuclear Information System (INIS)

    Gajewski, J.J.; Chou, S.K.

    1977-01-01

    Endo- and exo-2-methyl-6-methylenebicyclo[3.1.0]hexane (N and X) interconverted at 164 0 C at a rate comparable to that for cis to trans isomerization of the 2,3-dimethylmethylenecyclopropanes (C and T) allowing the possibility that the planar trimethylenemethane singlet is responsible for the racemization observed with optically active T. Pyrolysis of the four 2-methyl-6-ethylidenebicyclo[3.1.0]hexanes revealed an average of 8 percent preservation of the exo ethylidene stereochemistry in the bridgehead double inversion reaction. The kinetic deuterium isotope effect on the interconversion of endo- and exo-6,2-methyl-6-dideuteriomethylenebicyclo[3.1.0]hexanes, k/sub H 2 //k/sub D 2 / = 1.08 +- 0.02, suggests that exo methylene rotation occurs after rate-determining formation of a planar trimethylenemethane biradical since exo methylene rotation in the formation of anti- and syn-2-methylethylidenecyclopropane from trans-2,3-dimethyldideuteriomethylenecyclopropane has an isotope effect of 1.31 +- 0.04. Detailed mechanisms for the stereochemical and kinetic data from pyrolysis of T and C which involve mainly orthogonal and, to a lesser extent, planar or bisorthogonal trimethylenemethane biradicals are presented. The origin and magnitude of rotational kinetic isotope effects in these interconversions is discussed

  10. The electroweak phase transition in models with gauge singlets

    International Nuclear Information System (INIS)

    Ahriche, A.

    2007-01-01

    A strong first order phase transition is needed for generating the baryon asymmetry; and also to save it during the electroweak phase transition (EWPT). However this condition is not fulfilled within the Standard Model (SM), but in its extensions. It is widely believed that the existence of singlet scalars in some Standard Model extensions can easily make the EWPT strongly first order. In this work, we will examine the strength of the EWPT in the simplest extension of the SM with a real gauge singlet using the sphaleron energy at the critical temperature. We find that the phase transition is stronger by adding a singlet; and also that the criterion for a strong phase transition Ω(T c )/T c >or similar 1, where Ω = (v 2 + (x - x 0 ) 2 ) ( 1)/(2) and x(x 0 ) is the singlet vacuum expectation value in the broken (symmetric) phase, is not valid for models containing singlets, even though often used in the literature. The usual condition v c /T c >or similar 1 is more meaningful, and it is satisfied for the major part of the parameter space for physically allowed Higgs masses. Then it is convenient to study the EWPT in models with singlets that couple only to the Higgs doublets, by replacing the singlets by their vevs. (orig.)

  11. The electroweak phase transition in models with gauge singlets

    Energy Technology Data Exchange (ETDEWEB)

    Ahriche, A.

    2007-04-18

    A strong first order phase transition is needed for generating the baryon asymmetry; and also to save it during the electroweak phase transition (EWPT). However this condition is not fulfilled within the Standard Model (SM), but in its extensions. It is widely believed that the existence of singlet scalars in some Standard Model extensions can easily make the EWPT strongly first order. In this work, we will examine the strength of the EWPT in the simplest extension of the SM with a real gauge singlet using the sphaleron energy at the critical temperature. We find that the phase transition is stronger by adding a singlet; and also that the criterion for a strong phase transition {omega}(T{sub c})/T{sub c} >or similar 1, where {omega} = (v{sup 2} + (x - x{sub 0}){sup 2}){sup (}1)/(2) and x(x{sub 0}) is the singlet vacuum expectation value in the broken (symmetric) phase, is not valid for models containing singlets, even though often used in the literature. The usual condition v{sub c}/T{sub c} >or similar 1 is more meaningful, and it is satisfied for the major part of the parameter space for physically allowed Higgs masses. Then it is convenient to study the EWPT in models with singlets that couple only to the Higgs doublets, by replacing the singlets by their vevs. (orig.)

  12. Regulation of lifespan by the mitochondrial electron transport chain: reactive oxygen species-dependent and reactive oxygen species-independent mechanisms.

    Science.gov (United States)

    Scialo, Filippo; Mallikarjun, Venkatesh; Stefanatos, Rhoda; Sanz, Alberto

    2013-12-01

    Aging is a consequence of the accumulation of cellular damage that impairs the capacity of an aging organism to adapt to stress. The Mitochondrial Free Radical Theory of Aging (MFRTA) has been one of the most influential ideas over the past 50 years. The MFRTA is supported by the accumulation of oxidative damage during aging along with comparative studies demonstrating that long-lived species or individuals produce fewer mitochondrial reactive oxygen species and have lower levels of oxidative damage. Recently, however, species that combine high oxidative damage with a longer lifespan (i.e., naked mole rats) have been described. Moreover, most of the interventions based on antioxidant supplementation do not increase longevity, as would be predicted by the MFRTA. Studies to date provide a clear understanding that mitochondrial function regulates the rate of aging, but the underlying mechanisms remain unclear. Here, we review the reactive oxygen species (ROS)-dependent and ROS-independent mechanisms by which mitochondria can affect longevity. We discuss the role of different ROS (superoxide, hydrogen peroxide, and hydroxyl radical), both as oxidants as well as signaling molecules. We also describe how mitochondria can regulate longevity by ROS-independent mechanisms. We discuss alterations in mitochondrial DNA, accumulation of cellular waste as a consequence of glyco- and lipoxidative damage, and the regulation of DNA maintenance enzymes as mechanisms that can determine longevity without involving ROS. We also show how the regulation of longevity is a complex process whereby ROS-dependent and ROS-independent mechanisms interact to determine the maximum lifespan of species and individuals.

  13. LEFT LATERAL POSITIONING WITH HEAD ELEVATION INCREASE THE PARTIAL PRESSURE OF OXYGEN ON PATIENTS WITH MECHANICAL VENTILATION

    Directory of Open Access Journals (Sweden)

    Karmiza Karmiza

    2017-01-01

    Full Text Available Introduction: Breathing literally means the movement of oxygen from the atmosphere and reach the cells and carbon dioxide into the atmosphere. Partial pressure of oxygen (pO2 is one of the important components in the process of respiration, especially in patients with mechanical ventilation. There are several interventions that can be performed in an effort to improve the ventilation, one of them is patients positioning: left lateral position with 30 degrees head elevation. This study aimed to determine the effect of left lateral position with 30 degrees head elevation to the value of partial pressure of oxygen in patients with mechanical ventilation in intensive care unit RSUP DR. M. Djamil Padang. Method: This study was Pra Experiments with one group pretest posttest design. 15 samples taken by purposive sampling method. Data obtained by blood gasses analysis and it was conducted since May 8th untill June 5th, 2013. Univariate data presented in frequency distribution table, while the bivariate data using the paired T test. Result: Univariate analysis showed the value of the partial pressure of oxygen ( pO2 before intervention between 119-228 mmHg , while the value of the partial pressure of oxygen ( pO2 after intervention between 132-269 mmHg . Paired T test results showed a signifi cant difference between the value of the partial pressure of oxygen (pO2 before and after intervention (p = 0.040, p < 0.05 . Discussion: The left lateral position with 30 degrees head elevation could increase the partial pressure of oxygen (pO2 in patients with mechanical ventilation. The results of this study can be used for increasing the nursingcare quality of patients with mechanical ventilation in order to reduce the time of hospitalization. Further research on these positioning interventions can be developed for patients with primary respiratory problems or lung disease. Keywords: left lateral position, partial pressure of oxygen (pO2, mechanical ventilation

  14. Probing bactericidal mechanisms induced by cold atmospheric plasmas with Escherichia coli mutants

    International Nuclear Information System (INIS)

    Perni, Stefano; Shama, Gilbert; Hobman, J. L.; Lund, P. A.; Kershaw, C. J.; Hidalgo-Arroyo, G. A.; Penn, C. W.; Deng, X. T.; Walsh, J. L.; Kong, M. G.

    2007-01-01

    Mechanisms of plasma-induced microbial inactivation have commonly been studied with physicochemical techniques. In this letter, Escherichia coli K-12 and its ΔrecA, ΔrpoS, and ΔsoxS mutants are employed to discriminate effects of UV photons, OH radicals, and reactive oxygen species produced in atmospheric discharges. This microbiological approach exploits the fact that these E. coli mutants are defective in their resistance against various external stresses. By interplaying bacterial inactivation kinetics with optical emission spectroscopy, oxygen atoms are identified as a major contributor in plasma inactivation with minor contributions from UV photons, OH radicals, singlet oxygen metastables, and nitric oxide

  15. Probing bactericidal mechanisms induced by cold atmospheric plasmas with Escherichia coli mutants

    Science.gov (United States)

    Perni, Stefano; Shama, Gilbert; Hobman, J. L.; Lund, P. A.; Kershaw, C. J.; Hidalgo-Arroyo, G. A.; Penn, C. W.; Deng, X. T.; Walsh, J. L.; Kong, M. G.

    2007-02-01

    Mechanisms of plasma-induced microbial inactivation have commonly been studied with physicochemical techniques. In this letter, Escherichia coli K-12 and its ΔrecA, ΔrpoS, and ΔsoxS mutants are employed to discriminate effects of UV photons, OH radicals, and reactive oxygen species produced in atmospheric discharges. This microbiological approach exploits the fact that these E. coli mutants are defective in their resistance against various external stresses. By interplaying bacterial inactivation kinetics with optical emission spectroscopy, oxygen atoms are identified as a major contributor in plasma inactivation with minor contributions from UV photons, OH radicals, singlet oxygen metastables, and nitric oxide.

  16. Oxygen vacancy formation and the ion migration mechanism in layered perovskite (Sr,La)3Fe2O(7-δ).

    Science.gov (United States)

    Kagomiya, Isao; Jimbo, Keigo; Kakimoto, Ken-ichi; Nakayama, Masanobu; Masson, Olivier

    2014-06-14

    Metal oxides are widely used in devices such as sensors, fuel cells, and oxygen permeation membranes. Understanding the oxide ion migration mechanism would provide fundamental insights into the relationships between the structure and properties such as ionic conductivity. The Ruddlesden-Popper perovskite (Sr,La)n+1(Fe,Co)nO3n+1 (n = 2) has characteristic oxygen permeation and ion conduction properties, resulting from the layered perovskite structure. To elucidate the ion migration mechanism in Sr2.46La0.54Fe2O7-δ (SLF) we used a combination of experimental techniques [X-ray powder diffraction (XRPD) and enthalpy investigations of the oxygen vacancy formation reaction] and computational techniques [the bond valence sum (BVS) approach and ab initio density functional theory (DFT)]. The structural analyses of SLF by XRPD and DFT agreed well. They showed that the oxygen vacancies in SLF are located at the O1 oxygen site, which is on the vertex shared by two FeO6 octahedra in the perovskite layer. Enthalpy of the oxygen vacancy formation changed at 830 °C. This is similar to the ionic conduction behavior reported for Sr3Fe2O7. The XRPD study indicates that the host structural framework did not change with temperature, while the oxygen/vacancy arrangement in SLF did change at 830 °C. The BVS and DFT studies suggested a change in the ion migration pathway, in which the ion migration through O1 sites becomes more important at temperatures higher than 830 °C.

  17. Feasibility and reliability of an automated controller of inspired oxygen concentration during mechanical ventilation.

    Science.gov (United States)

    Saihi, Kaouther; Richard, Jean-Christophe M; Gonin, Xavier; Krüger, Thomas; Dojat, Michel; Brochard, Laurent

    2014-02-19

    Hypoxemia and high fractions of inspired oxygen (FiO2) are concerns in critically ill patients. An automated FiO2 controller based on continuous oxygen saturation (SpO2) measurement was tested. Two different SpO2-FiO2 feedback open loops, designed to react differently based on the level of hypoxemia, were compared. The results of the FiO2 controller were also compared with a historical control group. The system measures SpO2, compares with a target range (92% to 96%), and proposes in real time FiO2 settings to maintain SpO2 within target. In 20 patients under mechanical ventilation, two different FiO2-SpO2 open loops were applied by a dedicated research nurse during 3 hours, each in random order. The times spent in and outside the target SpO2 values were measured. The results of the automatic controller were then compared with a retrospective control group of 30 ICU patients. SpO2-FiO2 values of the control group were collected over three different periods of 6 hours. Time in the target range was higher than 95% with the controller. When the 20 patients were separated according to the median PaO2/FiO2 (160(133-176) mm Hg versus 239(201-285)), the loop with the highest slope was slightly better (P = 0.047) for the more-hypoxemic patients. Hyperoxemia and hypoxemia durations were significantly shorter with the controller compared with usual care: SpO2 target range was reached 90% versus 24%, 27% and 32% (P controller, compared with three historical control-group periods. A specific FiO2 controller is able to maintain SpO2 reliably within a predefined target range. Two different feedback loops can be used, depending on the initial PaO2/FiO2; with both, the automatic controller showed excellent performance when compared with usual care.

  18. Singlet-to-triplet ratio in the deuteron breakup reaction pd → pnp at 585 MeV

    International Nuclear Information System (INIS)

    Uzikov, Yu.N.; Komarov, V.I.; Rathmann, F.; Seyfarth, H.

    2001-01-01

    Available experimental data on the exclusive pd → pnp reaction at 585 MeV show a narrow peak in the proton-neutron final-state interaction region. It was supposed previously, on the basis of a phenomenological analysis of the shape of this peak, that the final spin-singlet pn state provided about one third of the observed cross section. By comparing the absolute value of the measured cross section with that of pd elastic scattering using the Faeldt-Wilkin extrapolation theorem, it is shown here that the pd → pnp data can be explained mainly by the spin-triplet final state with a singlet admixture of a few percent. The smallness of the singlet contribution is compatible with existing pN → pNπ data and the one-pion exchange mechanism of the pd → pnp reaction

  19. SHORT COMMUNICATION SINGLET-TRIPLET GAP STUDIES ON ...

    African Journals Online (AJOL)

    Preferred Customer

    2009-02-10

    yahoo.com. SHORT COMMUNICATION. SINGLET-TRIPLET GAP STUDIES ON ARYL-CYCLOPENTADIENYLIDENES: INDIRECT ELECTRONIC EFFECTS. E. Vessally*. Payame Noor University (PNU), Zanjan, Iran. (Received February 10, 2009; ...

  20. The antileishmanial activity of novel oxygenated chalcones and their mechanism of action

    DEFF Research Database (Denmark)

    Zhai, L; Chen, M; Blom, J

    1999-01-01

    resulted in a significant reduction of parasite load in the liver and the spleen compared with untreated control animals. The oxygenated chalcones also inhibited the respiration of the parasite and the activity of mitochondrial dehydrogenases. Electron microscopic studies illustrated that they altered......Our previous studies have shown that licochalcone A, an oxygenated chalcone, has antileishmanial and antimalarial activities, and alters the ultrastructure and function of the mitochondria of Leishmania spp. parasites. The present study was designed to investigate the antileishmanial activity...... the ultrastructure of the mitochondria of L. major promastigote. The data clearly indicate that this group of oxygenated chalcones has a strong antileishmanial activity and might be developed into a new antileishmanial drug. The antileishmanial activity of oxygenated chalcones might be the result of interference...

  1. Flavor-singlet hidden charm pentaquark

    Science.gov (United States)

    Irie, Yoya; Oka, Makoto; Yasui, Shigehiro

    2018-02-01

    One type of hidden charm pentaquark Pc s with quark content c c ¯u d s in light-flavor singlet state is studied in the quark model. This state is analogous to the Pc with c c ¯u u d in light-flavor octet, which was observed in LHC in 2015. Considering various combinations of color, spin, and light flavor as internal quantum numbers in Pc s, we investigate the mass ordering of the Pc s's by adopting both the one-gluon exchange interaction and the instanton-induced interaction in the quark model. The most stable configuration of Pc s is identified to be total spin 1 /2 in which the c c ¯ is combined to be color octet and spin 1, while the u d s cluster is in a color octet state. The other color octet configurations, the total spin 1 /2 state with the c c ¯ spin 0, and the state with total spin 3 /2 and c c ¯ spin 1, are found as excited states. We also discuss possible decay modes of these hidden charm pentaquarks.

  2. Singlet Fission in Rubrene Derivatives: Impact of Molecular Packing

    KAUST Repository

    Sutton, Christopher

    2017-03-13

    We examine the properties of six recently synthesized rubrene derivatives (with substitutions on the side phenyl rings) that show vastly different crystal structures. In order to understand how packing in the solid state affects the excited states and couplings relevant for singlet fission, the lowest excited singlet (S), triplet (T), multiexciton (TT), and charge-transfer (CT) states of the rubrene derivatives are compared to known singlet fission materials [tetracene, pentacene, 5,12-diphenyltetracene (DPT), and rubrene itself]. While a small difference of less than 0.2 eV is calculated for the S and TT energies, a range of 0.50 to 1.2 eV in the CT energies and nearly 3 orders of magnitude in the electronic couplings are computed for the rubrene derivatives in their crystalline packings, which strongly affects the role of the CT state in facilitating SF. To rationalize experimental observations of singlet fission occurring in amorphous phases of rubrene, DPT, and tetracene, we use molecular dynamics (MD) simulations to assess the impact of molecular packing and orientations and to gain a better understanding of the parameters that control singlet fission in amorphous films compared to crystalline packings. The MD simulations point to a crystalline-like packing for thin films of tetracene; on the other hand, DPT, rubrene, and the rubrene derivatives all show various degrees of disorder with a number of sites that have larger electronic couplings than in the crystal, which can facilitate singlet fission in such thin films. Our analysis underlines the potential of these materials as promising candidates for singlet fission and helps understand how various structural motifs affect the critical parameters that control the ability of a system to undergo singlet fission.

  3. Modeling of recovery mechanism of ozone zero phenomenaby adding small amount of nitrogen in atmospheric pressure oxygen dielectric barrier discharges

    Science.gov (United States)

    Akashi, Haruaki; Yoshinaga, Tomokazu

    2013-09-01

    Ozone zero phenomena in an atmospheric pressure oxygen dielectric barrier discharges have been one of the major problems during a long time operation of ozone generators. But it is also known that the adding a small amount of nitrogen makes the recover from the ozone zero phenomena. To make clear the mechanism of recovery, authors have been simulated the discharges with using the results of Ref. 3. As a result, the recovery process can be seen and ozone density increased. It is found that the most important species would be nitrogen atoms. The reaction of nitrogen atoms and oxygen molecules makes oxygen atoms which is main precursor species of ozone. This generation of oxygen atoms is effective to increase ozone. The dependence of oxygen atom density (nO) and nitrogen atom density (nN) ratio was examined in this paper. In the condition of low nN/nO ratio case, generation of nitrogen oxide is low, and the quenching of ozone by the nitrogen oxide would be low. But in the high ratio condition, the quenching of ozone by nitrogen oxide would significant. This work was supported by KAKENHI(23560352).

  4. Mechanism of framework oxygen exchange in Fe-zeolites: a combined DFT and mass spectrometry study.

    Science.gov (United States)

    Andrikopoulos, Prokopis C; Sobalik, Zdenek; Novakova, Jana; Sazama, Petr; Sklenak, Stepan

    2013-02-25

    The role of framework oxygen atoms in N(2)O decomposition [N(2)O(g)→N(2)(g) and 1/2O(2)(g)] over Fe-ferrierite is investigated employing a combined experimental (N(2)(18)O decomposition in batch experiments followed by mass spectroscopy measurements) and theoretical (density functional theory calculations) approach. The occurrence of the isotope exchange indicates that framework oxygen atoms are involved in the N(2)O decomposition catalyzed by Fe-ferrierite. Our study, using an Fe-ferrierite sample with iron exclusively present as Fe(II) cations accommodated in the cationic sites, shows that the mobility of framework oxygen atoms in the temperature range: 553 to 593 K is limited to the four framework oxygen atoms of the two AlO(4)(-) tetrahedra forming cationic sites that accomodate Fe(II). They exchange with the Fe extra-framework (18)O atom originating from the decomposed N(2)(18)O. We found, using DFT calculations, that O(2) molecules facilitate the oxygen exchange. However, the corresponding calculated energy barrier of 87 kcal  mol(-1) is still very high and it is higher than the assumed experimental value based on the occurrence of the sluggish oxygen exchange at 553 K. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Oxygen self-diffusion mechanisms in monoclinic Zr O2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

    Science.gov (United States)

    Yang, Jing; Youssef, Mostafa; Yildiz, Bilge

    2018-01-01

    In this work, we quantify oxygen self-diffusion in monoclinic-phase zirconium oxide as a function of temperature and oxygen partial pressure. A migration barrier of each type of oxygen defect was obtained by first-principles calculations. Random walk theory was used to quantify the diffusivities of oxygen interstitials by using the calculated migration barriers. Kinetic Monte Carlo simulations were used to calculate diffusivities of oxygen vacancies by distinguishing the threefold- and fourfold-coordinated lattice oxygen. By combining the equilibrium defect concentrations obtained in our previous work together with the herein calculated diffusivity of each defect species, we present the resulting oxygen self-diffusion coefficients and the corresponding atomistically resolved transport mechanisms. The predicted effective migration barriers and diffusion prefactors are in reasonable agreement with the experimentally reported values. This work provides insights into oxygen diffusion engineering in Zr O2 -related devices and parametrization for continuum transport modeling.

  6. Unraveling the photocatalytic mechanisms on TiO2 surfaces using the oxygen-18 isotopic label technique.

    Science.gov (United States)

    Pang, Xibin; Chen, Chuncheng; Ji, Hongwei; Che, Yanke; Ma, Wanhong; Zhao, Jincai

    2014-10-10

    During the last several decades TiO2 photocatalytic oxidation using the molecular oxygen in air has emerged as a promising method for the degradation of recalcitrant organic pollutants and selective transformations of valuable organic chemicals. Despite extensive studies, the mechanisms of these photocatalytic reactions are still poorly understood due to their complexity. In this review, we will highlight how the oxygen-18 isotope labeling technique can be a powerful tool to elucidate complicated photocatalytic mechanisms taking place on the TiO2 surface. To this end, the application of the oxygen-18 isotopic-labeling method to three representative photocatalytic reactions is discussed: (1) the photocatalytic hydroxylation of aromatics; (2) oxidative cleavage of aryl rings on the TiO2 surface; and (3) photocatalytic decarboxylation of saturated carboxylic acids. The results show that the oxygen atoms of molecular oxygen can incorporate into the corresponding products in aqueous solution in all three of these reactions, but the detailed incorporation pathways are completely different in each case. For the hydroxylation process, the O atom in O2 is shown to be incorporated through activation of O2 by conduction band electrons. In the cleavage of aryl rings, O atoms are inserted into the aryl ring through the site-dependent coordination of reactants on the TiO2 surface. A new pathway for the decarboxylation of saturated carboxylic acids with pyruvic acid as an intermediate is identified, and the O2 is incorporated into the products through the further oxidation of pyruvic acid by active species from the activation of O2 by conduction band electrons.

  7. External quantum efficiency exceeding 100% in a singlet-exciton-fission-based solar cell

    Science.gov (United States)

    Baldo, Marc

    2013-03-01

    Singlet exciton fission can be used to split a molecular excited state in two. In solar cells, it promises to double the photocurrent from high energy photons, thereby breaking the single junction efficiency limit. We demonstrate organic solar cells that exploit singlet exciton fission in pentacene to generate more than one electron per incident photon in the visible spectrum. Using a fullerene acceptor, a poly(3-hexylthiophene) exciton confinement layer, and a conventional optical trapping scheme, the peak external quantum efficiency is (109 +/-1)% at λ = 670 nm for a 15-nm-thick pentacene film. The corresponding internal quantum efficiency is (160 +/-10)%. Independent confirmation of the high internal efficiency is obtained by analysis of the magnetic field effect on photocurrent, which determines that the triplet yield approaches 200% for pentacene films thicker than 5 nm. To our knowledge, this is the first solar cell to generate quantum efficiencies above 100% in the visible spectrum. Alternative multiple exciton generation approaches have been demonstrated previously in the ultraviolet, where there is relatively little sunlight. Singlet exciton fission differs from these other mechanisms because spin conservation disallows the usual dominant loss process: a thermal relaxation of the high-energy exciton into a single low-energy exciton. Consequently, pentacene is efficient in the visible spectrum at λ = 670 nm because only the collapse of the singlet exciton into twotriplets is spin-allowed. Supported as part of the Center for Excitonics, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001088.

  8. Reactions of plutonium dioxide with water and oxygen-hydrogen mixtures: Mechanisms for corrosion of uranium and plutonium

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, John M.; Allen, Thomas H.; Morales, Luis A.

    1999-06-18

    Investigation of the interactions of plutonium dioxide with water vapor and with an oxygen-hydrogen mixture show that the oxide is both chemically reactive and catalytically active. Correspondence of the chemical behavior with that for oxidation of uranium in moist air suggests that similar catalytic processes participate in the mechanism of moisture-enhanced corrosion of uranium and plutonium. Evaluation of chemical and kinetic data for corrosion of the metals leads to a comprehensive mechanism for corrosion in dry air, water vapor, and moist air. Results are applied in confirming that the corrosion rate of Pu in water vapor decreases sharply between 100 and 200 degrees C.

  9. Reliable Prediction with Tuned Range-Separated Functionals of the Singlet-Triplet Gap in Organic Emitters for Thermally Activated Delayed Fluorescence (TADF)

    KAUST Repository

    Sun, Haitao

    2015-07-09

    The thermally activated delayed fluorescence (TADF) mechanism has recently attracted much interest in the field of organic light-emitting diodes (OLEDs). TADF relies on the presence of a very small energy gap between the lowest singlet and triplet excited states. Here, we demonstrate that time-dependent density functional theory (TD-DFT) in the Tamm-Dancoff Approximation can be very successful in the calculations of the lowest singlet and triplet excitation energies and the corresponding singlet-triplet gap when using nonempirically tuned range-separated functionals. Such functionals provide very good estimates in a series of 17 molecules used in TADF-based OLED devices, with mean absolute deviations of 0.15 eV for the vertical singlet excitation energies and 0.09 eV [0.07 eV] for the adiabatic [vertical] singlet-triplet energy gaps as well as low relative errors and high correlation coefficients compared to the corresponding experimental values. They significantly outperform conventional functionals, a feature which is rationalized on the basis of the amount of exact-exchange included and the delocalization error. The present work provides a reliable theoretical tool for the prediction and development of novel TADF-based materials with low singlet-triplet energetic splittings.

  10. A Mechanism for Oxygen Exchange between Ligated Oxometalloporphinates and Bulk Water

    NARCIS (Netherlands)

    Primus, J.; Teunis, K.; Mandon, D.; Veeger, C.; Rietjens, I.M.C.M.

    2000-01-01

    Oxygen exchange between high-valent metal–oxo complexes and bulk water has been monitored for nonligated model porphyrins (hemin, FeTDCPPS, MnTMPyP) and the axially ligated microperoxidase-8 (MP-8). Exchange extents up to 90 ere measured for MP-8 in spite of the presence of an axial histidine ligand

  11. Microalgae mediated bio-electrocatalytic fuel cell facilitates bioelectricity generation through oxygenic photomixotrophic mechanism.

    Science.gov (United States)

    Venkata Subhash, G; Chandra, Rashmi; Venkata Mohan, S

    2013-05-01

    Electrogenic activity of oxygenic photo-bioelectrocatalytic fuel cell (PhFCOX) under mixotrophic mode was evaluated using atmospheric CO2 and domestic wastewater as carbon sources for harnessing bioelectricity with mixed microalgae as anodic biocatalyst. PhFCOX operation showed good electrogenic activity (3.55 μW/m(2)) associated with higher biomass growth (2.87 g/l) and chlorophyll content (5.12 mg/l). Electrogenic activity was relatively higher during the day time (46 mV; 0.6 mA) compared to the night (6 mV; 0.01 mA). Performance of PhFCOX undergoing oxygenic photosynthesis (DO; 3.5 mg/l) was compared with the mixotrophic fuel cell (PhFCAX) with photosynthetic bacteria as biocatalyst under anoxygenic conditions (DO; 0.45 mg/l). The dissolved oxygen produced during photolysis of water in oxygenic photosynthesis is a major limiting factor affecting the electrogenic activity. Voltammetric and amperometric analysis along with electron transfer kinetics (Tafel analysis) supported the bio-electrochemical behavior of PhFCOX and PhFCAX. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Indomethacin decreases optic nerve oxygen tension by a mechanism other than cyclo-oxygenase inhibition

    DEFF Research Database (Denmark)

    Noergaard, M Hove; Pedersen, D Bach; Bang, K

    2008-01-01

    We investigated the effect of several Non-Steroidal Anti-Inflammatory Drugs (NSAIDs), on the preoptic nerve oxygen tension (ONPO2), as indomethacin previously has demonstrated a strong decreasing effect on ONPO2. We tested whether these NSAIDs, like indomethacin, also reduce the increasing effect...

  13. Silkworm (Bombyx mori) hemocytes do not produce reactive oxygen metabolites as a part of defense mechanisms

    Czech Academy of Sciences Publication Activity Database

    Hyršl, P.; Číž, Milan; Kubala, Lukáš; Lojek, Antonín

    2004-01-01

    Roč. 49, č. 3 (2004), s. 315-319 ISSN 0015-5632 R&D Projects: GA AV ČR IBS5004009 Institutional research plan: CEZ:AV0Z5004920 Keywords : hemocytes * Bombyx mori * reactive oxygen species Subject RIV: BO - Biophysics Impact factor: 1.034, year: 2004

  14. Role of dissolved oxygen on the degradation mechanism of Reactive Green 19 and electricity generation in photocatalytic fuel cell.

    Science.gov (United States)

    Lee, Sin-Li; Ho, Li-Ngee; Ong, Soon-An; Wong, Yee-Shian; Voon, Chun-Hong; Khalik, Wan Fadhilah; Yusoff, Nik Athirah; Nordin, Noradiba

    2018-03-01

    In this study, a membraneless photocatalytic fuel cell with zinc oxide loaded carbon photoanode and platinum loaded carbon cathode was constructed to investigate the impact of dissolved oxygen on the mechanism of dye degradation and electricity generation of photocatalytic fuel cell. The photocatalytic fuel cell with high and low aeration rate, no aeration and nitrogen purged were investigated, respectively. The degradation rate of diazo dye Reactive Green 19 and the electricity generation was enhanced in photocatalytic fuel cell with higher dissolved oxygen concentration. However, the photocatalytic fuel cell was still able to perform 37% of decolorization in a slow rate (k = 0.033 h -1 ) under extremely low dissolved oxygen concentration (approximately 0.2 mg L -1 ) when nitrogen gas was introduced into the fuel cell throughout the 8 h. However, the change of the UV-Vis spectrum indicates that the intermediates of the dye could not be mineralized under insufficient dissolved oxygen level. In the aspect of electricity generation, the maximum short circuit current (0.0041 mA cm -2 ) and power density (0.00028 mW cm -2 ) of the air purged photocatalytic fuel cell was obviously higher than that with nitrogen purging (0.0015 mA cm -2 and 0.00008 mW cm -2 ). Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Mechanism of oxidation of 3-hydroxy-2,7-naphthalenedisulfonic acid disodium salt with oxygen in subcritical water.

    Science.gov (United States)

    Imbierowicz, Mirosław

    2017-06-01

    The article presents the results of studies on the oxidation mechanism of 3-hydroxy-2,7-naphthalenedisulfonic acid disodium salt (R-salt) with oxygen in subcritical water. To this aim, a series of experiments were carried out which showed that at a temperature of 413 K and pH > 9 the oxidation reaction of a substrate with oxygen was relatively quick and after approximately 40 min the R-salt oxidation yield exceeded 95%. In an acidic medium (pH oxidation is small. In order to identify the mechanism of R-salt oxidation, experiments were carried out at 413-569 K in solutions with pH = 10.0 and at partial oxygen pressure p O2  = 1.73 MPa. As a result of these experiments, a stable oxidation product was isolated from the reaction mixture and subjected to spectroscopic analysis. The analysis of H NMR of this product proved that a stable intermediate product of R-salt oxidation was 4-sulfophthalic acid sodium salt. The results of the experiments have shown that destructive oxidation of R-salt can easily be obtained at a temperature of 413 K, but satisfactory reduction of TOC in wastewater containing this substrate requires the use of very high temperature: at 569 K only 60% reduction of TOC was achieved. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Relative effects of chromium and niobium on microstructure and mechanical properties as a function of oxygen content in TiAl alloys

    International Nuclear Information System (INIS)

    Lamirand, M.; Bonnentien, J.-L.; Ferriere, G.; Guerin, S.; Chevalier, J.-P.

    2007-01-01

    The effects of 2 at.% chromium and niobium on microstructure and mechanical properties of Ti-48Al-x(Cr, Nb) have been investigated for alloys with different oxygen content, ranging from ultra-high purity to doped alloys. Chromium and niobium additions have significant effects for the high purity alloys, whereas for alloys containing oxygen, no significant modification is observed due to the strong stabilizing effect of oxygen on the lamellar microstructure

  17. Mechanical indentation improves cerebral blood oxygenation signal quality of functional near-infrared spectroscopy (fNIRS) during breath holding

    Science.gov (United States)

    Vogt, William C.; Romero, Edwin; LaConte, Stephen M.; Rylander, Christopher G.

    2013-03-01

    Functional near-infrared spectroscopy (fNIRS) is a well-known technique for non-invasively measuring cerebral blood oxygenation, and many studies have demonstrated that fNIRS signals can be related to cognitive function. However, the fNIRS signal is attenuated by the skin, while scalp blood content has been reported to influence cerebral oxygenation measurements. Mechanical indentation has been shown to increase light transmission through soft tissues by causing interstitial water and blood flow away from the compressed region. To study the effects of indentation on fNIRS, a commercial fNIRS system with 16 emitter/detector pairs was used to measure cerebral blood oxygenation at 2 Hz. This device used diffuse reflectance at 730 nm and 850 nm to calculate deoxy- and oxy-hemoglobin concentrations. A borosilicate glass hemisphere was epoxied over each sensor to function as both an indenter and a lens. After placing the indenter/sensor assembly on the forehead, a pair of plastic bands was placed on top of the fNIRS headband and strapped to the head to provide uniform pressure and tightened to approx. 15 N per strap. Cerebral blood oxygenation was recorded during a breath holding regime (15 second hold, 15 second rest, 6 cycles) in 4 human subjects both with and without the indenter array. Results showed that indentation increased raw signal intensity by 85 +/- 35%, and that indentation increased amplitude of hemoglobin changes during breath cycles by 313% +/- 105%. These results suggest that indentation improves sensing of cerebral blood oxygenation, and may potentially enable sensing of deeper brain tissues.

  18. Muscle tissue oxygenation, pressure, electrical, and mechanical responses during dynamic and static voluntary contractions

    DEFF Research Database (Denmark)

    Vedsted, Pernille; Blangsted, Anne Katrine; Søgaard, Karen

    2006-01-01

    Dynamic muscle contractions have been shown to cause greater energy turnover and fatigue than static contractions performed at a corresponding force level. Therefore, we hypothesized that: (1) electro- (EMG) and mechanomyography (MMG), intramuscular pressure (IMP), and reduction in muscle oxygen...... similar in spite of major differences in the MMG and EMG responses of the muscle during contraction periods. This may relate to the surprisingly lower IMP in DYN than IST....... tension (rTO(2)) would be larger during dynamic (DYN) than intermittent static (IST) low force contractions; and that (2) oxygen tension would remain lower in the resting periods subsequent to DYN as compared to those following IST. Eight subjects performed elbow flexions with identical time...

  19. Effects of positive end-expiratory pressure and 30% inspired oxygen on pulmonary mechanics and atelectasis in cats undergoing non-bronchoscopic bronchoalveolar lavage.

    Science.gov (United States)

    Bernhard, Christa; Masseau, Isabelle; Dodam, John; Outi, Hilton; Krumme, Stacy; Bishop, Kaitlin; Graham, Amber; Reinero, Carol

    2017-06-01

    Objectives The objective of this study was to determine if modification of inspired oxygen concentration or positive end-expiratory pressure (PEEP) would alter bronchoalveolar lavage (BAL)-induced changes in pulmonary mechanics or atelectasis, as measured using ventilator-acquired pulmonary mechanics and thoracic CT. Methods Six experimentally asthmatic cats underwent anesthesia and non-bronchoscopic BAL, each under four randomized treatment conditions: 100% oxygen, zero PEEP; 30% oxygen, zero PEEP; 100% oxygen, PEEP 2 cmH 2 O; and 30% oxygen, PEEP 2 cmH 2 O. Pulse oximetry was used to estimate oxygen saturation (SpO 2 ). Ventilator-acquired pulmonary mechanics and thoracic CT scans were collected prior to BAL and at 1, 5 and 15 mins post-BAL. Results While receiving 100% oxygen, no cat had SpO 2 90% by 1 min later. There was a significant increase in airway resistance and a decrease in lung compliance following BAL, but there was no significant difference between treatment groups. Cats receiving no PEEP and 30% oxygen conserved better aeration of the lung parenchyma in BAL-sampled areas than those receiving no PEEP and 100% oxygen. Conclusions and relevance Alterations in pulmonary mechanics or atelectasis may not be reflected by SpO 2 following BAL. The use of 30% inspired oxygen concentration failed to show any significant improvement in pulmonary mechanics but did diminish atelectasis. In some cats, it was also associated with desaturation of hemoglobin. The use of PEEP in this study did not show any effect on our outcome parameters. Further studies using higher PEEP (5-10 cmH 2 O) and intermediate inspired oxygen concentration (40-60%) are warranted to determine if they would confer clinical benefit in cats undergoing diagnostic BAL.

  20. Different diffusion mechanisms of oxygen in ReBa{sub 2}Cu{sub 3}O{sub 7−x} (Re = Y, Ho) single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Vovk, R.V.; Boiko, Y.I.; Bogdanov, V.V.; Kamchatnaya, S.N.; Goulatis, I.L. [V. N. Karazin Kharkiv National University, 4 Svobody sq., 61077 Kharkiv (Ukraine); Chroneos, A. [Faculty of Engineering, Environment and Computing, Coventry University, Priory Street, Coventry CV1 5FB (United Kingdom); Department of Materials, Imperial College London, London SW7 2AZ (United Kingdom)

    2017-05-15

    Highlights: • Single file diffusion mechanism of oxygen ions. • Ho modifies the diffusion mechanism in the oxygen sublattice. • Ho changes the efficient interaction of ions in CuO-planes. - Abstract: In the present study, the time dependencies of the resistivity of ReBa{sub 2}Cu{sub 3}O{sub 7−x} (Re=Y, Ho) single crystals with varying degree of deviation from oxygen stoichiometry was investigated. It was shown that the accelerated transport of oxygen ions in the initial stage of the process can be carried out along the one-dimensional non-stoichiometric vacancies’ accumulation by the single file diffusion mechanism. The final phase redistribution of oxygen ions in ReBa{sub 2}Cu{sub 3}O{sub 7−x} (Re = Y, Ho) is described by the classical mechanism of volume diffusion. The substitution of yttrium by holmium significantly affects the charge redistribution and changes the efficient interaction of ions in CuO-planes, thereby modifying the mass transfer diffusion mechanisms in the oxygen sublattice. Thus, a significant length change of the time intervals occurs, corresponding to the oxygen ions’ single file and volume diffusion mechanisms.

  1. Recoil detection of the lightest neutralino in MSSM singlet extensions

    International Nuclear Information System (INIS)

    Barger, Vernon; Lewis, Ian; McCaskey, Mat; Shaughnessy, Gabe; Yencho, Brian; Langacker, Paul

    2007-01-01

    We investigate the correlated predictions of singlet extended MSSM models for direct detection and the cosmological relic density of the lightest neutralino. To illustrate the general effects of the singlet, we take heavy sleptons and squarks. We apply CERN LEP (g-2) μ , and perturbativity constraints. We find that the WMAP upper bound on the cold dark matter density limits much of the parameter space to regions where the lightest neutralino can be discovered in recoil experiments. The results for the next-to-minimal supersymmetric standard model and U(1) ' -extended minimal supersymmetric standard model are typically similar to the MSSM since their light neutralinos have similar compositions and masses. In the nearly minimal supersymmetric standard model the neutralino is often very light and its recoil detection is within the reach of the CDMS II experiment. In general, most points in the parameter spaces of the singlet models we consider are accessible to the WARP experiment

  2. Impurities near an antiferromagnetic-singlet quantum critical point

    International Nuclear Information System (INIS)

    Mendes-Santos, T.; Costa, N. C.; Batrouni, G.

    2017-01-01

    Heavy-fermion systems and other strongly correlated electron materials often exhibit a competition between antiferromagnetic (AF) and singlet ground states. We examine the effect of impurities in the vicinity of such an AF-singlet quantum critical point (QCP), through an appropriately defined “impurity susceptibility” χimp, using exact quantum Monte Carlo simulations. Our key finding is a connection within a single calculational framework between AF domains induced on the singlet side of the transition and the behavior of the nuclear magnetic resonance (NMR) relaxation rate 1/T1. Furthermore, we show that local NMR measurements provide a diagnostic for the location of the QCP, which agrees remarkably well with the vanishing of the AF order parameter and large values of χimp.

  3. Gamma rays from the annihilation of singlet scalar dark matter

    Science.gov (United States)

    Yaguna, Carlos E.

    2009-03-01

    We consider an extension of the Standard Model by a singlet scalar that accounts for the dark matter of the Universe. Within this model we compute the expected gamma ray flux from the annihilation of dark matter particles in a consistent way. To do so, an updated analysis of the parameter space of the model is first presented. By enforcing the relic density constraint from the very beginning, the viable parameter space gets reduced to just two variables: the singlet mass and the higgs mass. Current direct detection constraints are then found to require a singlet mass larger than 50 GeV. Finally, we compute the gamma ray flux and annihilation cross section and show that a large fraction of the viable parameter space lies within the sensitivity of Fermi-GLAST.

  4. Gamma rays from the annihilation of singlet scalar dark matter

    International Nuclear Information System (INIS)

    Yaguna, Carlos E.

    2009-01-01

    We consider an extension of the Standard Model by a singlet scalar that accounts for the dark matter of the Universe. Within this model we compute the expected gamma ray flux from the annihilation of dark matter particles in a consistent way. To do so, an updated analysis of the parameter space of the model is first presented. By enforcing the relic density constraint from the very beginning, the viable parameter space gets reduced to just two variables: the singlet mass and the higgs mass. Current direct detection constraints are then found to require a singlet mass larger than 50 GeV. Finally, we compute the gamma ray flux and annihilation cross section and show that a large fraction of the viable parameter space lies within the sensitivity of Fermi-GLAST

  5. Singlet fission efficiency in tetracene-based organic solar cells

    International Nuclear Information System (INIS)

    Wu, Tony C.; Thompson, Nicholas J.; Congreve, Daniel N.; Hontz, Eric; Yost, Shane R.; Van Voorhis, Troy; Baldo, Marc A.

    2014-01-01

    Singlet exciton fission splits one singlet exciton into two triplet excitons. Using a joint analysis of photocurrent and fluorescence modulation under a magnetic field, we determine that the triplet yield within optimized tetracene organic photovoltaic devices is 153% ± 5% for a tetracene film thickness of 20 nm. The corresponding internal quantum efficiency is 127% ± 18%. These results are used to prove the effectiveness of a simplified triplet yield measurement that relies only on the magnetic field modulation of fluorescence. Despite its relatively slow rate of singlet fission, the measured triplet yields confirm that tetracene is presently the best candidate for use with silicon solar cells

  6. Oxygen diffusion in bilayer polymer films

    DEFF Research Database (Denmark)

    Poulsen, Lars; Zebger, Ingo; Tofte, Jannik Pentti

    2004-01-01

    through the film of poly(ethylene-co-norbornene) and into the polystyrene film was monitored using the phosphorescence of singlet oxygen as a spectroscopic probe. To analyze the data, it was necessary to solve Fick's second law of diffusion for both polymer films. Tractable analytical and numerical...

  7. The effect of helium-oxygen-assisted mechanical ventilation on chronic obstructive pulmonary disease exacerbation: A systemic review and meta-analysis.

    Science.gov (United States)

    Wu, Xu; Shao, Chuan; Zhang, Liang; Tu, Jinjing; Xu, Hui; Lin, Zhihui; Xu, Shuguang; Yu, Biyun; Tang, Yaodong; Li, Shanqun

    2018-03-01

    Chronic obstructive pulmonary disease (COPD) is often accompanied by acute exacerbations. Patients of COPD exacerbation suffering from respiratory failure often need the support of mechanical ventilation. Helium-oxygen can be used to reduce airway resistance during mechanical ventilation. The aim of this study is to evaluate the effect of helium-oxygen-assisted mechanical ventilation on COPD exacerbation through a meta-analysis. A comprehensive literature search through databases of Pub Med (1966∼2016), Ovid MEDLINE (1965∼2016), Cochrane EBM (1991∼2016), EMBASE (1974∼2016) and Ovid MEDLINE was performed to identify associated studies. Randomized clinical trials met our inclusion criteria that focus on helium-oxygen-assisted mechanical ventilation on COPD exacerbation were included. The quality of the papers was evaluated after inclusion and information was extracted for meta-analysis. Six articles and 392 patients were included in total. Meta-analysis revealed that helium-oxygen-assisted mechanical ventilation reduced Borg dyspnea scale and increased arterial PH compared with air-oxygen. No statistically significant difference was observed between helium-oxygen and air-oxygen as regards to WOB, PaCO 2 , OI, tracheal intubation rates and mortality within hospital. Our study suggests helium-oxygen-assisted mechanical ventilation can help to reduce Borg dyspnea scale. In terms of the tiny change of PH, its clinical benefit is negligible. There is no conclusive evidence indicating the beneficial effect of helium-oxygen-assisted mechanical ventilation on clinical outcomes or prognosis of COPD exacerbation. © 2017 John Wiley & Sons Ltd.

  8. Influence of heat treatment and oxygen doping on the mechanical properties and biocompatibility of titanium-niobium binary alloys.

    Science.gov (United States)

    da Silva, Luciano Monteiro; Claro, Ana Paula Rosifini Alves; Donato, Tatiani Ayako Goto; Arana-Chavez, Victor E; Moraes, João Carlos Silos; Buzalaf, Marília Afonso Rabelo; Grandini, Carlos Roberto

    2011-05-01

    The most commonly used titanium (Ti)-based alloy for biological applications is Ti-6Al-4V, but some studies associate the vanadium (V) with the cytotoxic effects and adverse reactions in tissues, while aluminum (Al) has been associated with neurological disorders. Ti-Nb alloys belong to a new class of Ti-based alloys with no presence of Al and V and with elasticity modulus values that are very attractive for use as a biomaterial. It is well known that the presence of interstitial elements (such as oxygen, for example) changes the mechanical properties of alloys significantly, particularly the elastic properties, the same way that heat treatments can change the microstructure of these alloys. This article presents the effect of heat treatment and oxygen doping in some mechanical properties and the biocompatibility of three alloys of the Ti-Nb system, characterized by density measurements, X-ray diffraction, optical microscopy, Vickers microhardness, in vitro cytotoxicity, and mechanical spectroscopy. © 2011, Copyright the Authors. Artificial Organs © 2011, International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.

  9. Insertion of molecular oxygen into a palladium(II) methyl bond: a radical chain mechanism involving palladium(III) intermediates.

    Science.gov (United States)

    Boisvert, Luc; Denney, Melanie C; Hanson, Susan Kloek; Goldberg, Karen I

    2009-11-04

    The reaction of (bipy)PdMe(2) (1) (bipy = 2,2'-bipyridine) with molecular oxygen results in the formation of the palladium(II) methylperoxide complex (bipy)PdMe(OOMe) (2). The identity of the product 2 has been confirmed by independent synthesis. Results of kinetic studies of this unprecedented oxygen insertion reaction into a palladium alkyl bond support the involvement of a radical chain mechanism. Reproducible rates, attained in the presence of the radical initiator 2,2'-azobis(2-methylpropionitrile) (AIBN), reveal that the reaction is overall first-order (one-half-order in both [1] and [AIBN], and zero-order in [O(2)]). The unusual rate law (half-order in [1]) implies that the reaction proceeds by a mechanism that differs significantly from those for organic autoxidations and for the recently reported examples of insertion of O(2) into Pd(II) hydride bonds. The mechanism for the autoxidation of 1 is more closely related to that found for the autoxidation of main group and early transition metal alkyl complexes. Notably, the chain propagation is proposed to proceed via a stepwise associative homolytic substitution at the Pd center of 1 with formation of a pentacoordinate Pd(III) intermediate.

  10. The effect of oxygen transfer mechanism on the cathode performance based on proton-conducting solid oxide fuel cells

    KAUST Repository

    Hou, Jie

    2015-01-01

    Two types of proton-blocking composites, La2NiO4+δ-LaNi0.6Fe0.4O3-δ (LNO-LNF) and Sm0.2Ce0.8O2-δ-LaNi0.6Fe0.4O3-δ (SDC-LNF), were evaluated as cathode materials for proton-conducting solid oxide fuel cells (H-SOFCs) based on the BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte, in order to compare and investigate the influence of two different oxygen transfer mechanism on the performance of the cathode for H-SOFCs. The X-ray diffraction (XRD) results showed that the chemical compatibility of the components in both compounds was excellent up to 1000°C. Electrochemical studies revealed that LNO-LNF showed lower area specific polarization resistances in symmetrical cells and better electrochemical performance in single cell tests. The single cell with LNO-LNF cathode generated remarkable higher maximum power densities (MPDs) and lower interfacial polarization resistances (Rp) than that with SDC-LNF cathode. Correspondingly, the MPDs of the single cell with the LNO-LNF cathode were 490, 364, 266, 180 mW cm-2 and the Rp were 0.103, 0.279, 0.587, 1.367 Ω cm2 at 700, 650, 600 and 550°C, respectively. Moreover, after the single cell with LNO-LNF cathode optimized with an anode functional layer (AFL) between the anode and electrolyte, the power outputs reached 708 mW cm-2 at 700°C. These results demonstrate that the LNO-LNF composite cathode with the interstitial oxygen transfer mechanism is a more preferable alternative for H-SOFCs than SDC-LNF composite cathode with the oxygen vacancy transfer mechanism.

  11. Advances in the development of Chemical Oxygen-Iodine Laser

    Czech Academy of Sciences Publication Activity Database

    Kodymová, Jarmila; Špalek, Otomar; Jirásek, Vít; Čenský, Miroslav

    2004-01-01

    Roč. 54, č. 5 (2004), s. 561-574 ISSN 0011-4626 Institutional research plan: CEZ:AV0Z4032918; CEZ:AV0Z1010921 Keywords : chemical Oxygen-Iodine Laser * COIL * singlet oxygen Subject RIV: CA - Inorganic Chemistry Impact factor: 0.292, year: 2004

  12. The effect of oxygen exposure on pentacene electronic structure

    NARCIS (Netherlands)

    Vollmer, A; Jurchescu, OD; Arfaoui, [No Value; Salzmann, [No Value; Palstra, TTM; Rudolf, P; Niemax, J; Pflaum, J; Rabe, JP; Koch, N; Arfaoui, I.; Salzmann, I.

    We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. it is found that O-2 and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic

  13. Investigating the mechanical and barrier properties to oxygen and fuel of high density polyethylene–graphene nanoplatelet composites

    Energy Technology Data Exchange (ETDEWEB)

    Honaker, K., E-mail: honakers@egr.msu.edu; Vautard, F.; Drzal, L.T.

    2017-02-15

    Highlights: • Melt mixing used to investigate high density polyethylene and graphene nanoplatelet composite. • Addition of graphene nanoplatelets resulted in a stiffer polymer matrix. • Presence of graphene nanoplatelets causes a decrease in oxygen and fuel permeation. - Abstract: Graphene nanoplatelets (GnP) of different sizes were investigated for their ability to modify high density polyethylene (HDPE) for potential fuel system applications, focusing on compounding via melt mixing in a twin-screw extruder. Mechanical properties, crystallinity of the polymer, and permeation to oxygen and fuel were assessed as a function of GnP concentration. The surface of GnP acted as a nucleation site for the generation of HDPE crystallites, increasing the crystallinity. The flexural properties were improved, clearly influenced by platelet size and quality of dispersion. A sharp, 46% decrease of the impact resistance was observed, even at low GnP concentration (0.2 wt.%). With a 15 wt.% GnP-M-15 (platelets with a 15 μm diameter), a 73% reduction in oxygen permeation was observed and a 74% reduction in fuel vapor transmission. This correlation was similar throughout the GnP concentration range. The smaller diameter platelets had a lesser effect on the properties.

  14. Percutaneous Mechanical Circulation Support Combined with Extracorporeal Membrane Oxygenation (oxyRVAD) in Secondary Right Heart Failure.

    Science.gov (United States)

    Lepper, Philipp M; Hörsch, Sabrina I; Seiler, Frederik; Kamp, Annegret; Becker, Sören L; Lensch, Christian; Conzelmann, Lars O; Haake, Hendrik; Muellenbach, Ralf M; Bals, Robert; Kredel, Markus; Langer, Frank; Wilkens, Heinrike; Trudzinski, Franziska C

    2018-02-06

    Right heart failure (RHF) because of pulmonary hypertension (PH) is a frequently encountered clinical problem with high mortality. The last resort, if pharmacological therapy fails, is mechanical circulatory support. There is a lack of percutaneous systems to support the right ventricle (RV). Venoarterial extracorporeal membrane oxygenation is widely used as a bailout in acute RHF in non-left ventricular assist device patients. Venoarterial extracorporeal membrane oxygenation does not unload the left ventricle and may cause failure of the left ventricle if used for a longer period of time. We report the long-term use of an ECMO-based percutaneous right ventricular assist system (oxyRVAD) capable to deliver up to 6 L/min of blood flow with a returning cannula placed in the main pulmonary artery used in RHF originating from PH with poor oxygenation. We present a series of four patients on oxyRVAD (mean treatment duration 15 ± 7.6 days). Patients benefited from the system clinically; however, two patients eventually died while on oxyRVAD. Nevertheless, we provide a proof-of-concept of this system in PH patients, which is feasible and might provide a useful "bridge-to-recovery" or "bridge-to-transplant" option in the management of patients with severe RHF because of PH.

  15. First principles electronic structure investigation of order of singlet and triplet states of oxyhemoglobin and analysis of possible influence of muon trapping

    International Nuclear Information System (INIS)

    Badu, S. R.; Pink, R. H.; Scheicher, R. H.; Dubey, Archana; Sahoo, N.; Nagamine, K.; Das, T. P.

    2010-01-01

    Interest in the possibility of magnetic character for oxyhemoglobin (OxyHb) has been recently stimulated by the observations of muon spin-lattice relaxation effects studied (Nagamine et al., Proc Jpn Acad Ser B Phys Biol Sci 83:120–126, 2007) with the muon-spin rotation (μSR) technique. In view of this, we have carried out first-principles electronic structure investigations involving Hartree–Fock theory combined with many body perturbation effects for the singlet and triplet states of OxyHb. Our results indicate that using two recent x-ray structural data (Paoli et al., J Mol Biol 256:775, 1996; Park et al., J Mol Biol 360:690, 2006) for OxyHb, for only Hartree–Fock theory without many-body effects included, the singlet state lies above the triplet state by energies of about 0.08 and 0.13 a.u. for the two structures in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). Incorporation of many-body effects by the perturbation method reverses the order, with the triplet state located 0.18 and 0.14 a.u. above the singlet state for the structures in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). Physical reasons for these relative orderings of the singlet and triplet states will be discussed. It is clear that OxyHb by itself would be in a singlet state at room temperature or below, since from our calculation, the triplet state lies about KT above the singlet state with T having the value of 44,098 K and 56,449 K for the two structural data in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). As regards the muon spin-lattice relaxation effects obtained by recent μSR measurements (by Nagamine et al., Proc Jpn Acad Ser B Phys Biol Sci 83:120–126, 2007) at room temperature, the sensitive dependence of the singlet-triplet separation on many-body effects in our investigation suggests that it is possible that the singlet-triplet separation could be reversed or

  16. Final Report: Cathode Catalysis in Hydrogen/Oxygen Fuel Cells: New Catalysts, Mechanism, and Characterization

    Energy Technology Data Exchange (ETDEWEB)

    Gewirth, Andrew A. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry; Kenis, Paul J. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemical and Biomolecular Engineering; Nuzzo, Ralph G. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry; Rauchfuss, Thomas B. [Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry

    2016-01-18

    In this research, we prosecuted a comprehensive plan of research directed at developing new catalysts and new understandings relevant to the operation of low temperature hydrogen-oxygen fuel cells. The focal point of this work was one centered on the Oxygen Reduction Reaction (ORR), the electrochemical process that most fundamentally limits the technological utility of these environmentally benign energy conversion devices. Over the period of grant support, we developed new ORR catalysts, based on Cu dimers and multimers. In this area, we developed substantial new insight into design rules required to establish better ORR materials, inspired by the three-Cu active site in laccase which has the highest ORR onset potential of any material known. We also developed new methods of characterization for the ORR on conventional (metal-based) catalysts. Finally, we developed a new platform to study the rate of proton transfer relevant to proton coupled electron transfer (PCET) reactions, of which the ORR is an exemplar. Other aspects of work involved theory and prototype catalyst testing.

  17. Phosphorus doped TiO2 as oxygen sensor with low operating temperature and sensing mechanism

    International Nuclear Information System (INIS)

    Han, Zhizhong; Wang, Jiejie; Liao, Lan; Pan, Haibo; Shen, Shuifa; Chen, Jianzhong

    2013-01-01

    Nano-scale TiO 2 powders doped with phosphorus were prepared by sol–gel method. The characterization of the materials was performed by XRD, BET, FT-IR spectroscopy, Zeta potential measurement and XPS analysis. The results indicate that the phosphorus suppresses the crystal growth and phase transformation and, at the same time, increases the surface area and enhances the sensitivity and selectivity for the P-doped TiO 2 oxygen sensors. In this system, the operating temperature is low, only 116 °C, and the response time is short. The spectra of FT-IR and XPS show that the phosphorus dopant presents as the pentavalent-oxidation state in TiO 2 , further phosphorus can connect with Ti 4+ through the bond of Ti-O-P. The positive shifts of XPS peaks indicate that electron depleted layer of P-doped TiO 2 is narrowed compared with that of pure TiO 2 , and the results of Zeta potential illuminate that the density of surface charge carrier is intensified. The adsorptive active site and Lewis acid characteristics of the surface are reinforced by phosphorus doping, where phosphorus ions act as a new active site. Thus, the sensitivity of P-doped TiO 2 is improved, and the 5 mol% P-doped sample has the optimal oxygen sensing properties.

  18. Effects of exposure to high-temperature helium containing oxygen on the mechanical properties of molybdenum and TZM-Mo alloy at room temperature

    International Nuclear Information System (INIS)

    Noda, T.; Okada, M.; Watanabe, R.

    1980-01-01

    The effects of exposure to helium containing oxygen of 0.1-115 vpm at 1000 0 C on the mechanical properties of molybdenum and TZM-Mo alloy at room temperature were studied. The stress-relieved molybdenum specimen which was not recrystallized at test temperature showed the ductility after exposure to helium containing oxygen. The recrystallized molybdenum and TZM lost ductility after exposure to helium containing oxygen of 0.1-13 vpm in a few hours. The embrittlement of molybdenum was considered to be due to the grain boundary weakening. Molybdenum to which carbon was added seemed to hinder the grain boundary weakening by the oxygen contamination. Both stress-relieved and recrystallized TZM specimens picked up oxygen linearly with time of exposure to helium. The increase in oxygen content of TZM, which was considered to be caused by the internal oxidation of titanium and zirconium, results in the embrittlement of TZM. (orig.)

  19. Formation of long-lived reactive species of blood serum proteins induced by low-intensity irradiation of helium-neon laser and their involvement in the generation of reactive oxygen species.

    Science.gov (United States)

    Ivanov, Vladimir E; Usacheva, Anna M; Chernikov, Anatoly V; Bruskov, Vadim I; Gudkov, Sergey V

    2017-11-01

    It was demonstrated that low-intensity radiation of helium-neon (He-Ne) laser at 632.8nm, which leads to the transition of oxygen to a singlet state, causes the formation of reactive oxygen species (ROS) - hydrogen peroxide, hydroxyl and superoxide (hydroperoxide) radicals - in aqueous solutions. The oxygen effect - dependence of hydrogen peroxide formation on the concentration of molecular oxygen - was shown, and the participation of singlet oxygen, hydroxyl radicals and superoxide (hydroperoxide) radicals in this process was testified. Laser radiation-induced ROS in solutions of blood serum proteins, bovine serum albumin and bovine gamma-globulin, cause the formation of long-lived reactive protein species (LRPS) with a half-life of about 4h. The generation of LRPS caused by laser irradiation results in prolonged several-hour generation of ROS - hydrogen peroxide, hydroxyl and superoxide radicals. As affected by LRPS, coupled radical reactions lead to conversion of dissolved molecular oxygen to hydrogen peroxide. Irradiation with light sources away from the oxygen absorption band is not attended by formation of ROS and LRPS. A consideration is provided for the possible molecular mechanisms of ROS formation under the influence of He-Ne laser irradiation, the role of proteins in their generation and the biological significance of these processes. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Elucidating mechanisms for insect body size: partial support for the oxygen-dependent induction of moulting hypothesis.

    Science.gov (United States)

    Kivelä, Sami M; Viinamäki, Sonja; Keret, Netta; Gotthard, Karl; Hohtola, Esa; Välimäki, Panu

    2018-01-25

    Body size is a key life history trait, and knowledge of its mechanistic basis is crucial in life history biology. Such knowledge is accumulating for holometabolous insects, whose growth is characterised and body size affected by moulting. According to the oxygen-dependent induction of moulting (ODIM) hypothesis, moult is induced at a critical mass at which oxygen demand of growing tissues overrides the supply from the tracheal respiratory system, which principally grows only at moults. Support for the ODIM hypothesis is controversial, partly because of a lack of proper data to explicitly test the hypothesis. The ODIM hypothesis predicts that the critical mass is positively correlated with oxygen partial pressure ( P O 2 ) and negatively with temperature. To resolve the controversy that surrounds the ODIM hypothesis, we rigorously test these predictions by exposing penultimate-instar Orthosia gothica (Lepidoptera: Noctuidae) larvae to temperature and moderate P O 2  manipulations in a factorial experiment. The relative mass increment in the focal instar increased along with increasing P O 2 , as predicted, but there was only weak suggestive evidence of the temperature effect. Probably owing to a high measurement error in the trait, the effect of P O 2  on the critical mass was sex specific; high P O 2  had a positive effect only in females, whereas low P O 2  had a negative effect only in males. Critical mass was independent of temperature. Support for the ODIM hypothesis is partial because of only suggestive evidence of a temperature effect on moulting, but the role of oxygen in moult induction seems unambiguous. The ODIM mechanism thus seems worth considering in body size analyses. © 2018. Published by The Company of Biologists Ltd.

  1. Reactive oxygen species at phospholipid bilayers: distribution, mobility and permeation.

    Science.gov (United States)

    Cordeiro, Rodrigo M

    2014-01-01

    Reactive oxygen species (ROS) are involved in biochemical processes such as redox signaling, aging, carcinogenesis and neurodegeneration. Although biomembranes are targets for reactive oxygen species attack, little is known about the role of their specific interactions. Here, molecular dynamics simulations were employed to determine the distribution, mobility and residence times of various reactive oxygen species at the membrane-water interface. Simulations showed that molecular oxygen (O2) accumulated at the membrane interior. The applicability of this result to singlet oxygen ((1)O2) was discussed. Conversely, superoxide (O2(-)) radicals and hydrogen peroxide (H2O2) remained at the aqueous phase. Both hydroxyl (HO) and hydroperoxyl (HO2) radicals were able to penetrate deep into the lipid headgroups region. Due to membrane fluidity and disorder, these radicals had access to potential peroxidation sites along the lipid hydrocarbon chains, without having to overcome the permeation free energy barrier. Strikingly, HO2 radicals were an order of magnitude more concentrated in the headgroups region than in water, implying a large shift in the acid-base equilibrium between HO2 and O2(-). In comparison with O2, both HO and HO2 radicals had lower lateral mobility at the membrane. Simulations revealed that there were intermittent interruptions in the H-bond network around the HO radicals at the headgroups region. This effect is expected to be unfavorable for the H-transfer mechanism involved in HO diffusion. The implications for lipid peroxidation and for the effectiveness of membrane antioxidants were evaluated. © 2013.

  2. Mechanisms of electron transfer from structrual Fe(II) in reduced nontronite to oxygen for production of hydroxyl radicals

    Science.gov (United States)

    Yuan, Songhu; Liu, Xixiang; Liao, Wenjuan; Zhang, Peng; Wang, Xiaoming; Tong, Man

    2018-02-01

    Production of hydroxyl radicals (radOH) has been recently revealed upon oxygenation of sediments in redox-dynamic subsurface environments. In particular, Fe(II)-bearing clay minerals are the major sediment components contributing to radOH production upon oxygenation, and the produced radOH can oxidize contaminants and inactivate bacteria. Whereas, the mechanisms of radOH production from oxygenation of Fe(II)-bearing clay minerals remain elusive. The objectives of this study were to identify the structural variation of Fe(II) entities during the oxidation of Fe(II)-bearing clay minerals by O2, and to unravel the mechanisms of electron transfer within the mineral structure and from mineral to O2 for radOH production. Nontronite (NAu-2, 23% Fe) which was chemically reduced to 54.5% Fe(II) in total Fe was used as a model Fe(II)-bearing clay mineral. Production of radOH and oxidation of Fe(II) were measured during the oxidation of reduced NAu-2 by O2. A wide spectrum of spectroscopic techniques, including Fourier transform infrared spectroscopy (FTIR), Fe K-edge X-ray absorption spectroscopy (XAS), Mössbauer spectra, and X-ray photoelectron spectroscopy (XPS), were employed to explore the structural variation of Fe(II) entities in NAu-2 and the electron transfer within NAu-2 and from NAu-2 to O2. For 180 min oxidation of 1 g/L reduced NAu-2, a biphasic radOH production was observed, being quick within the initial 15 min and slow afterwards. Production of radOH correlates well with oxidation of Fe(II) in the reduced NAu-2. Within the initial 15 min, trioctahedral Fe(II)-Fe(II)-Fe(II) entities and edge Fe(II) in the reduced NAu-2 were preferentially and quickly oxidized, and electrons from the interior Fe(II)-Fe(II)-Fe(II) entities were most likely ejected from the basal siloxane plane to O2. Meanwhile, trioctahedral Fe(II)-Fe(II)-Fe(II) entities were mainly transformed to dioctahedral Fe(II)-Fe(II) entities. When the time of oxygenation was longer than 15 min

  3. The enhanced cytotoxicity of misonidazole in the thiol depleted state - An oxygen dependent mechanism

    International Nuclear Information System (INIS)

    Tuttle, S.W.; Varnes, M.E.; Donahue, L.; Biaglow, J.E.

    1985-01-01

    Incubating A549 cells in the presence of L-buthionine-S, R-sulfoximine and misonidazole under aerobic conditions results in lowered rates of cell growth and greater cytotoxicity than is seen with either drug alone. The authors previously demonstrated the accumulation of hydrogen peroxide from cells treated with misonidazole following the inhibition of GSH-peroxidase with thiol depleting agents. They hypothesize that the enhancement of misonidazole toxicity by L-BSO results from the increased exposure to hydrogen peroxide, and the possible formation of the highly reactive hydroxyl radical in the presence of trace metals via Fenton chemistry. Support for this hypothesis comes from their observations that addition of radical scavengers (such as SOD and catalase) and nutritional antioxidants (vitamin E) to the culture medium will partially inhibit the cytotoxic effects. Further work is being done to measure the products of reaction of toxic oxygen species with cellular macromolecules, i.e. lipids

  4. Fundamental roles of reactive oxygen species and protective mechanisms in the female reproductive system

    Directory of Open Access Journals (Sweden)

    Okada Futoshi

    2005-09-01

    Full Text Available Abstract Controlled oxidation, such as disulfide bond formation in sperm nuclei and during ovulation, plays a fundamental role in mammalian reproduction. Excess oxidation, however, causes oxidative stress, resulting in the dysfunction of the reproductive process. Antioxidation reactions that reduce the levels of reactive oxygen species are of prime importance in reproductive systems in maintaining the quality of gametes and support reproduction. While anti-oxidative enzymes, such as superoxide dismutase and peroxidase, play a central role in eliminating oxidative stress, reduction-oxidation (redox systems, comprised of mainly glutathione and thioredoxin, function to reduce the levels of oxidized molecules. Aldo-keto reductase, using NADPH as an electron donor, detoxifies carbonyl compounds resulting from the oxidation of lipids and proteins. Thus, many antioxidative and redox enzyme genes are expressed and aggressively protect gametes and embryos in reproductive systems.

  5. Spectral analysis and self-adjusting mechanism for oscillation phenomenon in hydrogen-oxygen continuously rotating detonation engine

    Directory of Open Access Journals (Sweden)

    Liu Yusi

    2015-06-01

    Full Text Available The continuously rotating detonation engine (CRDE is a new concept of engines for aircraft and spacecraft. Quasi-stable continuously rotating detonation (CRD can be observed in an annular combustion chamber, but the sustaining, stabilizing and adjusting mechanisms are not yet clear. To learn more deeply into the CRDE, experimental studies have been carried out to investigate hydrogen-oxygen CRDE. Pressure histories are obtained during each shot, which show that stable CRD waves are generated in the combustor, when feeding pressures are higher than 0.5 MPa for fuel and oxidizer, respectively. Each shot can keep running as long as fresh gas feeding maintains. Close-up of the pressure history shows the repeatability of pressure peaks and indicates the detonation velocity in hydrogen–oxygen CRD, which proves the success of forming a stable CRD in the annular chamber. Spectrum of the pressure history matches the close-up analysis and confirms the CRD. It also shows multi-wave phenomenon and affirms the fact that in this case a single detonation wave is rotating in the annulus. Moreover, oscillation phenomenon is found in pressure peaks and a self-adjusting mechanism is proposed to explain the phenomenon.

  6. Mechanism and kinetics of low-temperature oxidation of a biodiesel surrogate: methyl propanoate radicals with oxygen molecule.

    Science.gov (United States)

    Le, Xuan T; Mai, Tam V T; Ratkiewicz, Artur; Huynh, Lam K

    2015-04-23

    This paper presents a computational study on the low-temperature mechanism and kinetics of the reaction between molecular oxygen and alkyl radicals of methyl propanoate (MP), which plays an important role in low-temperature oxidation and/or autoignition processes of the title fuel. Their multiple reaction pathways either accelerate the oxidation process via chain branching or inhibit it by forming relatively stable products. The potential energy surfaces of the reactions between three primary MP radicals and molecular oxygen, namely, C(•)H2CH2COOCH3 + O2, CH3C(•)HCOOCH3 + O2, and CH3CH2COOC(•)H2 + O2, were constructed using the accurate composite CBS-QB3 method. Thermodynamic properties of all species as well as high-pressure rate constants of all reaction channels were derived with explicit corrections for tunneling and hindered internal rotations. Our calculation results are in good agreement with a limited number of scattered data in the literature. Furthermore, pressure- and temperature-dependent rate constants for all reaction channels on the multiwell-multichannel potential energy surfaces were computed with the quantum Rice-Ramsperger-Kassel (QRRK) and the modified strong collision (MSC) theories. This procedure resulted in a thermodynamically consistent detailed kinetic submechanism for low-temperature oxidation governed by the title process. A simplified mechanism, which consists of important reactions, is also suggested for low-temperature combustion at engine-like conditions.

  7. Characterization of the Sr(2+)- and Cd(2+)-Substituted Oxygen-Evolving Complex of Photosystem II by Quantum Mechanics/Molecular Mechanics Calculations.

    Science.gov (United States)

    Pitari, Fabio; Bovi, Daniele; Narzi, Daniele; Guidoni, Leonardo

    2015-09-29

    The Mn4CaO5 cluster in the oxygen-evolving complex is the catalytic core of the Photosystem II (PSII) enzyme, responsible for the water splitting reaction in oxygenic photosynthesis. The role of the redox-inactive ion in the cluster has not yet been fully clarified, although several experimental data are available on Ca2+-depleted and Ca2+-substituted PSII complexes, indicating Sr2+-substituted PSII as the only modification that preserves oxygen evolution. In this work, we investigated the structural and electronic properties of the PSII catalytic core with Ca2+ replaced with Sr2+ and Cd2+ in the S2 state of the Kok−Joliot cycle by means of density functional theory and ab initio molecular dynamics based on a quantum mechanics/ molecular mechanics approach. Our calculations do not reveal significant differences between the substituted and wild-type systems in terms of geometries, thermodynamics, and kinetics of two previously identified intermediate states along the S2 to S3 transition, namely, the open cubane S2 A and closed cubane S2 B conformers. Conversely, our calculations show different pKa values for the water molecule bound to the three investigated heterocations. Specifically, for Cd-substituted PSII, the pKa value is 5.3 units smaller than the respective value in wild type Ca-PSII. On the basis of our results, we conclude that, assuming all the cations sharing the same binding site, the induced difference in the acidity of the binding pocket might influence the hydrogen bonding network and the redox levels to prevent the further evolution of the cycle toward the S3 state.

  8. Flavor-singlet spectrum in multi-flavor QCD

    Energy Technology Data Exchange (ETDEWEB)

    Aoki, Yasamichi; Rinaldi, Enrico

    2017-06-18

    Studying SU(3) gauge theories with increasing number of light fermions is relevant both for understanding the strong dynamics of QCD and for constructing strongly interacting extensions of the Standard Model (e.g. UV completions of composite Higgs models). In order to contrast these many-flavors strongly interacting theories with QCD, we study the flavor-singlet spectrum as an interesting probe. In fact, some composite Higgs models require the Higgs boson to be the lightest flavor-singlet scalar in the spectrum of a strongly interacting new sector with a well defined hierarchy with the rest of the states. Moreover, introducing many light flavors at fixed number of colors can influence the dynamics of the lightest flavor-singlet pseudoscalar. We present the on-going study of these flavor-singlet channels using multiple interpolating operators on high-statistics ensembles generated by the LatKMI collaboration and we compare results with available data obtained by the Lattice Strong Dynamics collaboration. For the theory with 8 flavors, the two collaborations have generated configurations that complement each others with the aim to tackle the massless limit using the largest possible volumes.

  9. Guidance for Mutual Disposition of Chromophores for Singlet Fission

    Czech Academy of Sciences Publication Activity Database

    Havlas, Zdeněk; Michl, Josef

    2016-01-01

    Roč. 56, č. 1 (2016), s. 96-106 ISSN 0021-2148 R&D Projects: GA ČR GA15-19143S Institutional support: RVO:61388963 Keywords : chromophores * energy transfer * photophysics * singlet fission * theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.455, year: 2016

  10. Status of the scalar singlet dark matter model

    Science.gov (United States)

    Athron, Peter; Balázs, Csaba; Bringmann, Torsten; Buckley, Andy; Chrząszcz, Marcin; Conrad, Jan; Cornell, Jonathan M.; Dal, Lars A.; Edsjö, Joakim; Farmer, Ben; Jackson, Paul; Kahlhoefer, Felix; Krislock, Abram; Kvellestad, Anders; McKay, James; Mahmoudi, Farvah; Martinez, Gregory D.; Putze, Antje; Raklev, Are; Rogan, Christopher; Saavedra, Aldo; Savage, Christopher; Scott, Pat; Serra, Nicola; Weniger, Christoph; White, Martin

    2017-08-01

    One of the simplest viable models for dark matter is an additional neutral scalar, stabilised by a Z_2 symmetry. Using the GAMBIT package and combining results from four independent samplers, we present Bayesian and frequentist global fits of this model. We vary the singlet mass and coupling along with 13 nuisance parameters, including nuclear uncertainties relevant for direct detection, the local dark matter density, and selected quark masses and couplings. We include the dark matter relic density measured by Planck, direct searches with LUX, PandaX, SuperCDMS and XENON100, limits on invisible Higgs decays from the Large Hadron Collider, searches for high-energy neutrinos from dark matter annihilation in the Sun with IceCube, and searches for gamma rays from annihilation in dwarf galaxies with the Fermi-LAT. Viable solutions remain at couplings of order unity, for singlet masses between the Higgs mass and about 300 GeV, and at masses above ˜ 1 TeV. Only in the latter case can the scalar singlet constitute all of dark matter. Frequentist analysis shows that the low-mass resonance region, where the singlet is about half the mass of the Higgs, can also account for all of dark matter, and remains viable. However, Bayesian considerations show this region to be rather fine-tuned.

  11. Atmospheric and Solar Neutrinos with a Heavy Singlet

    CERN Document Server

    King, S F

    1998-01-01

    We follow a minimalistic approach to neutrino masses, by introducing a single heavy singlet $N$ into the standard model (or supersymmetric standard model) with a heavy Majorana mass $M$, which couples as a single right-handed neutrino in a Dirac fashion to leptons, and induces a single light see-saw mass $m_{\

  12. Bounds on neutrino mixing with exotic singlet neutrinos E

    Indian Academy of Sciences (India)

    This allows us to neglect the masses of light (known) neutrinos. In the SM the process occurs at tree level via light neutrino exchange in t- and u-channels. The neu- trino mixing in special cases (e.g. mixing of exotic and/or singlets), induces non-diagonal light–heavy neutrino neutral currents and additional contribution to the ...

  13. Real gauge singlet scalar extension of the Standard Model: A ...

    Indian Academy of Sciences (India)

    2013-03-05

    Mar 5, 2013 ... Abstract. The simplest extension of Standard Model (SM) is considered in which a real SM gauge singlet scalar with an additional discrete symmetry Z2 is introduced to SM. This additional scalar can be a viable candidate of cold dark matter (CDM) since the stability of S is achieved by the application of Z2 ...

  14. Explorative computational study of the singlet fission process

    NARCIS (Netherlands)

    Havenith, Remco W. A.; de Gier, Hilde D.; Broer, Ria

    2012-01-01

    Different ab initio methods, namely multi-reference and nonorthogonal configuration interaction techniques, are explored for their applicability in studying the singlet fission problem. It has been shown for 2-methyl-1,5-hexadiene that the (TT)-T-1 state can be identified using multi-reference

  15. 1,3-Diphenylisobenzofuran: a Model Chromophore for Singlet Fission

    Czech Academy of Sciences Publication Activity Database

    Johnson, J. C.; Michl, Josef

    2017-01-01

    Roč. 375, č. 5 (2017), č. článku 80. ISSN 2365-0869 R&D Projects: GA ČR GA15-19143S Institutional support: RVO:61388963 Keywords : 1,3-diphenylisobenzofuran * photophysics * solar energy * singlet fission * covalent dimers Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.033, year: 2016

  16. Status of the scalar singlet dark matter model

    Energy Technology Data Exchange (ETDEWEB)

    Athron, Peter; Balazs, Csaba [Monash University, School of Physics and Astronomy, Melbourne, VIC (Australia); Australian Research Council Centre of Excellence for Particle Physics at the Tera-scale (Australia); Bringmann, Torsten; Dal, Lars A.; Krislock, Abram; Raklev, Are [University of Oslo, Department of Physics, Oslo (Norway); Buckley, Andy [University of Glasgow, SUPA, School of Physics and Astronomy, Glasgow (United Kingdom); Chrzaszcz, Marcin [Universitaet Zuerich, Physik-Institut, Zurich (Switzerland); Polish Academy of Sciences, H. Niewodniczanski Institute of Nuclear Physics, Krakow (Poland); Conrad, Jan; Edsjoe, Joakim; Farmer, Ben [AlbaNova University Centre, Oskar Klein Centre for Cosmoparticle Physics, Stockholm (Sweden); Stockholm University, Department of Physics, Stockholm (Sweden); Cornell, Jonathan M. [McGill University, Department of Physics, Montreal, QC (Canada); Jackson, Paul; White, Martin [Australian Research Council Centre of Excellence for Particle Physics at the Tera-scale (Australia); University of Adelaide, Department of Physics, Adelaide, SA (Australia); Kahlhoefer, Felix [DESY, Hamburg (Germany); Kvellestad, Anders; Savage, Christopher [NORDITA, Stockholm (Sweden); McKay, James; Scott, Pat [Imperial College London, Department of Physics, Blackett Laboratory, London (United Kingdom); Mahmoudi, Farvah [Univ. Lyon, Univ. Lyon 1, ENS de Lyon, CNRS, Centre de Recherche Astrophysique de Lyon UMR5574, Saint-Genis-Laval (France); CERN, Theoretical Physics Department, Geneva (Switzerland); Martinez, Gregory D. [University of California, Physics and Astronomy Department, Los Angeles, CA (United States); Putze, Antje [LAPTh, Universite de Savoie, CNRS, Annecy-le-Vieux (France); Rogan, Christopher [Harvard University, Department of Physics, Cambridge, MA (United States); Saavedra, Aldo [Australian Research Council Centre of Excellence for Particle Physics at the Tera-scale (Australia); The University of Sydney, Centre for Translational Data Science, Faculty of Engineering and Information Technologies, School of Physics, Sydney, NSW (Australia); Serra, Nicola [Universitaet Zuerich, Physik-Institut, Zurich (Switzerland); Weniger, Christoph [University of Amsterdam, GRAPPA, Institute of Physics, Amsterdam (Netherlands); Collaboration: The GAMBIT Collaboration

    2017-08-15

    One of the simplest viable models for dark matter is an additional neutral scalar, stabilised by a Z{sub 2} symmetry. Using the GAMBIT package and combining results from four independent samplers, we present Bayesian and frequentist global fits of this model. We vary the singlet mass and coupling along with 13 nuisance parameters, including nuclear uncertainties relevant for direct detection, the local dark matter density, and selected quark masses and couplings. We include the dark matter relic density measured by Planck, direct searches with LUX, PandaX, SuperCDMS and XENON100, limits on invisible Higgs decays from the Large Hadron Collider, searches for high-energy neutrinos from dark matter annihilation in the Sun with IceCube, and searches for gamma rays from annihilation in dwarf galaxies with the Fermi-LAT. Viable solutions remain at couplings of order unity, for singlet masses between the Higgs mass and about 300 GeV, and at masses above ∝ 1 TeV. Only in the latter case can the scalar singlet constitute all of dark matter. Frequentist analysis shows that the low-mass resonance region, where the singlet is about half the mass of the Higgs, can also account for all of dark matter, and remains viable. However, Bayesian considerations show this region to be rather fine-tuned. (orig.)

  17. Status of the scalar singlet dark matter model

    International Nuclear Information System (INIS)

    Athron, Peter; Balazs, Csaba; Bringmann, Torsten; Dal, Lars A.; Krislock, Abram; Raklev, Are; Buckley, Andy; Chrzaszcz, Marcin; Conrad, Jan; Edsjoe, Joakim; Farmer, Ben; Cornell, Jonathan M.; Jackson, Paul; White, Martin; Kahlhoefer, Felix; Kvellestad, Anders; Savage, Christopher; McKay, James; Scott, Pat; Mahmoudi, Farvah; Martinez, Gregory D.; Putze, Antje; Rogan, Christopher; Saavedra, Aldo; Serra, Nicola; Weniger, Christoph

    2017-01-01

    One of the simplest viable models for dark matter is an additional neutral scalar, stabilised by a Z 2 symmetry. Using the GAMBIT package and combining results from four independent samplers, we present Bayesian and frequentist global fits of this model. We vary the singlet mass and coupling along with 13 nuisance parameters, including nuclear uncertainties relevant for direct detection, the local dark matter density, and selected quark masses and couplings. We include the dark matter relic density measured by Planck, direct searches with LUX, PandaX, SuperCDMS and XENON100, limits on invisible Higgs decays from the Large Hadron Collider, searches for high-energy neutrinos from dark matter annihilation in the Sun with IceCube, and searches for gamma rays from annihilation in dwarf galaxies with the Fermi-LAT. Viable solutions remain at couplings of order unity, for singlet masses between the Higgs mass and about 300 GeV, and at masses above ∝ 1 TeV. Only in the latter case can the scalar singlet constitute all of dark matter. Frequentist analysis shows that the low-mass resonance region, where the singlet is about half the mass of the Higgs, can also account for all of dark matter, and remains viable. However, Bayesian considerations show this region to be rather fine-tuned. (orig.)

  18. Flavor-singlet spectrum in multi-flavor QCD

    Science.gov (United States)

    Aoki, Yasumichi; Aoyama, Tatsumi; Bennett, Ed; Kurachi, Masafumi; Maskawa, Toshihide; Miura, Kohtaroh; Nagai, Kei-ichi; Ohki, Hiroshi; Rinaldi, Enrico; Shibata, Akihiro; Yamawaki, Koichi; Yamazaki, Takeshi

    2018-03-01

    Studying SU(3) gauge theories with increasing number of light fermions is relevant both for understanding the strong dynamics of QCD and for constructing strongly interacting extensions of the Standard Model (e.g. UV completions of composite Higgs models). In order to contrast these many-flavors strongly interacting theories with QCD, we study the flavor-singlet spectrum as an interesting probe. In fact, some composite Higgs models require the Higgs boson to be the lightest flavor-singlet scalar in the spectrum of a strongly interacting new sector with a well defined hierarchy with the rest of the states. Moreover, introducing many light flavors at fixed number of colors can influence the dynamics of the lightest flavor-singlet pseudoscalar. We present the on-going study of these flavor-singlet channels using multiple interpolating operators on high-statistics ensembles generated by the LatKMI collaboration and we compare results with available data obtained by the Lattice Strong Dynamics collaboration. For the theory with 8 flavors, the two collaborations have generated configurations that complement each others with the aim to tackle the massless limit using the largest possible volumes.

  19. Delayed fluorescence from upper excited singlet states of aromatic ketones

    International Nuclear Information System (INIS)

    Nickel, B.; Roden, G.

    1980-01-01

    With liquid solutions of the aromatic ketones anthraquinone and xanthone, a P-type delayed fluorescence from upper excited singlet states, resulting from triplet-triplet annihilation, has been observed. Some peculiarities of the triplet-triplet annihilation of aromatic ketones are discussed. (orig.)

  20. Morphological Tuning of the Energetics in Singlet Fission Organic Solar Cells

    NARCIS (Netherlands)

    Lin, Yun Hui L; Fusella, Michael A.; Kozlov, Oleg V.; Lin, Xin; Kahn, Antoine; Pshenichnikov, Maxim S.; Rand, Barry P.

    2016-01-01

    Effective singlet fission solar cells require both fast and efficient singlet fission as well as favorable energetics for harvesting the resulting triplet excitons. Notable progress has been made to engineer materials with rapid and efficient singlet fission, but the ability to control the

  1. Sea quark matrix elements and flavor singlet spectroscopy on the lattice

    International Nuclear Information System (INIS)

    Lagae, J.F.

    1996-01-01

    I summarize the results of three recent lattice studies which use stochastic estimator techniques in order to investigate the flavor singlet dynamics in QCD. These include a measurement of the pion-nucleon σ-term, the computation of the flavor singlet axial coupling constant of the nucleon and a determination of flavor singlet meson screening lengths in finite temperature QCD

  2. Effects of Intermolecular Coupling on Excimer Formation and Singlet Fission

    Science.gov (United States)

    Mauck, Catherine McKay

    The development of organic photovoltaic devices benefits from understanding the fundamental processes underlying charge generation in thin films of organic semiconductors. This dissertation exploits model systems of pi-stacked chromophores such as perylene-3,4:9,10-bis(dicarboximide) (PDI) and 3,6-bis(aryl)diketopyrrolopyrrole (DPP) to study these processes using ultrafast electronic and vibrational spectroscopy. In particular, the characterization of covalent molecular dimers, thin films, and solution aggregates can reveal how supramolecular order affects photophysical properties. PDI and DPP are organic semiconductors that have been widely studied in organic photovoltaics, due to their strong visible absorption and excellent chemical stability. As solution-phase monomers, they are highly fluorescent, but in the thin film environment of photovoltaic devices these planar aromatic molecules couple to one another, stacking largely through pi-pi interactions. In self-assembled stacks of PDI, strong interchromophore coupling may disrupt charge separation through the formation of excimer states, preventing the generation of free carriers. By studying molecular dimers of PDI with different pi-stacked geometry, femtosecond visible pump mid-infrared probe spectroscopy allows direct observation of the structural dynamics associated with excimer state relaxation, showing that this low-energy state is primarily coupled to the core modes that shift as planarization and rotation lead to the most stable excimer geometry. PDI is also able to undergo singlet fission in thin films and aggregates. Singlet fission is the process in which a singlet excited state is downconverted into two triplet excitons, when the energy of its first singlet excited state is at least twice the energy of the lowest triplet state in an appropriately coupled molecular system. This spin-allowed, ultrafast process enables a theoretical yield of two charge carriers per incident photon, making it a

  3. Mechanisms of photoaddition of xanthotoxin to thymine and DNA

    International Nuclear Information System (INIS)

    Kittler, L.; Hradecna, Z.

    1980-01-01

    It has been shown that singlet oxygen is not involved in the photochemically induced covalent addition reaction of xanthotoxin to thymine or DNA. Although both heavy water and azide ions are known, to increase and decrease, respectively, the lifetime of singlet oxygen drastically, none of those additives was capable of influencing the amount of formed photoproducts. This is thought to mean that singlet oxygen drastically does not play a significant role in the photoaddition of xanthotoxin, independent of whether or not the drug is intercalated prior to the photoreaction. (author)

  4. Oxygen kinetics and mechanism at electrocatalysts on the base of palladium-iron system

    International Nuclear Information System (INIS)

    Tarasevich, M.R.; Zhutaeva, G.V.; Bogdanovskaya, V.A.; Radina, M.V.; Ehrenburg, M.R.; Chalykh, A.E.

    2007-01-01

    Binary nanodispersed carbon XC72 supported PdFe catalysts with different atomic palladium-to-iron ratios are synthesized and studied in oxygen reduction reaction in acid solution at 60 o C. The Pd:Fe ratio was well controlled by the initial concentrations of Pd and Fe in the precursor solutions. The nanoparticles were characterized by transmission electron microscopy, X-ray diffractometry and X-ray photoelectron spectroscopy. The optimum Pd:Fe ratio for this reaction was determined to be 3:1. The comparison of activities of the catalysts with component ratios equaled 3:1 and 10:1 is shown that the activities are differed from each other by 10-15 times in advantage of catalyst with lesser content of palladium. This phenomenon can be related to the different particle size of both catalysts and different distribution of particles by size discovered by TEM method. The achievement of maximum activity near the ratio of Pd:Fe = 3:1 is due to as effect of alloy-forming and the influence of binary system component ratio and synthesis conditions on dispersity degree of metallic phase nanoparticles. Under optimal conditions of precursor mixture high-temperature pyrolysis, iron produces the stabilizing effect palladium. It gives rise to obtaining the uniform and finely divided (7-8 nm) metallic particles

  5. The Mechanism of Hyperbaric Oxygen Therapy in the Treatment of Chronic Wounds and Diabetic Foot Ulcers.

    Science.gov (United States)

    Johnston, Benjamin R; Ha, Austin Y; Brea, Bielinsky; Liu, Paul Y

    2016-02-01

    Non-healing wounds are a growing public health concern, and more than $25 billion per year in the US are spent caring for patients with chronic wounds. Many of these patients are referred to specialized wound centers, where hyperbaric oxygen therapy (HBO2T) has become a mainstay in healing wounds, especially diabetic foot ulcers (DFU). However, it is costly, with a typical course of therapy running into the tens of thousands of dollars. Presently, as many as 30-40% of DFU patients with Wagner's Grade 3 and 4 ulcers treated with HBO2T fail to heal by 24 weeks. Unfortunately, the patient will have already received lengthy therapy (30-60 daily treatments over 6-10 week time period) before having the wound deemed non-responsive. Currently, practitioners employ a combination of clinical markers, diagnostic testing and a four-week preliminary healing response, but this approach is inaccurate and delays definitive identification of HBO2T responder and non-responder phenotypes.

  6. Diabetes-Induced Reactive Oxygen Species: Mechanism of Their Generation and Role in Renal Injury

    Science.gov (United States)

    Fakhruddin, Selim; Alanazi, Wael

    2017-01-01

    Diabetes induces the onset and progression of renal injury through causing hemodynamic dysregulation along with abnormal morphological and functional nephron changes. The most important event that precedes renal injury is an increase in permeability of plasma proteins such as albumin through a damaged glomerular filtration barrier resulting in excessive urinary albumin excretion (UAE). Moreover, once enhanced UAE begins, it may advance renal injury from progression of abnormal renal hemodynamics, increased glomerular basement membrane (GBM) thickness, mesangial expansion, extracellular matrix accumulation, and glomerulosclerosis to eventual end-stage renal damage. Interestingly, all these pathological changes are predominantly driven by diabetes-induced reactive oxygen species (ROS) and abnormal downstream signaling molecules. In diabetic kidney, NADPH oxidase (enzymatic) and mitochondrial electron transport chain (nonenzymatic) are the prominent sources of ROS, which are believed to cause the onset of albuminuria followed by progression to renal damage through podocyte depletion. Chronic hyperglycemia and consequent ROS production can trigger abnormal signaling pathways involving diverse signaling mediators such as transcription factors, inflammatory cytokines, chemokines, and vasoactive substances. Persistently, increased expression and activation of these signaling molecules contribute to the irreversible functional and structural changes in the kidney resulting in critically decreased glomerular filtration rate leading to eventual renal failure. PMID:28164134

  7. Reactive Oxygen Species Donors Increase the Responsiveness of Dorsal Horn Neurons and Induce Mechanical Hyperalgesia in Rats

    Directory of Open Access Journals (Sweden)

    Hee Young Kim

    2015-01-01

    Full Text Available Our previous studies suggest that reactive oxygen species (ROS scavengers have analgesic effect on neuropathic pain through spinal mechanisms in the rat. The studies suggest that superoxide in spinal cord is one of important mediators of persistent pain. To test the hypothesis that increase of superoxide-derived intermediates leads to central sensitization and pain, the effects of an intrathecal injection of chemical ROS donors releasing either OH∙, OCl-, or H2O2 were examined on pain behaviors. Following treatment with t-BOOH (OH∙ donor, dorsal horn neuron responses to mechanical stimuli in normal rats and the changes of neuronal excitability were explored on substantia gelatinosa (SG neurons using whole-cell patch clamping recordings. Intrathecal administration of t-BOOH or NaOCl (OCl- donor, but not H2O2, significantly decreased mechanical thresholds of hind paws. The responses of wide dynamic range neurons to mechanical stimuli increased after a local application of t-BOOH. The t-BOOH increased the frequency and the amplitude of excitatory postsynaptic potentials, depolarized membrane potential in SG neurons, and increased the frequency of action potentials evoked by depolarizing current pulses. These results suggest that elevated ROS, especially OH∙, in the spinal cord sensitized dorsal horn neurons and produced hyperalgesia in normal rats.

  8. Sunlight mediated inactivation mechanisms of Enterococcus faecalis and Escherichia coli in clear water versus waste stabilization pond water.

    Science.gov (United States)

    Kadir, Khalid; Nelson, Kara L

    2014-03-01

    Escherichia coli and enterococci have been previously reported to differ in the mechanisms and conditions that affect their sunlight-mediated inactivation in waste stabilization ponds. This study was undertaken to further characterize these mechanisms, using simulated sunlight and single strains of laboratory-grown E. coli and Enterococcus faecalis, with a focus on characterizing the contribution of exogenous reactive oxygen species to the inactivation process. We found that direct damage by UVB light (280-320 nm) was not a significant inactivation mechanism for either organism. E. coli inactivation was strongly dependent on dissolved oxygen concentrations and the presence of UVB wavelengths but E. coli were not susceptible to inactivation by exogenous sensitizers present in waste stabilization pond water. In contrast, E. faecalis inactivation in pond water occurred primarily through exogenous mechanisms, with strong evidence that singlet oxygen is an important transient reactive species. The exogenous mechanism could utilize wavelengths into the visible spectrum and sensitizers were mainly colloidal, distributed between 0.2 and ∼1 μm in size. Singlet oxygen is likely an important endogenous species in both E. faecalis and E. coli inactivation due to sunlight. Although the two organisms had similar inactivation rates in buffered, clear water, the inactivation rate of E. faecalis was 7 times greater than that of E. coli in air-saturated pond water at circumneutral pH due to its susceptibility to exogenous sensitizers and longer wavelengths. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Mechanisms of growth and patterns of gene expression in oxygen-deprived rice coleoptiles.

    Science.gov (United States)

    Narsai, Reena; Edwards, Joshua M; Roberts, Thomas H; Whelan, James; Joss, Gregory H; Atwell, Brian J

    2015-04-01

    Coleoptiles of rice (Oryza sativa) seedlings grown under water commonly elongate by up to 1 mm h(-1) to reach the atmosphere. We initially analysed this highly specialized phenomenon by measuring epidermal cell lengths along the coleoptile axis to determine elongation rates. This revealed a cohort of cells in the basal zone that elongated rapidly following emergence from the embryo, reaching 200 μm within 12 h. After filming coleoptiles in vivo for a day, kinematic analysis was applied. Eight time-sliced 'segments' were defined by their emergence from the embryo at four-hourly intervals, revealing a mathematically simple growth model. Each segment entering the coleoptile from the embryo elongated at a constant velocity, resulting in accelerating growth for the entire organ. Consistent with the epidermal cell lengths, relative rates of elongation (mm mm(-1) h(-1)) were tenfold greater in the small, newly emerged basal segments than the older distal tip segments. This steep axial gradient defined two contrasting growth zones (bases versus tips) in which we measured ATP production and protein, RNA and DNA content, and analysed the global transcriptome under steady-state normoxia, hypoxia (3% O2) and anoxia. Determination of the transcriptome revealed tip-specific induction of genes encoding TCP [Teosinte Branched1 (Tb1) of maize, Cycloidea (Cyc), and Proliferating Cell Factor (Pcf)] transcription factors, RNA helicases, ribosomal proteins and proteins involved in protein folding, whilst expression of F-box domain-containing proteins in the ubiquitin E3-SCF complex (Skp, Cullin, F-box containing complex) was induced specifically in bases under low oxygen conditions. We ascribed the sustained elongation under hypoxia to hypoxia-specific responses such as controlled suppression of photosystem components and induction of RNA binding/splicing functions, indicating preferential allocation of energy to cell extension. © 2015 The Authors The Plant Journal © 2015 John Wiley

  10. Impacts of ENSO on air-sea oxygen exchange: Observations and mechanisms

    Science.gov (United States)

    Eddebbar, Yassir A.; Long, Matthew C.; Resplandy, Laure; Rödenbeck, Christian; Rodgers, Keith B.; Manizza, Manfredi; Keeling, Ralph F.

    2017-05-01

    Models and observations of atmospheric potential oxygen (APO ≃ O2 + 1.1 * CO2) are used to investigate the influence of El Niño-Southern Oscillation (ENSO) on air-sea O2 exchange. An atmospheric transport inversion of APO data from the Scripps flask network shows significant interannual variability in tropical APO fluxes that is positively correlated with the Niño3.4 index, indicating anomalous ocean outgassing of APO during El Niño. Hindcast simulations of the Community Earth System Model (CESM) and the Institut Pierre-Simon Laplace model show similar APO sensitivity to ENSO, differing from the Geophysical Fluid Dynamics Laboratory model, which shows an opposite APO response. In all models, O2 accounts for most APO flux variations. Detailed analysis in CESM shows that the O2 response is driven primarily by ENSO modulation of the source and rate of equatorial upwelling, which moderates the intensity of O2 uptake due to vertical transport of low-O2 waters. These upwelling changes dominate over counteracting effects of biological productivity and thermally driven O2 exchange. During El Niño, shallower and weaker upwelling leads to anomalous O2 outgassing, whereas deeper and intensified upwelling during La Niña drives enhanced O2 uptake. This response is strongly localized along the central and eastern equatorial Pacific, leading to an equatorial zonal dipole in atmospheric anomalies of APO. This dipole is further intensified by ENSO-related changes in winds, reconciling apparently conflicting APO observations in the tropical Pacific. These findings suggest a substantial and complex response of the oceanic O2 cycle to climate variability that is significantly (>50%) underestimated in magnitude by ocean models.

  11. Left Ventricular Mechanical Support with the Impella during Extracorporeal Membrane Oxygenation

    Directory of Open Access Journals (Sweden)

    Kasra Moazzami

    2017-03-01

    Full Text Available Background: Venoarterial extracorporeal membrane oxygenation (ECMO provides systemic arterial support without directly unloading the left heart, which causes an elevated left ventricular (LV pressure. The aim of the present study was to investigate the adjunctive application of the Impella device for LV unloading in patients during ECMO.Methods: This retrospective cohort study included patients who received Impella support in addition to venoarterial ECMO between April 2012 and December 2015. ECMO cannulation was performed peripherally or centrally, while the Impella device was surgically inserted into the femoral artery or the right axillary artery. Results: Among 62 patients, 10 (16.1% received an Impella device during ECMO support. Following Impella support, right atrial pressure improved from a median of 18 (IQR, 14–24 mmHg to 13 (IQR, 10–15 mmHg and pulmonary wedge pressure improved from 30 (IQR, 26–35 mmHg to 16 (IQR, 12–19 mmHg in all the patients (p value < 0.001. Follow-up transthoracic echocardiograms (n = 6 showed a median decrease of 0.8 cm in LV end-diastolic volume (p value = 0.021. There were 5 (50% in-hospital deaths due to sustained brain injury (n = 3 and refractory cardiogenic shock (n = 2. The remaining 5 patients were discharged and successfully bridged to more permanent LV assist device (n = 2 or heart transplantation (n = 3.Conclusion: The findings of the present study indicate that the application of the Impella device during ECMO support is effective in LV unloading and confers optimal hemodynamic support.

  12. The effect of acute exposure to hyperbaric oxygen on respiratory system mechanics in the rat.

    Science.gov (United States)

    Rubini, Alessandro; Porzionato, Andrea; Zara, Susi; Cataldi, Amelia; Garetto, Giacomo; Bosco, Gerardo

    2013-10-01

    This study was designed to investigate the possible effects of acute hyperbaric hyperoxia on respiratory mechanics of anaesthetised, positive-pressure ventilated rats. We measured respiratory mechanics by the end-inflation occlusion method in nine rats previously acutely exposed to hyperbaric hyperoxia in a standard fashion. The method allows the measurements of respiratory system elastance and of both the "ohmic" and of the viscoelastic components of airway resistance, which respectively depend on the newtonian pressure dissipation due to the ohmic airway resistance to air flow, and on the viscoelastic pressure dissipation caused by respiratory system tissues stress-relaxation. The activities of inducible and endothelial NO-synthase in the lung's tissues (iNOS and eNOS respectively) also were investigated. Data were compared with those obtained in control animals. We found that the exposure to hyperbaric hyperoxia increased respiratory system elastance and both the "ohmic" and viscoelastic components of inspiratory resistances. These changes were accompanied by increased iNOS but not eNOS activities. Hyperbaric hyperoxia was shown to acutely induce detrimental effects on respiratory mechanics. A possible causative role was suggested for increased nitrogen reactive species production because of increased iNOS activity.

  13. Reactive oxygen species scavengers ameliorate mechanical allodynia in a rat model of cancer-induced bone pain

    Directory of Open Access Journals (Sweden)

    Ya-Qun Zhou

    2018-04-01

    Full Text Available Cancer-induced bone pain (CIBP is a frequent complication in patients suffering from bone metastases. Previous studies have demonstrated a pivotal role of reactive oxygen species (ROS in inflammatory and neuropathic pain, and ROS scavengers exhibited potent antinociceptive effect. However, the role of spinal ROS remains unclear. In this study, we investigated the analgesic effect of two ROS scavengers in a well-established CIBP model. Our results found that intraperitoneal injection of N-tert-Butyl-α-phenylnitrone (PBN, 50 and 100 mg/kg and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (Tempol, 100 and 200 mg/kg significantly suppressed the established mechanical allodynia in CIBP rats. Moreover, repeated injection of PBN and Tempol showed cumulative analgesic effect without tolerance. However, early treatment with PBN and Tempol failed to prevent the development of CIBP. Naive rats received repetitive injection of PBN and Tempol showed no significant change regarding the nociceptive responses. Finally, PBN and Tempol treatment notably suppressed the activation of spinal microglia in CIBP rats. In conclusion, ROS scavengers attenuated established CIBP by suppressing the activation of microglia in the spinal cord. Keywords: Cancer-induced bone pain, Reactive oxygen species, PBN, Tempol

  14. Decreases in maximal oxygen uptake following long-duration spaceflight: Role of convective and diffusive O2transport mechanisms.

    Science.gov (United States)

    Ade, C J; Broxterman, R M; Moore, A D; Barstow, T J

    2017-04-01

    We have previously predicted that the decrease in maximal oxygen uptake (V̇o 2max ) that accompanies time in microgravity reflects decrements in both convective and diffusive O 2 transport to the mitochondria of the contracting myocytes. The aim of this investigation was therefore to quantify the relative changes in convective O 2 transport (Q̇o 2 ) and O 2 diffusing capacity (Do 2 ) following long-duration spaceflight. In nine astronauts, resting hemoglobin concentration ([Hb]), V̇o 2max , maximal cardiac output (Q̇ Tmax ), and differences in arterial and venous O 2 contents ([Formula: see text]-[Formula: see text]) were obtained retrospectively for International Space Station Increments 19-33 (April 2009-November 2012). Q̇o 2 and Do 2 were calculated from these variables via integration of Fick's Principle of Mass Conservation and Fick's Law of Diffusion. V̇o 2max significantly decreased from pre- to postflight (-53.9 ± 45.5%, P = 0.008). The significant decrease in Q̇ Tmax (-7.8 ± 9.1%, P = 0.05), despite an unchanged [Hb], resulted in a significantly decreased Q̇o 2 (-11.4 ± 10.5%, P = 0.02). Do 2 significantly decreased from pre- to postflight by -27.5 ± 24.5% ( P = 0.04), as did the peak [Formula: see text]-[Formula: see text] (-9.2 ± 7.5%, P = 0.007). With the use of linear regression analysis, changes in V̇o 2max were significantly correlated with changes in Do 2 ( R 2  = 0.47; P = 0.04). These data suggest that spaceflight decreases both convective and diffusive O 2 transport. These results have practical implications for future long-duration space missions and highlight the need to resolve the specific mechanisms underlying these spaceflight-induced changes along the O 2 transport pathway. NEW & NOTEWORTHY Long-duration spaceflight elicited a significant decrease in maximal oxygen uptake. Given the adverse physiological adaptations to microgravity along the O 2 transport pathway that have been reported, an integrative

  15. Arteriolar oxygen reactivity: where is the sensor and what is the mechanism of action?

    Science.gov (United States)

    2016-01-01

    Abstract Arterioles in the peripheral microcirculation are exquisitely sensitive to changes in PO2 in their environment: increases in PO2 cause vasoconstriction while decreases in PO2 result in vasodilatation. However, the cell type that senses O2 (the O2 sensor) and the signalling pathway that couples changes in PO2 to changes in arteriolar tone (the mechanism of action) remain unclear. Many (but not all) ex vivo studies of isolated cannulated resistance arteries and large, first‐order arterioles support the hypothesis that these vessels are intrinsically sensitive to PO2 with the smooth muscle, endothelial cells, or red blood cells serving as the O2 sensor. However, in situ studies testing these hypotheses in downstream arterioles have failed to find evidence of intrinsic O2 sensitivity, and instead have supported the idea that extravascular cells sense O2. Similarly, ex vivo studies of isolated, cannulated resistance arteries and large first‐order arterioles support the hypotheses that O2‐dependent inhibition of production of vasodilator cyclooxygenase products or O2‐dependent destruction of nitric oxide mediates O2 reactivity of these upstream vessels. In contrast, most in vivo studies of downstream arterioles have disproved these hypotheses and instead have provided evidence supporting the idea that O2‐dependent production of vasoconstrictors mediates arteriolar O2 reactivity, with significant regional heterogeneity in the specific vasoconstrictor involved. Oxygen‐induced vasoconstriction may serve as a protective mechanism to reduce the oxidative burden to which a tissue is exposed, a process that is superimposed on top of the local mechanisms which regulate tissue blood flow to meet a tissue's metabolic demand. PMID:27324312

  16. Reduction of enzyme dosage by oxygen delignification and mechanical refining for enzymatic hydrolysis of green liquor-pretreated hardwood.

    Science.gov (United States)

    Koo, Bon-Wook; Treasure, Trevor H; Jameel, Hasan; Phillips, Richard B; Chang, Hou-Min; Park, Sunkyu

    2011-10-01

    In this study, a strategy to reduce enzyme dosage is evaluated by applying two post-treatments, oxygen delignification and mechanical refining. The sugar conversion for GL12 substrates was increased from 51.5% to 77.9% with post-treatments at the enzyme dosage of 10 FPU. When the amount of enzyme was reduced to 5 FPU with post-treatments, the conversion of 71.8% was obtained, which was significant higher than the conversion without any post-treatment using 10 FPU (51.5%). This clearly demonstrates the benefit of post-treatments that allows more than 50% of enzyme reduction at the same level of enzymatic conversion. Enzyme-accessible surface area and pore volume were evaluated by Simons' staining and DSC thermoporometry methods, and strong correlations were found with the sugar conversion.

  17. Comparative analysis of nitrite uptake and hemoglobin-nitrite reactions in erythrocytes: sorting out uptake mechanisms and oxygenation dependencies

    DEFF Research Database (Denmark)

    Jensen, Frank Bo; Rohde, Sabina

    2010-01-01

    (hagfish and lamprey) anion exchanger-1 (AE1) in the membrane, with the aim to unravel the mechanisms and oxygenation dependencies of nitrite transport. Added nitrite rapidly diffused into the RBCs until equilibrium. The distribution ratio of nitrite across the membrane agreed with that expected from HNO2...... diffusion and AE1-mediated facilitated NO2- diffusion. Participation of HNO2 diffusion was emphasized by rapid transmembrane nitrite equilibration also in the natural AE1 knockouts. Following the equilibration, nitrite was consumed by reacting with Hb, which created a continued inward diffusion controlled....... We propose a model for RBC nitrite uptake that involves both HNO2 diffusion and AE1-mediated transport and which explains both the present and previous (sometimes puzzling) results....

  18. Lysosomal membrane permeabilization: Carbon nanohorn-induced reactive oxygen species generation and toxicity by this neglected mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Mei, E-mail: happy_deercn@163.com [Nanotube Research Center, National Institute of Advanced Industrial Science and Technology 5-2, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Zhang, Minfang; Tahara, Yoshio; Chechetka, Svetlana; Miyako, Eijiro [Nanotube Research Center, National Institute of Advanced Industrial Science and Technology 5-2, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Iijima, Sumio [Nanotube Research Center, National Institute of Advanced Industrial Science and Technology 5-2, 1-1-1 Higashi, Tsukuba 305-8565 (Japan); Faculty of Science and Technology, Meijo University, 1-501 Shiogamaguchi, Tenpaku, Nagoya 468-8502 (Japan); Yudasaka, Masako, E-mail: m-yudasaka@aist.go.jp [Nanotube Research Center, National Institute of Advanced Industrial Science and Technology 5-2, 1-1-1 Higashi, Tsukuba 305-8565 (Japan)

    2014-10-01

    Understanding the molecular mechanisms responsible for the cytotoxic effects of carbon nanomaterials is important for their future biomedical applications. Carbon nanotubular materials induce the generation of reactive oxygen species (ROS), which causes cell death; however, the exact details of this process are still unclear. Here, we identify a mechanism of ROS generation that is involved in the apoptosis of RAW264.7 macrophages caused by excess uptake of carbon nanohorns (CNHs), a typical type of carbon nanotubule. CNH accumulated in the lysosomes, where they induced lysosomal membrane permeabilization (LMP) and the subsequent release of lysosomal proteases, such as cathepsins, which in turn caused mitochondrial dysfunction and triggered the generation of ROS in the mitochondria. The nicotinamide adenine dinucleotide phosphate oxidase was not directly involved in CNH-related ROS production, and the ROS generation cannot be regulated by mitochondrial electron transport chain. ROS fed back to amplify the mitochondrial dysfunction, leading to the subsequent activation of caspases and cell apoptosis. Carbon nanotubules commonly accumulate in the lysosomes after internalization in cells; however, lysosomal dysfunction has not attracted much attention in toxicity studies of these materials. These results suggest that LMP, a neglected mechanism, may be the primary reason for carbon nanotubule toxicity. - Highlights: • We clarify an apoptotic mechanism of RAW264.7 cells caused by carbon nanohorns. • In the meantime, the mechanism of CNH-induced ROS generation is identified. • LMP is the initial factor of CNH-induced ROS generation and cell death. • Cathepsins work as mediators that connect LMP and mitochondrial dysfunction.

  19. Effects of manual rib-cage compression versus PEEP-ZEEP maneuver on respiratory system compliance and oxygenation in patients receiving mechanical ventilation.

    Science.gov (United States)

    Santos, Flavio Renato Antunes Dos; Schneider Júnior, Luiz Carlos; Forgiarini Junior, Luiz Alberto; Veronezi, Jefferson

    2009-06-01

    Patients unable to perform breathing functions may be submitted to invasive mechanical ventilation. Chest physiotherapy acts directly on the treatment of these patients for the purpose of improving their lung function. The objective of this study was to evaluate the effects of manual rib-cage compression versus the positive end expiratory pressure-zero end expiratory pressure (PEEP-ZEEP) maneuver, on compliance of the respiratory system and oxygenation in patients under invasive mechanical ventilation. A double centric, prospective, randomized and crossover study, with patients under invasive mechanical ventilation, in controlled mode for more than 48 hours was carried out. The protocols of chest physiothe-rapy were randomly applied at an interval of 24 hours. Data of respiratory system compliance and oxygenation were collected before application of the protocols and 30 minutes after. Twelve patients completed the study. Intragroup analysis, for both techniques showed a statistically significant difference in tidal volume (p=0.002), static compliance (p=0.002) and dynamic compliance (p=0.002). In relation to oxygenation, in the group of manual rib-cage compression, peripheral oxygen saturation increased with a significant difference (p=0.011). Manual rib-cage compression and PEEP-ZEEP maneuver have positive clinical effects. In relation to oxygenation we found a favorable behavior of peripheral oxygen saturation in the group of manual rib-cage compression.

  20. [Mechanisms of signaling associated with reactive nitrogen and oxygen in apoptosis].

    Science.gov (United States)

    Piłat, Justyna; Ługowski, Mateusz; Saczko, Jolanta; Choromańska, Anna; Chwiłkowska, Agnieszka; Banaś, Teresa; Kulbacka, Julita

    2016-05-01

    The knowledge of apoptotic mechanisms is essential in many biologic aspects related to both normal and neoplastic cells. Cell death by apoptosis is a very desirable way to eliminate unwanted cells: prevents release of the cellular content, which, in contrast to necrosis, provides no activation of inflammatory reactions. Apoptosis is a multistep process in where an extremely important role is played by caspases. Functions of caspases and their modifications are fundamental to understanding the signaling pathways responsible for regulation of apoptosis. These enzymes belong to a family of cysteine proteases that have the potential to destroy the enzymatic and structural proteins, and in the final stages of apoptosis, to lead to the disintegration of the cell. Apoptosis can be modulated by certain signaling pathway. © 2016 MEDPRESS.

  1. Mechanism of Oxygen Atom Transfer from Fe(V)(O) to Olefins at Room Temperature.

    Science.gov (United States)

    Singh, Kundan K; Tiwari, Mrityunjay K; Dhar, Basab B; Vanka, Kumar; Sen Gupta, Sayam

    2015-07-06

    In biological oxidations, the intermediate Fe(V)(O)(OH) has been proposed to be the active species for catalyzing the epoxidation of alkenes by nonheme iron complexes. However, no study has been reported yet that elucidates the mechanism of direct O-atom transfer during the reaction of Fe(V)(O) with alkenes to form the corresponding epoxide. For the first time, we study the mechanism of O-atom transfer to alkenes using the Fe(V)(O) complex of biuret-modified Fe-TAML at room temperature. The second-order rate constant (k2) for the reaction of different alkenes with Fe(V)(O) was determined under single-turnover conditions. An 8000-fold rate difference was found between electron-rich (4-methoxystyrene; k2 = 216 M(-1) s(-1)) and electron-deficient (methyl trans-cinnamate; k2 = 0.03 M(-1) s(-1)) substrates. This rate difference indicates the electrophilic character of Fe(V)(O). The use of cis-stilbene as a mechanistic probe leads to the formation of both cis- and trans-stilbene epoxides (73:27). This suggests the formation of a radical intermediate, which would allow C-C bond rotation to yield both stereoisomers of stilbene-epoxide. Additionally, a Hammett ρ value of -0.56 was obtained for the para-substituted styrene derivatives. Detailed DFT calculations show that the reaction proceeds via a two-step process through a doublet spin surface. Finally, using biuret-modified Fe-TAML as the catalyst and NaOCl as the oxidant under catalytic conditions epoxide was formed with modest yields and turnover numbers.

  2. Electroweak baryogenesis and dark matter from a singlet Higgs

    Energy Technology Data Exchange (ETDEWEB)

    Cline, James M. [Department of Physics, McGill University, 3600 Rue University, Montréal, Québec, H3A 2T8 Canada (Canada); Kainulainen, Kimmo, E-mail: jcline@physics.mcgill.ca, E-mail: kimmo.kainulainen@jyu.fi [Department of Physics, University of Jyväskylä, P.O. Box 35 (YFL), FI-40014 Jyväskylä (Finland)

    2013-01-01

    If the Higgs boson H couples to a singlet scalar S via λ{sub m}|H|{sup 2}S{sup 2}, a strong electroweak phase transition can be induced through a large potential barrier that exists already at zero temperature. In this case properties of the phase transition can be computed analytically. We show that electroweak baryogenesis can be achieved using CP violation from a dimension-6 operator that couples S to the top-quark mass, suppressed by a new physics scale that can be well above 1 TeV. Moreover the singlet is a dark matter candidate whose relic density is ∼<3% of the total dark matter density, but which nevertheless interacts strongly enough with nuclei (through Higgs exchange) to be just below the current XENON100 limits. The DM mass is predicted to be in the range 80–160 GeV.

  3. Confinement sensitivity in quantum dot singlet-triplet relaxation

    Science.gov (United States)

    Wesslén, C. J.; Lindroth, E.

    2017-11-01

    Spin-orbit mediated phonon relaxation in a two-dimensional quantum dot is investigated using different confining potentials. Elliptical harmonic oscillator and cylindrical well results are compared to each other in the case of a two-electron GaAs quantum dot subjected to a tilted magnetic field. The lowest energy set of two-body singlet and triplet states are calculated including spin-orbit and magnetic effects. These are used to calculate the phonon induced transition rate from the excited triplet to the ground state singlet for magnetic fields up to where the states cross. The roll of the cubic Dresselhaus effect, which is found to be much more important than previously assumed, and the positioning of ‘spin hot-spots’ are discussed and relaxation rates for a few different systems are exhibited.

  4. Mixing of Singlet and Triplet Pairing for Surface Superconductivity

    Science.gov (United States)

    Gor'kov, L. P.; Rashba, E. I.

    2002-07-01

    We consider structure of the Cooper wave function for superconductivity in a surface layer. Broken space inversion at the surface results in lifted spin degeneracy and in two branches of the gapped energy spectrum as caused by the spin-orbit interaction. The pair wave function consists of a mixture of both singlet and triplet components. Anisotropy of the Knight shift measurable in the NMR experiments is calculated in the whole temperature regime. Implications for a few known experimental situations is briefly discussed.

  5. Generation of deviation parameters for amino acid singlets, doublets ...

    Indian Academy of Sciences (India)

    consecutive amino acids (ABC) for triplets in the selected dataset, Ni (X) = number of counts for X in the ith protein, Yi. = Ti for singlets, Ti-1 for doublets, Ti-2 for triplets where Ti is the total number of amino acids in the ith protein, i varies from 1 to n and n = total number of proteins considered (in this case, 408). Based on the ...

  6. Singlet-paired coupled cluster theory for open shells

    International Nuclear Information System (INIS)

    Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

    2016-01-01

    Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework. The recently introduced singlet-paired coupled cluster doubles (CCD0) method is one such model, which recovers correct behavior for strong correlation without requiring symmetry breaking in the reference. Here, we extend singlet-paired coupled cluster for application to open shells via restricted open-shell singlet-paired coupled cluster singles and doubles (ROCCSD0). The ROCCSD0 approach retains the benefits of standard coupled cluster theory and recovers correct behavior for strongly correlated, open-shell systems using a spin-preserving ROHF reference.

  7. IDMS: inert dark matter model with a complex singlet

    Science.gov (United States)

    Bonilla, Cesar; Sokolowska, Dorota; Darvishi, Neda; Diaz-Cruz, J. Lorenzo; Krawczyk, Maria

    2016-06-01

    We study an extension of the inert doublet model (IDM) that includes an extra complex singlet of the scalars fields, which we call the IDMS. In this model there are three Higgs particles, among them a SM-like Higgs particle, and the lightest neutral scalar, from the inert sector, remains a viable dark matter (DM) candidate. We assume a non-zero complex vacuum expectation value for the singlet, so that the visible sector can introduce extra sources of CP violation. We construct the scalar potential of IDMS, assuming an exact Z 2 symmetry, with the new singlet being Z 2-even, as well as a softly broken U(1) symmetry, which allows a reduced number of free parameters in the potential. In this paper we explore the foundations of the model, in particular the masses and interactions of scalar particles for a few benchmark scenarios. Constraints from collider physics, in particular from the Higgs signal observed at the Large Hadron Collider with {M}h≈ 125 {{GeV}}, as well as constraints from the DM experiments, such as relic density measurements and direct detection limits, are included in the analysis. We observe significant differences with respect to the IDM in relic density values from additional annihilation channels, interference and resonance effects due to the extended Higgs sector.

  8. NLO electroweak corrections in general scalar singlet models

    Science.gov (United States)

    Costa, Raul; Sampaio, Marco O. P.; Santos, Rui

    2017-07-01

    If no new physics signals are found, in the coming years, at the Large Hadron Collider Run-2, an increase in precision of the Higgs couplings measurements will shift the discussion to the effects of higher order corrections. In Beyond the Standard Model (BSM) theories this may become the only tool to probe new physics. Extensions of the Standard Model (SM) with several scalar singlets may address several of its problems, namely to explain dark matter, the matter-antimatter asymmetry, or to improve the stability of the SM up to the Planck scale. In this work we propose a general framework to calculate one loop-corrections to the propagators and to the scalar field vacuum expectation values of BSM models with an arbitrary number of scalar singlets. We then apply our method to a real and to a complex scalar singlet models. We assess the importance of the one-loop radiative corrections first by computing them for a tree level mixing sum constraint, and then for the main Higgs production process gg → H. We conclude that, for the currently allowed parameter space of these models, the corrections can be at most a few percent. Notably, a non-zero correction can survive when dark matter is present, in the SM-like limit of the Higgs couplings to other SM particles.

  9. Surface reaction mechanisms during ozone and oxygen plasma assisted atomic layer deposition of aluminum oxide.

    Science.gov (United States)

    Rai, Vikrant R; Vandalon, Vincent; Agarwal, Sumit

    2010-09-07

    We have elucidated the reaction mechanism and the role of the reactive intermediates in the atomic layer deposition (ALD) of aluminum oxide from trimethyl aluminum in conjunction with O(3) and an O(2) plasma. In situ attenuated total reflection Fourier transform infrared spectroscopy data show that both -OH groups and carbonates are formed on the surface during the oxidation cycle. These carbonates, once formed on the surface, are stable to prolonged O(3) exposure in the same cycle. However, in the case of plasma-assisted ALD, the carbonates decompose upon prolonged O(2) plasma exposure via a series reaction kinetics of the type, A (CH(3)) --> B (carbonates) --> C (Al(2)O(3)). The ratio of -OH groups to carbonates on the surface strongly depends on the oxidizing agent, and also the duration of the oxidation cycle in plasma-assisted ALD. However, in both O(3) and O(2) plasma cycles, carbonates are a small fraction of the total number of reactive sites compared to the hydroxyl groups.

  10. Correlated Pair States Formed by Singlet Fission and Exciton-Exciton Annihilation.

    Science.gov (United States)

    Scholes, Gregory D

    2015-12-24

    Singlet fission to form a pair of triplet excitations on two neighboring molecules and the reverse process, triplet-triplet annihilation to upconvert excitation, have been extensively studied. Comparatively little work has sought to examine the properties of the intermediate state in both of these processes-the bimolecular pair state. Here, the eigenstates constituting the manifold of 16 bimolecular pair excitations and their relative energies in the weak-coupling regime are reported. The lowest-energy states obtained from the branching diagram method are the triplet pairs with overall singlet spin |X1⟩ ≈ (1)[TT] and quintet spin |Q⟩ ≈ (5)[TT]. It is shown that triplet pair states can be separated by a triplet-triplet energy-transfer mechanism to give a separated, yet entangled triplet pair (1)[T···T]. Independent triplets are produced by decoherence of the separated triplet pair. Recombination of independent triplets by exciton-exciton annihilation to form the correlated triplet pair (i.e., nongeminate recombination) happens with 1/3 of the rate of either triplet migration or recombination of the separated correlated triplet pair (geminate recombination).

  11. Antibody-induced generation of reactive oxygen radicals by brain macrophages in canine distemper encephalitis: a mechanism for bystander demyelination.

    Science.gov (United States)

    Griot, C; Bürge, T; Vandevelde, M; Peterhans, E

    1989-01-01

    The mechanism of inflammatory demyelination in canine distemper encephalitis (CDE) is uncertain but macrophages are thought to play an important effector role in this lesion. Serum and cerebrospinal fluid (CSF), containing anti-canine distemper virus and anti-myelin antibodies from dogs with CDE were tested for their ability to generate reactive oxygen species (ROS) in macrophages in primary dog brain cell cultures using a chemiluminescence (CL) assay. The majority of serum samples and several CSF samples from animals with inflammatory demyelination elicited a CL signal in infected dog brain cell cultures. In contrast, none of these samples induced a positive response in uninfected cultures which contained large numbers of myelin antigen-presenting cells, although defined anti-myelin antibodies lead to a marked secretion of ROS in this system. It was concluded that antiviral antibody-induced secretion of ROS, known to be highly toxic for brain tissue, may play an important role in white matter damage in inflammatory lesions supporting a previous hypothesis of bystander demyelination in CDE. No evidence was found for a similar antibody-dependent cellular cytotoxicity-like mechanism mediated by anti-myelin antibodies in CDE, which does not support the concept of autoimmunity in this disease.

  12. Aquatic acidification: a mechanism underpinning maintained oxygen transport and performance in fish experiencing elevated carbon dioxide conditions.

    Science.gov (United States)

    Hannan, Kelly D; Rummer, Jodie L

    2018-03-07

    Aquatic acidification, caused by elevating levels of atmospheric carbon dioxide (CO 2 ), is increasing in both freshwater and marine ecosystems worldwide. However, few studies have examined how acidification will affect oxygen (O 2 ) transport and, therefore, performance in fishes. Although data are generally lacking, the majority of fishes investigated in this meta-analysis exhibited no effect of elevated CO 2 at the level of O 2 uptake, suggesting that they are able to maintain metabolic performance during a period of acidosis. Notably, the mechanisms that fish employ to maintain performance and O 2 uptake have yet to be verified. Here, we summarize current data related to one recently proposed mechanism underpinning the maintenance of O 2 uptake during exposure to aquatic acidification, and reveal knowledge gaps that could be targeted for future research. Most studies have examined O 2 uptake rates while fishes were resting and did not calculate aerobic scope, even though aerobic scope can aid in predicting changes to whole-animal metabolic performance. Furthermore, research is lacking on different age classes, freshwater species and elasmobranchs, all of which might be impacted by future acidification conditions. Finally, this Review further seeks to emphasize the importance of developing collaborative efforts between molecular, physiological and ecological approaches in order to provide more comprehensive predictions as to how future fish populations will be affected by climate change. © 2018. Published by The Company of Biologists Ltd.

  13. Application of isotope exchange based mass spectrometry to understand the mechanism of inhibition of sickle hemoglobin polymerization upon oxygenation.

    Science.gov (United States)

    Das, Rajdeep; Mitra, Amrita; Bhat, Vijay; Mandal, Amit Kumar

    2017-07-01

    Sickle hemoglobin (HbS) polymerization initiates in the deoxy state with the binding of hydrophobic patch formed by the isopropyl group of βVal6 residue of a hemoglobin tetramer with the hydrophobic pocket of another tetramer, whose hydrophobic patch binds to the hydrophobic groove of a third molecule. Subsequent elongation of a single stranded polymer followed by the formation of a double strand and finally combination of seven such pairs of double strands results in a fourteen stranded fibrous polymer. Precipitation of this fiber inside the erythrocytes results in sickling of red blood cells. Surprisingly, the polymerization does not occur in the oxy state of HbS. Due to the unavailability of crystal structure of oxy form of HbS, the molecular basis of inhibition of polymerization in the oxy state is unknown to date. In the present study, we have attempted to understand the molecular mechanism of inhibition of polymerization by exploiting the exchange of backbone amide hydrogens of HbS with deuterated solvent. Hydrogen/deuterium exchange kinetics of peptide amide hydrogens of both oxy and deoxy form of HbS were monitored through ESI mass spectrometry. Upon oxygenation changes in the conformational flexibility across different regions of α and β globin chains in the tetrameric HbS molecule were investigated. It was observed that oxygenation led to perturbation in the conformation of several residues around the hydrophobic patch, groove of a tetramer and axial, lateral contacts across the double strands that are involved in HbS polymerization. Copyright © 2017 Elsevier Inc. All rights reserved.

  14. Numerical simulation of physicochemical interactions between oxygen atom and phosphatidylcholine due to direct irradiation of atmospheric pressure nonequilibrium plasma to biological membrane with quantum mechanical molecular dynamics

    Science.gov (United States)

    Uchida, Satoshi; Yoshida, Taketo; Tochikubo, Fumiyoshi

    2017-10-01

    Plasma medicine is one of the most attractive applications using atmospheric pressure nonequilibrium plasma. With respect to direct contact of the discharge plasma with a biological membrane, reactive oxygen species play an important role in induction of medical effects. However, complicated interactions between the plasma radicals and membrane have not been understood well. In the present work, we simulated elemental processes at the first stage of physicochemical interactions between oxygen atom and phosphatidylcholine using the quantum mechanical molecular dynamics code in a general software AMBER. The change in the above processes was classified according to the incident energy of oxygen atom. At an energy of 1 eV, the abstraction of a hydrogen atom and recombination to phosphatidylcholine were simultaneously occurred in chemical attachment of incident oxygen atom. The exothermal energy of the reaction was about 80% of estimated one based on the bond energies of ethane. An oxygen atom over 10 eV separated phosphatidylcholine partially. The behaviour became increasingly similar to physical sputtering. The reaction probability of oxygen atom was remarkably high in comparison with that of hydrogen peroxide. These results suggest that we can uniformly estimate various physicochemical dynamics of reactive oxygen species against membrane lipids.

  15. Viable dark matter via radiative symmetry breaking in a scalar singlet Higgs portal extension of the standard model.

    Science.gov (United States)

    Steele, T G; Wang, Zhi-Wei; Contreras, D; Mann, R B

    2014-05-02

    We consider the generation of dark matter mass via radiative electroweak symmetry breaking in an extension of the conformal standard model containing a singlet scalar field with a Higgs portal interaction. Generating the mass from a sequential process of radiative electroweak symmetry breaking followed by a conventional Higgs mechanism can account for less than 35% of the cosmological dark matter abundance for dark matter mass M(s)>80 GeV. However, in a dynamical approach where both Higgs and scalar singlet masses are generated via radiative electroweak symmetry breaking, we obtain much higher levels of dark matter abundance. At one-loop level we find abundances of 10%-100% with 106 GeVdark matter mass. The dynamical approach also predicts a small scalar-singlet self-coupling, providing a natural explanation for the astrophysical observations that place upper bounds on dark matter self-interaction. The predictions in all three approaches are within the M(s)>80 GeV detection region of the next generation XENON experiment.

  16. Reactive oxygen species on bone mineral density and mechanics in Cu,Zn superoxide dismutase (Sod1) knockout mice

    International Nuclear Information System (INIS)

    Smietana, Michael J.; Arruda, Ellen M.; Faulkner, John A.; Brooks, Susan V.; Larkin, Lisa M.

    2010-01-01

    Research highlights: → Reactive oxygen species (ROS) are considered to be a factor in the onset of a number of age-associated conditions, including loss of BMD. → Cu,Zn-superoxide dismutase (Sod1) deficient mice have increased ROS, reduced bone mineral density, decreased bending stiffness, and decreased strength compared to WT controls. → Increased ROS caused by the deficiency of Sod1, may be responsible for the changes in BMD and bone mechanics and therefore represent an appropriate model for studying mechanisms of age-associated bone loss. -- Abstract: Reactive oxygen species (ROS) play a role in a number of degenerative conditions including osteoporosis. Mice deficient in Cu,Zn-superoxide dismutase (Sod1) (Sod1 -/- mice) have elevated oxidative stress and decreased muscle mass and strength compared to wild-type mice (WT) and appear to have an accelerated muscular aging phenotype. Thus, Sod1 -/- mice may be a good model for evaluating the effects of free radical generation on diseases associated with aging. In this experiment, we tested the hypothesis that the structural integrity of bone as measured by bending stiffness (EI; N/mm 2 ) and strength (MPa) is diminished in Sod1 -/- compared to WT mice. Femurs were obtained from male and female WT and Sod1 -/- mice at 8 months of age and three-point bending tests were used to determine bending stiffness and strength. Bones were also analyzed for bone mineral density (BMD; mg/cc) using micro-computed tomography. Femurs were approximately equal in length across all groups, and there were no significant differences in BMD or EI with respect to gender in either genotype. Although male and female mice demonstrated similar properties within each genotype, Sod1 -/- mice exhibited lower BMD and EI of femurs from both males and females compared with gender matched WT mice. Strength of femurs was also lower in Sod1 -/- mice compared to WT as well as between genders. These data indicate that increased oxidative stress

  17. Lithium-Oxygen Batteries: At a Crossroads?

    DEFF Research Database (Denmark)

    Vegge, Tejs; García Lastra, Juan Maria; Siegel, Donald Jason

    2017-01-01

    In this current opinion, we critically review and discuss some of the most important recent findings in the field of rechargeable lithium-oxygen batteries. We discuss recent discoveries like the evolution of reactive singlet oxygen and the use of organic additives to bypass reactive LiO2 reaction...... intermediates, and their possible implications on the potential for commercialization of lithium-oxygen batteries. Finally, we perform a critical assessment of lithium-superoxide batteries and the reversibility of lithium-hydroxide batteries....

  18. Robust triplet-triplet annihilation photon upconversion by efficient oxygen scavenging.

    Science.gov (United States)

    Dzebo, Damir; Moth-Poulsen, Kasper; Albinsson, Bo

    2017-08-09

    We hereby present a simple method for reducing the effect of oxygen quenching in Triplet-Triplet Annihilation Upconversion (TTA-UC) systems. A number of commercially available thioethers and one thiol have been tested as singlet oxygen scavengers. Recording of the upconverted emission from a well-studied PdOEP (sensitizer)-DPA (annihilator/emitter) couple has been made over time with steady-state excitation capturing the steady-state kinetics of the TTA-UC process as the solubilized oxygen is depleted by reaction with the scavengers. The efficiency of the TTA-UC process is compared between chemical oxygen scavenging and mechanical removal by inert gas purging or the freeze-pump-thaw method. Selected methods are combined to explore the highest attainable TTA-UC quantum yield. A maximum TTA-UC quantum yield of 21% with the shortest UC onset time was obtained with dimethylthiomethane (DMTM) as the scavenger in an air-saturated solvent and slightly higher quantum yields were obtained in combination with other deoxygenation techniques. Samples containing DMTM displayed little decrease in the quantum yield over four hours of continuous high intensity irradiation, which illustrates the robustness of applying chemical oxygen removal in TTA-UC instead of more time-consuming mechanical processes that usually require specialized equipment.

  19. Influence of Oxygen Content and Microstructure on the Mechanical Properties and Biocompatibility of Ti–15 wt%Mo Alloy Used for Biomedical Applications

    Directory of Open Access Journals (Sweden)

    José R. S. Martins, Jr.

    2014-01-01

    Full Text Available The Ti–15Mo alloy has its mechanical properties strongly altered by heat treatments and by addition of interstitial elements, such as, oxygen, for example. In this sense, the objective of this paper is to analyze the effect of the introduction of oxygen in selected mechanical properties and the biocompatibility of Ti–15Mo alloy. The samples used in this study were prepared by arc-melting and characterized by density measurements, X-ray diffraction, scanning electron microscopy, microhardness, modulus of elasticity, and biocompatibility tests. Hardness measurements were shown to be sensitive to concentration of oxygen. The modulus results showed interstitial influence in value; this was verified under several conditions to which the samples were exposed. Cytotoxicity tests conducted in vitro showed that the various processing conditions did not alter the biocompatibility of the material.

  20. Singlet Fission of Non-polycyclic Aromatic Molecules in Organic Photovoltaics.

    Science.gov (United States)

    Kawata, So; Pu, Yong-Jin; Saito, Ayaka; Kurashige, Yuki; Beppu, Teruo; Katagiri, Hiroshi; Hada, Masaki; Kido, Junji

    2016-02-24

    Singlet fission of thienoquinoid compounds in organic photovoltaics is demonstrated. The escalation of the thienoquinoid length of the compounds realizes a suitable packing structure and energy levels for singlet fission. The magnetic-field dependence of the photocurrent and the external quantum efficiency of the devices reveal singlet fission of the compounds and dissociation of triplet excitons into charges. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Absolute rate constant, kinetic isotope effect, and mechanism of the reaction of ethylene oxide with oxygen(3P) atoms

    International Nuclear Information System (INIS)

    Bogan, D.J.; Hand, C.W.

    1978-01-01

    The kinetics of the reaction of ethylene oxide with O( 3 P) atoms has been investigated in detail using a discharge flow system with mass spectrometric and photometric detection. Absolute measurements of the rate constant, kinetic isotope effect, and stoichiometry have been made. The overall stoichiometry is 3 +- 1 oxygen atoms consumed per ethylene oxide molecule. Arrhenius parameters for the reaction of C 2 H 4 O with O are A = 10/sup (9.28+-0.08)/ L mol -1 s -1 and E = 5250 +- 150 cal mol -1 over the temperature range 298 to 691 0 K, and Arrhenius parameters for the kinetic isotope effect are A/sub H//A/sub D/ = 0.9 +- 0.20 and E/sub D/--E/sub H/ = 1460 +- 230 cal mol -1 , over the temperature range 482 to 691 0 K. The magnitude of the preexponential factor and the temperature dependence of the isotope effect establish that hydrogen abstraction, rather than insertion to form a dioxetane intermediate, is the sole reactive channel for ethylene oxide plus O( 3 P). The Arrhenius parameters are discussed and compared to other hydrogen abstraction reactions of O( 3 P). Comparison is also made to the reactions of O( 3 P) with other strained three-membered ring compounds. The final products H 2 , H 2 O, HCHO, CO, and CO 2 were identified, and a mechanism is proposed to account for their formation from the radical products of the initial step

  2. Potential mechanisms of carbon monoxide and high oxygen packaging in maintaining color stability of different bovine muscles.

    Science.gov (United States)

    Liu, Chenglong; Zhang, Yimin; Yang, Xiaoyin; Liang, Rongrong; Mao, Yanwei; Hou, Xu; Lu, Xiao; Luo, Xin

    2014-06-01

    The objectives were to compare the effects of packaging methods on color stability, metmyoglobin-reducing-activity (MRA), total-reducing-activity and NADH concentration of different bovine muscles and to explore potential mechanisms in the enhanced color stability by carbon monoxide modified atmosphere packaging (CO-MAP, 0.4% CO/30% CO2/69.6% N2). Steaks from longissimus lumborum (LL), psoas major (PM) and longissimus thoracis (LT) packaged in CO-MAP, high-oxygen modified atmosphere packaging (HiOx-MAP, 80% O2/20% CO2) or vacuum packaging were stored for 0day, 4days, 9days, and 14days or stored for 9days then displayed in air for 0day, 1day, or 3days. The CO-MAP significantly increased red color stability of all muscles, and especially for PM. The PM and LT were more red than LL in CO-MAP, whereas PM had lowest redness in HiOx-MAP. The content of MetMb in CO-MAP was lower than in HiOx-MAP. Steaks in CO-MAP maintained a higher MRA compared with those in HiOx-MAP during storage. After opening packages, the red color of steaks in CO-MAP deteriorated more slowly compared with that of steaks in HiOx-MAP. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Reactive oxygen species regulatory mechanisms associated with rapid response of MC3T3-E1 cells for vibration stress

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ling; Gan, Xueqi; Zhu, Zhuoli; Yang, Yang; He, Yuting; Yu, Haiyang, E-mail: yhyang6812@scu.edu.cn

    2016-02-12

    Although many previous studies have shown that refractory period-dependent memory effect of vibration stress is anabolic for skeletal homeostasis, little is known about the rapid response of osteoblasts simply derived from vibration itself. In view of the potential role of reactive oxygen species (ROS) in mediating differentiated activity of osteoblasts, whether and how ROS regulates the rapid effect of vibration deserve to be demonstrated. Our findings indicated that MC3T3-E1 cells underwent decreased gene expression of Runx2, Col-I and ALP and impaired ALP activity accompanied by increased mitochondrial fission immediately after vibration loading. Moreover, we also revealed the involvement of ERK-Drp1 signal transduction in ROS regulatory mechanisms responsible for the rapid effect of vibration stress. - Highlights: • ROS contributed to the rapid response of MC3T3-E1 cells for vibration stress. • Imbalance of mitochondrial dynamics were linked to the LMHFV-derived rapid response. • The role of ERK-Drp1 signal pathway in the LMHFV-derived osteoblast rapid response.

  4. Fabrication and characterization of nanostructured mechanically alloyed Pt-Co catalyst for oxygen gas-diffusion-electrode

    International Nuclear Information System (INIS)

    Pharkya, P.; Farhat, Z.; Czech, E.; Hawthorne, H.; Alfantazi, A.

    2003-01-01

    The use of PEM fuel cells depends largely upon the cost of materials, processing and fabrication. The cost of Pt catalyst is a significant cost of a fuel cell. Alternative low cost catalyst that promotes high rate of oxygen reduction is needed. To achieve this, a mechanochemical technique was employed to refine the catalyst layer structure (i.e. increasing the effective catalyst surface area) and reducing the amount of Pt used, by alloying with a cheaper element. An investigation is carried out to study the relationship between the new catalyst structure refinement, morphology, microstructure and its electrocatalytic behaviour. Nanostructured Pt, Co and Pt 0.2 5 Co 0.75 alloy was fabricated from high purity Pt (99.9%) and Co (99.5%) powders using a Laboratory Planetary Ball Mill 'Pulverisette 6'. Optimum milling conditions, that produce fine, uniform and mechanically alloyed microstructure, were determined during fabrication, by varying process parameters (i.e., rpm, milling time, ball to powder ratio, milling atmosphere, surface-agents and milling/cooling cycle). Mechanically induced chemical and physical reactions and thermal effects were monitored 'in-situ' using a GTM system, which recorded temperature and pressure changes during milling. The alloy catalysts were characterized using TEM, SEM, EDX, XRD and BET techniques. Electrochemical tests were carried out on prepared powders. Exchange currents were determined from a potentiodynamic polarization tests and used to compare relative electrocatalytic behaviour of the new catalyst. Structure/property relationships were discussed and conclusions were drawn on the production of improved low cost catalyst. (author)

  5. Toward Singlet-Triplet Bistable Nonalternant Kekulé Hydrocarbons: Azulene-to-Naphthalene Rearrangement.

    Science.gov (United States)

    Das, Soumyajit; Wu, Jishan

    2015-12-04

    Recent developments of open-shell singlet diradicaloids motivated the search for stable singlet-triplet bistable nonalternant polycyclic hydrocarbons. During the synthesis of this type of molecule, such as the dibenzo-cyclohepta[def]fluorene 3, an unexpected azulene-to-naphthalene rearrangement was observed at room temperature, which resulted in new nonalternant hydrocarbons 8a/8b with a closed-shell singlet ground state. These studies provided insight into the unique chemistry of azulene and challenges for the synthesis of singlet-triplet bistable polycyclic hydrocarbons.

  6. Kinetics and mechanisms of the oxidation of alcohols and hydroxylamines by hydrogen peroxide, catalyzed by methyltrioxorhenium, MTO, and the oxygen binding properties of cobalt Schiff base complexes

    Energy Technology Data Exchange (ETDEWEB)

    Zauche, Timothy [Iowa State Univ., Ames, IA (United States)

    1999-02-12

    Catalysis is a very interesting area of chemistry, which is currently developing at a rapid pace. A great deal of effort is being put forth by both industry and academia to make reactions faster and more productive. One method of accomplishing this is by the development of catalysts. Enzymes are an example of catalysts that are able to perform reactions on a very rapid time scale and also very specifically; a goal for every man-made catalyst. A kinetic study can also be carried out for a reaction to gain a better understanding of its mechanism and to determine what type of catalyst would assist the reaction. Kinetic studies can also help determine other factors, such as the shelf life of a chemical, or the optimum temperature for an industrial scale reaction. An area of catalysis being studied at this time is that of oxygenations. Life on this earth depends on the kinetic barriers for oxygen in its various forms. If it were not for these barriers, molecular oxygen, water, and the oxygenated materials in the land would be in a constant equilibrium. These same barriers must be overcome when performing oxygenation reactions on the laboratory or industrial scale. By performing kinetic studies and developing catalysts for these reactions, a large number of reactions can be made more economical, while making less unwanted byproducts. For this dissertation the activation by transition metal complexes of hydrogen peroxide or molecular oxygen coordination will be discussed.

  7. Nanoparticle Toxicity Mechanisms: Genotoxicity

    Science.gov (United States)

    Botta, Alain; Benameur, Laı̈la

    Despite the relatively small amount of convincing experimental data, the potentially genotoxic nature of certain nanoparticles seems plausible, owing in particular to the presence of reactive oxygen species (ROS) such as the superoxide anion O2 • - , the hydroxyl radical • OH, and singlet oxygen 1O2, and reactive nitrogen species (RNS) such as nitrogen monoxide NO, the peroxynitrite anion ONOO - , the peroxynitrite radical ONOO • , and dinitrogen trioxide N2O3, a powerful nitration agent.

  8. Entanglement and Metrology with Singlet-Triplet Qubits

    Science.gov (United States)

    Shulman, Michael Dean

    Electron spins confined in semiconductor quantum dots are emerging as a promising system to study quantum information science and to perform sensitive metrology. Their weak interaction with the environment leads to long coherence times and robust storage for quantum information, and the intrinsic tunability of semiconductors allows for controllable operations, initialization, and readout of their quantum state. These spin qubits are also promising candidates for the building block for a scalable quantum information processor due to their prospects for scalability and miniaturization. However, several obstacles limit the performance of quantum information experiments in these systems. For example, the weak coupling to the environment makes inter-qubit operations challenging, and a fluctuating nuclear magnetic field limits the performance of single-qubit operations. The focus of this thesis will be several experiments which address some of the outstanding problems in semiconductor spin qubits, in particular, singlet-triplet (S-T0) qubits. We use these qubits to probe both the electric field and magnetic field noise that limit the performance of these qubits. The magnetic noise bath is probed with high bandwidth and precision using novel techniques borrowed from the field of Hamiltonian learning, which are effective due to the rapid control and readout available in S-T 0 qubits. These findings allow us to effectively undo the undesired effects of the fluctuating nuclear magnetic field by tracking them in real-time, and we demonstrate a 30-fold improvement in the coherence time T2*. We probe the voltage noise environment of the qubit using coherent qubit oscillations, which is partially enabled by control of the nuclear magnetic field. We find that the voltage noise bath is frequency-dependent, even at frequencies as high as 1MHz, and it shows surprising and, as of yet, unexplained temperature dependence. We leverage this knowledge of the voltage noise environment, the

  9. Reactive oxygen species produced by irradiation of some phthalocyanine derivatives

    Czech Academy of Sciences Publication Activity Database

    Černý, J.; Karásková, M.; Rakušan, J.; Nešpůrek, Stanislav

    2010-01-01

    Roč. 210, č. 1 (2010), s. 82-88 ISSN 1010-6030 R&D Projects: GA AV ČR KAN400720701 Institutional research plan: CEZ:AV0Z40500505 Keywords : singlet oxygen * photosensitizer * phthalocyanine Subject RIV: CG - Electrochemistry Impact factor: 2.243, year: 2010

  10. Vibrational dynamics of aniline (N2)1 clusters in their first excited singlet state

    Science.gov (United States)

    Hineman, M. F.; Kim, S. K.; Bernstein, E. R.; Kelley, D. F.

    1992-04-01

    The first excited singlet state S1 vibrational dynamics of aniline(N2)1 clusters are studied and compared to previous results on aniline(CH4)1 and aniline(Ar)1. Intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) rates fall between the two extremes of the CH4 (fast IVR, slow VP) and Ar (slow IVR, fast VP) cluster results as is predicted by a serial IVR/VP model using Fermi's golden rule to describe IVR processes and a restricted Rice-Ramsperger-Kassel-Marcus (RRKM) theory to describe unimolecular VP rates. The density of states is the most important factor determining the rates. Two product states, 00 and 10b1, of bare aniline and one intermediate state ˜(00) in the overall IVR/VP process are observed and time resolved measurements are obtained for the 000 and ˜(000) transitions. The results are modeled with the serial mechanism described above.

  11. Photophysics of trioxatriangulenium ion. Electrophilic reactivity in the ground state and excited singlet state

    DEFF Research Database (Denmark)

    Reynisson, J.; Wilbrandt, R.; Brinck, V.

    2002-01-01

    . The physical and chemical properties of the excited singlet state of the trioxatriangulenium (TOTA(+)) carbenium ion are investigated by experimental and Computational means. The degeneracy of the lowest excited states is counteracted by Jahn-Teller-type distortion, which leads to vibronic broadening...... of the long wavelength absorption band. A strong fluorescence is observed at 520 nm (tau(n) = 14.6 ns, phi(n) = 0.12 in deaerated acetonitrile). The fluorescence is quenched by 10 aromatic electron donors predominantly via a dynamic charge transfer mechanism, but ground state complexation is shown...... triphenylenes is studied separately. Phosphorescence spectra, triplet lifetimes, and triplet-triplet absorption spectra are provided. In the discussion, TOTA(+) is compared to the unsubstituted xanthenium ion and its 9-phenyl derivative with respect to the excited state properties....

  12. Electrocatalysts with platinum, cobalt and nickel preparations by mechanical alloyed and CVD for the reaction of oxygen reduction

    International Nuclear Information System (INIS)

    Garcia C, M. A.

    2008-01-01

    In this research, the molecular oxygen reduction reaction (ORR) was investigated on electrocatalysts of Co, Ni, Pt and their alloys CoNi, PtCo, PtNi and PtCoNi by using H 2 SO 4 0.5 and KOH 0.5 M solutions as electrolytes. The electrocatalysts were synthesized by Mechanical Alloying (MA) and Chemical Vapor Deposition (CVD) processes. For MA, metallic powders were processed during 20 h of milling in a high energy SPEX 8000 mill. For CVD, a hot-wall reactor was utilized and Co, Ni and Pt acetilactetonates were used as precursors. Films were deposited at a total pressure of 1 torr and temperatures of 400-450 C. Electrocatalysts were characterized by X-Ray Diffraction (XRD). Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Energy Dispersive X-Ray Spectroscopy (EDS). Electrocatalysts prepared by mechanical alloying showed a homogeneously dispersed agglomeration of particles with nano metric size. Electrocatalysts obtained by CVD showed, in some cases, non uniform films, with particles of nano metric size, as well. The electrocatalytic performance was evaluated by using the Rotating Disk Electrode technique (RDE). Electrocatalysts prepared by MA showed higher activity than those obtained by CVD. All electrocatalysts were evaluated in alkaline media. Only electrocatalysts containing Pt were evaluated in acid media, because those materials with Co, Ni and their alloys showed instability in acidic media. Most electrocatalysts followed a mechanism for the ORR producing a certain proportion of H 2 O 2 . All electrocatalysts, exhibited a fair or good electrocatalytic activity in comparison with other similar reported materials. It was found that MA and CVD are appropriate processes to prepare electrocatalysts for the ORR with particles of nano metric size and performing with an acceptable catalytic activity. PtCoNi 70-23-7% by MA and PtCoNi-CVD electrocatalysts showed the highest activity in alkaline media, while in acidic electrolyte PtCoNi 70

  13. Involvement of type I and type II mechanisms on the photoinactivation of non-enveloped DNA and RNA bacteriophages.

    Science.gov (United States)

    Costa, Liliana; Faustino, Maria A F; Tomé, João P C; Neves, Maria G P M S; Tomé, Augusto C; Cavaleiro, José A S; Cunha, Angela; Almeida, Adelaide

    2013-03-05

    Microbial photodynamic inactivation (PDI), involving the use of a photosensitizer (PS), light and molecular oxygen, with the subsequent production of reactive oxygen species (ROS), has been considered a promising and effective technology for viral inactivation. Although singlet oxygen is generally accepted as the main damaging species in PDI, ROS like free radicals may also be involved in the process, inducing damages to proteins, lipids, nucleic acids and other molecular structures. In this study, the relative importance of each mechanism (type I and type II) on the photoinactivation of non-enveloped DNA (T4-like phage) and RNA (Qβ phage) viruses was evaluated. For this purpose, two cationic porphyrins (Tri-Py(+)-Me-PF and Tetra-Py(+)-Me) and four different ROS scavengers were used. The scavenging effect of sodium azide and L-histidine (singlet oxygen quenchers) and of D-mannitol and L-cysteine (free radical scavengers) was assessed by exposure of both phages (T4-like and Qβ) to each cationic porphyrin (5.0μM for T4-like phage and 0.5μM for Qβ phage) and white light (40Wm(-2)) in the presence of different concentrations of the scavengers (5, 10, 50 and 100mM). Sodium azide and L-histidine gave the best protection, reducing the phototoxic effect of Tri-Py(+)-Me-PF on T4-like phage respectively by 80% and 72% and in the presence of Tetra-Py(+)-Me by 90% and 78%. Free radical scavengers D-mannitol and L-cysteine did not significantly reduce the rate of T4-like phage photoinactivation (around 20% protection, for both PS). The sodium azide protection on Qβ phage photoinactivation, in the presence of Tri-Py(+)-Me-PF, was lower (39%) when compared with T4-like phage. D-mannitol did not exert on Qβ phage any protective effect after 90min of irradiation. The effect of the simultaneous presence of singlet oxygen and free radicals scavengers at 100mM confirmed that singlet oxygen (type II mechanism) is clearly the main ROS involved in T4-like and Qβ phages

  14. High temperature mechanisms and kinetics of SiC oxidation under low partial pressures of oxygen: application to the fuel cladding of gas fast reactors

    International Nuclear Information System (INIS)

    Hun, N.

    2011-01-01

    Gas Fast Reactor (GFR) is one of the different Generation IV concepts under investigation for energy production. SiC/SiC composites are candidates of primary interest for a GFR fuel cladding use, thanks to good corrosion resistance among other properties. The mechanisms and kinetics of SiC oxidation under operating conditions have to be identified and quantified as the corrosion can decrease the mechanical properties of the composite. An experimental device has been developed to study the oxidation of silicon carbide under high temperature and low oxygen partial pressure. The results pointed out that not only parabolic oxidation, but also interfacial reactions and volatilization occur under such conditions. After determining the kinetics of each mechanism, as functions of oxygen partial pressure and temperature, the data are used for the modeling of the composites oxidation. The model will be used to predict the lifetime of the composite in operating conditions. (author) [fr

  15. Natural NMSSM with a light singlet Higgs and singlino LSP

    International Nuclear Information System (INIS)

    Potter, C.T.

    2016-01-01

    Supersymmetry (SUSY) is an attractive extension of the Standard Model (SM) of particle physics which solves the SM hierarchy problem. Motivated by the theoretical μ-term problem of the Minimal Supersymmetric Model (MSSM), the Next-to MSSM (NMSSM) can also account for experimental deviations from the SM like the anomalous muon magnetic moment and the dark matter relic density. Natural SUSY, motivated by naturalness considerations, exhibits small fine tuning and a characteristic phenomenology with light higgsinos, stops, and gluinos. We describe a scan in NMSSM parameter space motivated by Natural SUSY and guided by the phenomenology of an NMSSM with a slightly broken Peccei-Quinn symmetry and a lightly coupled singlet. We identify a scenario which survives experimental constraints with a light singlet Higgs and a singlino lightest SUSY particle. We then discuss how the scenario is not presently excluded by searches at the Large Hadron Collider (LHC) and which channels are promising for discovery at the LHC and International Linear Collider. (orig.)

  16. An XML file format for exchanging singlet lens specifications

    Science.gov (United States)

    Gay, Shawn C.; Gangadhara, Sanjay

    2015-10-01

    Zemax has developed an XML schema for the distribution of singlet lens specifications based on the ISO 10110 standard. In OpticStudio 15, this kind of XML data can be exported from the ISO Element Drawing analysis. The data file is then used in a feature that automates exchange of lens data between designer and manufacturer, the Cost Estimator. This Cost Estimator feature submits the XML data to various manufacturers to obtain cost estimates for prototype lens production. The workflow centered on the XML data exchange facilitates rapid cost estimate retrieval and eliminates the need for redundant manual data entry. The XML Schema Definition (XSD) for the XML format can be used with Microsoft developer tools to automatically create .NET classes to serialize and deserialize the singlet lens data to/from XML files. The format provides flexible unit specification for most parameters. Choosing XML as the basis for the file format has provided several benefits, such as the above mentioned automated serialization capabilities in .NET, a human-readable text-based format, and ready support for consumption by web services.

  17. Discrete R symmetries for the MSSM and its singlet extensions

    CERN Document Server

    Lee, Hyun Min; Ratz, Michael; Ross, Graham G; Schieren, Roland; Schmidt-Hoberg, Kai; Vaudrevange, Patrick K S

    2011-01-01

    We determine the anomaly free discrete R symmetries, consistent with the MSSM, that commute with SU(5) and suppress the $\\mu$ parameter and nucleon decay. We show that the order M of such $Z_M^R$ symmetries has to divide 24 and identify 5 viable symmetries. The simplest possibility is a $Z_4^R$ symmetry which commutes with SO(10). We present a string-derived model with this $Z_4^R$ symmetry and the exact MSSM spectrum below the GUT scale; in this model $Z_4^R$ originates from the Lorentz symmetry of compactified dimensions. We extend the discussion to include the singlet extensions of the MSSM and find $Z_4^R$ and $Z_8^R$ are the only possible symmetries capable of solving the $\\mu$ problem in the NMSSM. We also show that a singlet extension of the MSSM based on a $Z_{24}^R$ symmetry can provide a simultaneous solution to the $\\mu$ and strong CP problem with the axion coupling in the favoured window.

  18. Prevalence and variability of use of home mechanical ventilators, positive airway pressure and oxygen devices in the Lombardy region, Italy.

    Science.gov (United States)

    Vitacca, Michele; Barbano, Luca; Colombo, Daniele; Leoni, Olivia; Guffanti, Enrico

    2018-01-29

    Few studies have analyzed the prevalence and accessibility of home mechanical ventilation (HMV) in Italy. We aimed to investigate the prevalence and prescription variability of HMV as well as of long-term oxygen therapy (LTOT) and continuous positive airway pressure (CPAP), in the Lombardy Region. Prescribing rates of HMV (both noninvasive and tracheostomies), CPAP (auto-CPAP, CPAP/other sleep machines) and LTOT (liquid-O2, O2-gas, concentrators) in the 15 Local Healthcare districts of Lombardy were gathered from billing data for 2012 and compared. Crude rates (per 100,000 population) and rates for the different healthcare districts were calculated. In 2012, 6325 patients were on HMV (crude prescription rate: 63/100,000) with a high variation across districts (8/100,000 in Milano 1 vs 150/100,000 in Pavia). There were 14,237 patients on CPAP (crude prescription rate: 142/100,000; CPAP/other sleep machines 95.3% vs auto-CPAP 4.7%) with also high intra-regional variation (56/100,000 in Mantova vs. 260/100,000 in Pavia). There were 21,826 patients on LTOT (prescription rate: 217/100,000 rate; liquid-O2 94%, O2-gas 2.08%, O2-concentrators 3.8%), with again high intra-regional variation (100/100,000 in Bergamo vs 410/100,000 in Valle Camonica). The crude rate of HMV prescriptions in Lombardy is very high, with a high intra-regional variability in prescribing HMV, LTOT and CPAP which is partly explainable by the accessibility to specialist centers with HMV/sleep-study facilities. Analysis of administrative data and variability mapping can help identify areas of reduced access for an improved standardization of services. An audit among Health Payer and prescribers to interpret the described huge variability could be welcomed.

  19. Efficient singlet-singlet energy transfer in a novel host-guest assembly composed of an organic cavitand, aromatic molecules, and a clay nanosheet.

    Science.gov (United States)

    Ishida, Yohei; Kulasekharan, Revathy; Shimada, Tetsuya; Takagi, Shinsuke; Ramamurthy, V

    2013-02-12

    A supramolecular host-guest assembly composed of a cationic organic cavitand (host), neutral aromatic molecules (guests), and an anionic clay nanosheet has been prepared and demonstrated that in this arrangement efficient singlet-singlet energy transfer could take place. The novelty of this system is the use of a cationic organic cavitand that enabled neutral organic molecules to be placed on an anionic saponite nanosheet. Efficient singlet-singlet energy transfer between neutral pyrene and 2-acetylanthracene enclosed within a cationic organic cavitand (octa amine) arranged on a saponite nanosheet was demonstrated through steady-state and time-resolved emission studies. The high efficiency was realized from the suppression of aggregation, segregation, and self-fluorescence quenching. We believe that the studies presented here using a novel supramolecular assembly have expanded the types of molecules that could serve as candidates for efficient energy-transfer systems, such as in an artificial light-harvesting system.

  20. Comparison between noninvasive mechanical ventilation and standard oxygen therapy in children up to 3 years old with respiratory failure after extubation: a pilot prospective randomized clinical study.

    Science.gov (United States)

    Fioretto, José R; Ribeiro, Cristiane F; Carpi, Mario F; Bonatto, Rossano C; Moraes, Marcos A; Fioretto, Eduardo B; Fagundes, Djalma J

    2015-02-01

    The effectiveness of noninvasive positive-pressure ventilation in preventing reintubation due to respiratory failure in children remains uncertain. A pilot study was designed to evaluate the frequency of extubation failure, develop a randomization approach, and analyze the feasibility of a powered randomized trial to compare noninvasive positive-pressure ventilation and standard oxygen therapy post extubation for preventing reintubation within 48 hours in children with respiratory failure. Prospective pilot study. PICU at a university-affiliated hospital. Children aged between 28 days and 3 years undergoing invasive mechanical ventilation for greater than or equal to 48 hours with respiratory failure after programmed extubation. Patients were prospectively enrolled and randomly assigned into noninvasive positive-pressure ventilation group and inhaled oxygen group after programmed extubation from May 2012 to May 2013. Length of stay in PICU and hospital, oxygenation index, blood gas before and after tracheal extubation, failure and reason for tracheal extubation, complications, mechanical ventilation variables before tracheal extubation, arterial blood gas, and respiratory and heart rates before and 1 hour after tracheal extubation were analyzed. One hundred eight patients were included (noninvasive positive-pressure ventilation group, n = 55 and inhaled oxygen group, n = 53), with 66 exclusions. Groups did not significantly differ for gender, age, disease severity, Pediatric Risk of Mortality at admission, tracheal intubation, and mechanical ventilation indications. There was no statistically significant difference in reintubation rate (noninvasive positive-pressure ventilation group, 9.1%; inhaled oxygen group, 11.3%; p > 0.05) and length of stay (days) in PICU (noninvasive positive-pressure ventilation group, 3 [1-16]; inhaled oxygen group, 2 [1-25]; p > 0.05) or hospital (noninvasive positive-pressure ventilation group, 19 [7-141]; inhaled oxygen group, 17 [8

  1. The effect of adrenaline and high Ca2+ on the mechanical performance and oxygen consumption of the isolated perfused trout

    DEFF Research Database (Denmark)

    Rytter, D.; Gesser, Hans

    2007-01-01

    In heart muscle from mammals, catecholamines frequently evoke an oxygen waste and reduce efficiency. It was examined if this also applies to fish in which heart muscle activity is often restricted by oxygen availability. In the isolated perfused heart from rainbow trout, adrenaline (0.5 μ......M) increased power output by  97%, when afterload was adjusted to maximum both before and after adrenaline addition, and by  68%, when afterload remained at the maximum obtained before adrenaline addition. Oxygen consumption was enhanced by a similar amount (  70%) in both situations. Hence, efficiency, i.......e. power output/oxygen consumption, increased significantly from 25 to 30% for the heart always exposed to maximal afterload, whereas it stayed unchanged at 24% for the heart exposed to control afterload only. Adrenaline increases the Ca2+activity participating in activation, but doing this by elevating...

  2. Effect of Oxygen Content Upon the Microstructural and Mechanical Properties of Type 316L Austenitic Stainless Steel Manufactured by Hot Isostatic Pressing

    Science.gov (United States)

    Cooper, Adam J.; Cooper, Norman I.; Dhers, Jean; Sherry, Andrew H.

    2016-09-01

    Although hot isostatic pressing (HIP) has been shown to demonstrate significant advances over more conventional manufacture routes, it is important to appreciate and quantify the detrimental effects of oxygen involvement during the HIP manufacture process on the microstructural and material properties of the resulting component. This paper quantifies the effects of oxygen content on the microstructure and Charpy impact properties of HIP'd austenitic stainless steel, through combination of detailed metallographic examination and mechanical testing on HIP'd Type 316L steel containing different concentrations (100 to 190 ppm) of oxygen. Micron-scale pores were visible in the microstructure of the HIP'd materials postmetallographic preparation, which result from the removal of nonmetallic oxide inclusions during metallographic preparation. The area fraction of the resulting pores is shown to correlate with the oxygen concentration which influences the Charpy impact toughness over the temperature range of 77 K to 573 K (-196 °C to 300 °C), and demonstrates the influence of oxygen involved during the HIP manufacture process on Charpy toughness. The same test procedures and microstructural analyses were performed on commercially available forged 316L. This showed comparatively fewer inclusions and exhibited higher Charpy impact toughness over the tested temperature range.

  3. Search for Colour Singlet and Colour Reconnection Effects in Hadronic Z Decays at LEP

    CERN Document Server

    Achard, P; Aguilar-Benítez, M; Alcaraz, J; Alemanni, G; Allaby, James V; Aloisio, A; Alviggi, M G; Anderhub, H; Andreev, V P; Anselmo, F; Arefev, A; Azemoon, T; Aziz, T; Bagnaia, P; Bajo, A; Baksay, G; Baksay, L; Baldew, S V; Banerjee, S; Banerjee, Sw; Barczyk, A; Barillère, R; Bartalini, P; Basile, M; Batalova, N; Battiston, R; Bay, A; Becattini, F; Becker, U; Behner, F; Bellucci, L; Berbeco, R; Berdugo, J; Berges, P; Bertucci, B; Betev, B L; Biasini, M; Biglietti, M; Biland, A; Blaising, J J; Blyth, S C; Bobbink, Gerjan J; Böhm, A; Boldizsar, L; Borgia, B; Bottai, S; Bourilkov, D; Bourquin, Maurice; Braccini, S; Branson, J G; Brochu, F; Burger, J D; Burger, W J; Cai, X D; Capell, M; Cara Romeo, G; Carlino, G; Cartacci, A M; Casaus, J; Cavallari, F; Cavallo, N; Cecchi, C; Cerrada, M; Chamizo-Llatas, M; Chang, Y H; Chemarin, M; Chen, A; Chen, G; Chen, G M; Chen, H F; Chen, H S; Chiefari, G; Cifarelli, Luisa; Cindolo, F; Clare, I; Clare, R; Coignet, G; Colino, N; Costantini, S; de la Cruz, B; Cucciarelli, S; van Dalen, J A; De Asmundis, R; Déglon, P L; Debreczeni, J; Degré, A; Dehmelt, K; Deiters, K; Della Volpe, D; Delmeire, E; Denes, P; De Notaristefani, F; De Salvo, A; Diemoz, M; Dierckxsens, M; Dionisi, C; Dittmar, M; Doria, A; Dova, M T; Duchesneau, D; Duda, M; Echenard, B; Eline, A; El-Hage, A; El-Mamouni, H; Engler, A; Eppling, F J; Extermann, P; Falagán, M A; Falciano, S; Favara, A; Fay, J; Fedin, O; Felcini, M; Ferguson, T; Fesefeldt, H S; Fiandrini, E; Field, J H; Filthaut, F; Fisher, P H; Fisher, W; Fisk, I; Forconi, G; Freudenreich, Klaus; Furetta, C; Galaktionov, Yu; Ganguli, S N; García-Abia, P; Gataullin, M; Gentile, S; Giagu, S; Gong, Z F; Grenier, G; Grimm, O; Grünewald, M W; Guida, M; van Gulik, R; Gupta, V K; Gurtu, A; Gutay, L J; Haas, D; Hatzifotiadou, D; Hebbeker, T; Hervé, A; Hirschfelder, J; Hofer, H; Hohlmann, M; Holzner, G; Hou, S R; Hu, Y; Jin, B N; Jones, L W; de Jong, P; Josa-Mutuberria, I; Käfer, D; Kaur, M; Kienzle-Focacci, M N; Kim, J K; Kirkby, Jasper; Kittel, E W; Klimentov, A; König, A C; Kopal, M; Koutsenko, V F; Kräber, M H; Krämer, R W; Krüger, A; Kunin, A; Ladrón de Guevara, P; Laktineh, I; Landi, G; Lebeau, M; Lebedev, A; Lebrun, P; Lecomte, P; Lecoq, P; Le Coultre, P; Le Goff, J M; Leiste, R; Levtchenko, M; Levchenko, P M; Li, C; Likhoded, S; Lin, C H; Lin, W T; Linde, Frank L; Lista, L; Liu, Z A; Lohmann, W; Longo, E; Lü, Y S; Luci, C; Luminari, L; Lustermann, W; Ma Wen Gan; Malgeri, L; Malinin, A; Maña, C; Mans, J; Martin, J P; Marzano, F; Mazumdar, K; McNeil, R R; Mele, S; Merola, L; Meschini, M; Metzger, W J; Mihul, A; Milcent, H; Mirabelli, G; Mnich, J; Mohanty, G B; Muanza, G S; Muijs, A J M; Musicar, B; Musy, M; Nagy, S; Natale, S; Napolitano, M; Nessi-Tedaldi, F; Newman, H; Nisati, A; Novák, T; Nowak, H; Ofierzynski, R A; Organtini, G; Pal, I; Palomares, C; Paolucci, P; Paramatti, R; Passaleva, G; Patricelli, S; Paul, T; Pauluzzi, M; Paus, C; Pauss, Felicitas; Pedace, M; Pensotti, S; Perret-Gallix, D; Petersen, B; Piccolo, D; Pierella, F; Pioppi, M; Piroué, P A; Pistolesi, E; Plyaskin, V; Pohl, M; Pozhidaev, V; Pothier, J; Prokofev, D; Prokofiev, D O; Quartieri, J; Rahal-Callot, G; Rahaman, M A; Raics, P; Raja, N; Ramelli, R; Rancoita, P G; Ranieri, R; Raspereza, A V; Razis, P A; Ren, D; Rescigno, M; Reucroft, S; Riemann, S; Riles, K; Roe, B P; Romero, L; Rosca, A; Rosier-Lees, S; Roth, S; Rosenbleck, C; Rubio, J A; Ruggiero, G; Rykaczewski, H; Sakharov, A; Saremi, S; Sarkar, S; Salicio, J; Sánchez, E; Schäfer, C; Shchegelskii, V; Schopper, Herwig Franz; Schotanus, D J; Sciacca, C; Servoli, L; Shevchenko, S; Shivarov, N; Shoutko, V; Shumilov, E; Shvorob, A V; Son, D; Souga, C; Spillantini, P; Steuer, M; Stickland, D P; Stoyanov, B; Strässner, A; Sudhakar, K; Sultanov, G G; Sun, L Z; Sushkov, S; Suter, H; Swain, J D; Szillási, Z; Tang, X W; Tarjan, P; Tauscher, Ludwig; Taylor, L; Tellili, B; Teyssier, D; Timmermans, C; Ting, Samuel C C; Ting, S M; Tonwar, S C; Tóth, J; Tully, C; Tung, K L; Ulbricht, J; Valente, E; Van de Walle, R T; Vásquez, R; Veszpremi, V; Vesztergombi, G; Vetlitskii, I; Vicinanza, D; Viertel, Gert M; Villa, S; Vivargent, M; Vlachos, S; Vodopyanov, I; Vogel, H; Vogt, H; Vorobev, I; Vorobyov, A A; Wadhwa, M; Wang, Q; Wang, X L; Wang, Z M; Weber, M; Wienemann, P; Wilkens, H; Wynhoff, S; Xia, L; Xu, Z Z; Yamamoto, J; Yang, B Z; Yang, C G; Yang, H J; Yang, M; Yeh, S C; Zalite, A; Zalite, Yu; Zhang, Z P; Zhao, J; Zhu, G Y; Zhu, R Y; Zhuang, H L; Zichichi, A; Zimmermann, B; Zöller, M

    2004-01-01

    A search is performed in symmetric 3-jet hadronic Z decay events for evidence of colour singlet production or colour reconnection effects. Asymmetries in the angular separation of particles are found to be sensitive indicators of such effects. Upper limits on the level of colour singlet production and colour reconnection effects are established for a variety of models.

  4. Advances in the development of chemical oxygen-iodine laser

    Czech Academy of Sciences Publication Activity Database

    Kodymová, Jarmila; Špalek, Otomar; Jirásek, Vít; Čenský, Miroslav

    2004-01-01

    Roč. 54, č. 5 (2004), s. 561-574 ISSN 0011-4626 R&D Projects: GA MŠk LN00A100 Grant - others:EOARD(XE) USAF Institutional research plan: CEZ:AV0Z1010921 Keywords : chemical oxygen-iodine laser * COIL * singlet oxygen * atomic iodine Subject RIV: BH - Optics, Masers, Lasers Impact factor: 0.292, year: 2004

  5. Oxygen negative glow: reactive species and emissivity

    International Nuclear Information System (INIS)

    Sahli, Khaled

    1991-01-01

    This research thesis addresses the study of a specific type of oxygen plasma created by electron beams (1 keV, 20 mA/cm 2 ), negative glow of a luminescent discharge in abnormal regime. The objective is to test the qualities of this plasma as source of two 'active' species of oxygen (singlet molecular oxygen and atomic oxygen) which are useful in applications. The experiment mainly bears on the use of VUV (120 to 150 nm) absorption spectroscopy measurements of concentrations of these both species, and on the recording of plasma emissivity space profiles in the visible region (450 to 850 nm). It appears that low concentrations of singlet oxygen definitely exclude this type of discharge for iodine laser applications. On the contrary, concentrations measured for atomic oxygen show it is a good candidate for the oxidation of large surfaces by sheets of beams. The satisfying comparison of emissivity results with a published model confirm the prevailing role of fast electrons, and gives evidence of an important effect of temperature: temperature can reach 1000 K, and this is in agreement with the presented measurement [fr

  6. Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

    KAUST Repository

    Pace, Natalie A.

    2017-11-30

    The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. In this paper, we investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically, and is strongly dependent on side-chain identity. These results show that it may be necessary to carefully engineer the solid-state microstructure of these “singlet fission polymers” in order to produce the long-lived triplets needed to realize efficient photovoltaic devices.

  7. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

    International Nuclear Information System (INIS)

    Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Juergen

    2011-01-01

    Highlights: → Oxygen exchange kinetics of Pt on YSZ investigated by means of Pt model electrodes. → Two different geometry dependencies of the polarization resistance identified. → At higher temperatures the oxygen exchange reaction proceeds via a Pt surface path. → At lower temperatures a bulk path through the Pt thin film electrode is discussed. - Abstract: The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 deg. C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 deg. C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

  8. [Studying the influence of some reactive oxygen species on physical and chemical parameters of blood].

    Science.gov (United States)

    Martusevich, A K; Martusevich, A A; Solov'eva, A G; Peretyagin, S P

    2014-01-01

    The aim of this work was to estimate the dynamics of blood physical and chemical parameters when blood specimens were processed by singlet oxygen in vitro. Our experiments were executed with whole blood specimens of healthy people (n=10). Each specimen was divided into five separate portions of 5 ml. The first portion was a control (without any exposures). The second one was processed by an oxygen-ozone mixture (at ozone concentration of 500 mcg/l, the third portion--by oxygen, and the fourth and fifth ones were processed by a gas mixture with singlet oxygen (50 and 100% of generator power). In blood samples after processing we studied the activity of lactate dehydrogenase, aldehyde dehydrogenase and superoxide dismutase, erythrocyte and plasma levels of glucose and lactate, acid-base balance and the partial pressure of gases in blood. It was found out, that blood processing by singlet oxygen leads to optimization of energy, detoxication and antioxidant enzymes functioning with changes in plasma and erythrocyte level of glucose and lactate, normalization of blood gases level and acid-base balance. Our results show, that the effect of singlet oxygen on enzyme activity is more pronounced than exposure to an oxygen-ozone gas mixture.

  9. Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path.

    Science.gov (United States)

    Opitz, Alexander K; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

    2011-11-30

    The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded.The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

  10. Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO2 electrocatalysts.

    Science.gov (United States)

    Takashima, Toshihiro; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2012-01-25

    Manganese oxides function as efficient electrocatalysts for water oxidation to molecular oxygen in strongly alkaline conditions, but are inefficient at neutral pH. To provide new insight into the mechanism underlying the pH-dependent activity of the electrooxidation reaction, we performed UV-vis spectroelectrochemical detection of the intermediate species for water oxidation by a manganese oxide electrode. Layered manganese oxide nanoparticles, δ-MnO(2) (K(0.17)[Mn(4+)(0.90)Mn(3+)(0.07)□(0.03)]O(2)·0.53H(2)O) deposited on fluorine-doped tin oxide electrodes were shown to catalyze water oxidation at pH from 4 to 13. At this pH range, a sharp rise in absorption at 510 nm was observed with a concomitant increase of anodic current for O(2) evolution. Using pyrophosphate as a probe molecule, the 510 nm absorption was attributable to Mn(3+) on the surface of δ-MnO(2). The onset potential of the water oxidation current was constant at approximately 1.5 V vs SHE from pH 4 to pH 8, but sharply shifted to negative at pH > 8. Strikingly, this behavior was well reproduced by the pH dependence of the onset of 510 nm absorption, indicating that Mn(3+) acts as the precursor of water oxidation. Mn(3+) is unstable at pH reaction resulting in the formation of Mn(2+) and Mn(4+), whereas it is effectively stabilized by the comproportionation of Mn(2+) and Mn(4+) in alkaline conditions. Thus, the low activity of manganese oxides for water oxidation under neutral conditions is most likely due to the inherent instability of Mn(3+), whose accumulation at the surface of catalysts requires the electrochemical oxidation of Mn(2+) at a potential of approximately 1.4 V. This new model suggests that the control of the disproportionation and comproportionation efficiencies of Mn(3+) is essential for the development of Mn catalysts that afford water oxidation with a small overpotential at neutral pH. © 2011 American Chemical Society

  11. Kinetics and Mechanisms of Oxygen Surface Exchange on La0.6Sr0.4FeO3-delta Thin Films

    DEFF Research Database (Denmark)

    Mosleh, Majid; Søgaard, Martin; Hendriksen, Peter Vang

    2009-01-01

    coefficient (kV) determined from Kchem shows a slope (log kV vs log PO2) between 0.51 and 0.85. It is further found that kV is proportional to the product of the oxygen partial pressure and the vacancy concentration (kVPO2). Different reaction mechanisms that can account for the observed PO2 and -dependence...

  12. Singlet-triplet interaction in linear triatomic molecules

    Science.gov (United States)

    Osherov, V. I.; Osherov, M. V.; Poluyanov, L. V.

    2018-01-01

    We present here two-electronic model, which describes singlet-triplet interaction 1 π -3Σ+ in linear triatomic molecules. The analysis takes into account spin-orbital coupling terms in electronic Hamiltonian, as well as its symmetry properties. We give the symmetry operators of electronic Hamiltonian including space operators (acting on electronic coordinates) and matrix operators (acting on electronic spin). We consider only deformation π -modes and our resulting 5 × 5 vibronic matrix describes actual relativistic pseudo-Renner effect (1 π -3 Σ) × π . The eigenvalues of vibronic matrix (i.e. potential energy surfaces) have axial symmetry and represented by analytical expressions, include five electrostatic and three spin-orbital parameters.

  13. Evolution of truncated moments of singlet parton distributions

    International Nuclear Information System (INIS)

    Forte, S.; Magnea, L.; Piccione, A.; Ridolfi, G.

    2001-01-01

    We define truncated Mellin moments of parton distributions by restricting the integration range over the Bjorken variable to the experimentally accessible subset x 0 ≤x≤1 of the allowed kinematic range 0≤x≤1. We derive the evolution equations satisfied by truncated moments in the general (singlet) case in terms of an infinite triangular matrix of anomalous dimensions which couple each truncated moment to all higher moments with orders differing by integers. We show that the evolution of any moment can be determined to arbitrarily good accuracy by truncating the system of coupled moments to a sufficiently large but finite size, and show how the equations can be solved in a way suitable for numerical applications. We discuss in detail the accuracy of the method in view of applications to precision phenomenology

  14. Generation of macroscopic singlet states in atomic ensembles

    Science.gov (United States)

    Tóth, Géza; Mitchell, Morgan W.

    2010-05-01

    We study squeezing of the spin uncertainties by quantum non-demolition (QND) measurement in non-polarized spin ensembles. Unlike the case of polarized ensembles, the QND measurements can be performed with negligible back-action, which allows, in principle, perfect spin squeezing as quantified by Tóth et al (2007 Phys. Rev. Lett. 99 250405). The generated spin states approach many-body singlet states and contain a macroscopic number of entangled particles even when individual spin is large. We introduce the Gaussian treatment of unpolarized spin states and use it to estimate the achievable spin squeezing for realistic experimental parameters. Our proposal might have applications for magnetometry with a high spatial resolution or quantum memories storing information in decoherence free subspaces.

  15. Two-singlet model for light cold dark matter

    International Nuclear Information System (INIS)

    Abada, Abdessamad; Ghaffor, Djamal; Nasri, Salah

    2011-01-01

    We extend the standard model by adding two gauge-singlet Z 2 -symmetric scalar fields that interact with visible matter only through the Higgs particle. One is a stable dark matter WIMP, and the other one undergoes a spontaneous breaking of the symmetry that opens new channels for the dark matter annihilation, hence lowering the mass of the WIMP. We study the effects of the observed dark matter relic abundance on the WIMP annihilation cross section and find that in most regions of the parameters' space, light dark matter is viable. We also compare the elastic-scattering cross section of our dark matter candidate off a nucleus with existing (CDMSII and XENON100) and projected (SuperCDMS and XENON1T) experimental exclusion bounds. We find that most of the allowed mass range for light dark matter will be probed by the projected sensitivity of the XENON1T experiment.

  16. Signal for a light singlet scalar at the LHC

    Science.gov (United States)

    Chang, We-Fu; Modak, Tanmoy; Ng, John N.

    2018-03-01

    In the general Higgs portal-like models, the extra neutral scalar, S , can mix with the Standard Model (SM) Higgs boson, H . We perform an exploratory study focusing on the direct search for such a light singlet S at the Large Hadron Collider (LHC). After careful study of the SM background, we find the process p p →t t ¯ S followed by S →b b ¯ can be used to investigate S with mass in the 20 Higgs factories. With similar luminosity, the current Large Electron-Positron Collider (LEP) limits on the mixing between S and H can be improved by at least one or two order of magnitudes.

  17. Seeking small molecules for singlet fission: a heteroatom substitution strategy.

    Science.gov (United States)

    Zeng, Tao; Ananth, Nandini; Hoffmann, Roald

    2014-09-10

    We design theoretically small molecule candidates for singlet fission chromophores, aiming to achieve a balance between sufficient diradical character and kinetic persistence. We develop a perturbation strategy based on the captodative effect to introduce diradical character into small π-systems. Specifically, this can be accomplished by replacing pairs of not necessarily adjacent C atoms with isoelectronic and isosteric pairs of B and N atoms. Three rules of thumb emerge from our studies to aid further design: (i) Lewis structures provide insight into likely diradical character; (ii) formal radical centers of the diradical must be well-separated; (iii) stabilization of radical centers by a donor (N) and an acceptor (B) is essential. Following the rules, we propose candidate molecules. Employing reliable multireference calculations for excited states, we identify three likely candidate molecules for SF chromophores. These include a benzene, a napthalene, and an azulene, where four C atoms are replaced by a pair of B and a pair of N atoms.

  18. Resummation of singlet parton evolution at small x

    CERN Document Server

    Altarelli, Guido; Forte, Stefano; Altarelli, Guido; Ball, Richard D.; Forte, Stefano

    2000-01-01

    We propose an improvement of the splitting functions at small x which overcomes the apparent problems encountered by the BFKL approach. We obtain a stable expansion for the x-evolution function chi(M) near M=0 by including in it a sequence of terms derived from the one- and two-loop anomalous dimension gamma. The requirement of momentum conservation is always satisfied. The residual ambiguity on the splitting functions is effectively parameterized in terms of the value of lambda, which fixes the small x asymptotic behaviour x^-lambda of the singlet parton distributions. We derive from this improved evolution function an expansion of the splitting function which leads to good apparent convergence, and to a description of scaling violations valid both at large and small x.

  19. Oxygen Therapy

    Science.gov (United States)

    ... best for you. Oxygen is usually delivered through nasal prongs (an oxygen cannula) or a face mask. Oxygen equipment can attach to other medical equipment such as CPAP machines and ventilators. Oxygen therapy can help you ...

  20. Ultrafast intramolecular charge transfer in tetrapyrazinoporphyrazines controls the quantum yields of fluorescence and singlet oxygen

    Czech Academy of Sciences Publication Activity Database

    Nováková, V.; Zimčík, P.; Miletín, M.; Váchová, L.; Kopecký, K.; Lang, Kamil; Chábera, P.; Polívka, T.

    2010-01-01

    Roč. 12, č. 11 (2010), s. 2555-2563 ISSN 1463-9076 R&D Projects: GA ČR GA203/07/1424 Institutional research plan: CEZ:AV0Z40320502 Keywords : photoinduced electron-transfer * phthalocyanine -fullerene ensembles * nonlinear-optical properties Subject RIV: CA - Inorganic Chemistry Impact factor: 3.454, year: 2010

  1. Magnetic field protects plants against high light by slowing down production of singlet oxygen

    Czech Academy of Sciences Publication Activity Database

    Hakala-Yatkin, M.; Sarvikas, P.; Paturi, P.; Mattila, H.; Tyystjärvi, T.; Nedbal, Ladislav; Tyystjärvi, E.

    2011-01-01

    Roč. 142, č. 1 (2011), s. 26-34 ISSN 0031-9317 Institutional research plan: CEZ:AV0Z60870520 Keywords : photosynthetic reaction-center * Photosystem-II * alpha-tocopherol * environmental-stress * manganese complex * evolving complex * oxidative stress Subject RIV: EH - Ecology, Behaviour Impact factor: 3.112, year: 2011

  2. Design of porphyrin-based conjugated microporous polymers with enhanced singlet oxygen productivity

    Czech Academy of Sciences Publication Activity Database

    Hynek, Jan; Rathouský, Jiří; Demel, Jan; Lang, Kamil

    2016-01-01

    Roč. 6, č. 50 (2016), s. 44279-44287 ISSN 2046-2069 R&D Projects: GA ČR(CZ) GA16-15020S Institutional support: RVO:61388980 ; RVO:61388955 Keywords : Conjugated microporous polymers * Crystalline materials * Metal organic framework * biomimetic catalysis Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 3.108, year: 2016

  3. A Gas-Solid Singlet Delta Oxygen Generator for the Chemical Iodine Laser

    National Research Council Canada - National Science Library

    Alfano, Angelo

    2002-01-01

    ... at 1.27 microns by passing chlorine gas through aqueous, basic hydrogen peroxide (H2O2/OH). Unfortunately, the process of nonradiative relaxation used in COIL results in the creation of undesired heat and not the desired light emission...

  4. Plasmachemical generation of atomic iodine for iodine lasers pumped by singlet oxygen

    Czech Academy of Sciences Publication Activity Database

    Jirásek, Vít; Schmiedberger, Josef; Čenský, Miroslav; Picková, Irena; Kodymová, Jarmila; Špalek, Otomar

    2008-01-01

    Roč. 102, č. 16 (2008), s. 1327-1331 ISSN 0009-2770 Grant - others:US Air Force EOARD(US) FA8655-06-1-3034 Institutional research plan: CEZ:AV0Z10100523 Keywords : COIL * chemical laser * atomic iodine * RF discharge Subject RIV: BH - Optics, Masers, Laser s Impact factor: 0.593, year: 2008 http://chemicke-listy.cz/docs/full/2008_16_s1327-s1331.pdf

  5. A ReaxFF-based molecular dynamics study of the mechanisms of interactions between reactive oxygen plasma species and the Candida albicans cell wall

    Science.gov (United States)

    Zhao, T.; Shi, L.; Zhang, Y. T.; Zou, L.; Zhang, L.

    2017-10-01

    Atmospheric pressure non-equilibrium plasmas have attracted significant attention and have been widely used to inactivate pathogens, yet the mechanisms underlying the interactions between plasma-generated species and bio-organisms have not been elucidated clearly. In this paper, reactive molecular dynamics simulations are employed to investigate the mechanisms of interactions between reactive oxygen plasma species (O, OH, and O2) and β-1,6-glucan (a model for the C. albicans cell wall) from a microscopic point of view. Our simulations show that O and OH species can break structurally important C-C and C-O bonds, while O2 molecules exhibit only weak, non-bonded interactions with β-1,6-glucan. Hydrogen abstraction from hydroxyl or CH groups occurs first in all bond cleavage mechanisms. This is followed by a cascade of bond cleavage and double bond formation events. These lead to the destruction of the fungal cell wall. O and OH have similar effects related to their bond cleavage mechanisms. Our simulation results provide fundamental insights into the mechanisms underlying the interactions between reactive oxygen plasma species and the fungal cell wall of C. albicans at the atomic level.

  6. Evaluation of phototoxicity of dendritic porphyrin-based phosphorescent oxygen probes: an in vitro study†

    Science.gov (United States)

    Lebedev, Artem Y.; Marchi, Enrico; Yuan, Min; Esipova, Tatiana V.; Bergamini, Giacomo; Wilson, David F.

    2013-01-01

    Biological oxygen measurements by phosphorescence quenching make use of exogenous phosphorescent probes, which are introduced directly into the medium of interest (e.g. blood or interstitial fluid) where they serve as molecular sensors for oxygen. The byproduct of the quenching reaction is singlet oxygen, a highly reactive species capable of damaging biological tissue. Consequently, potential probe phototoxicity is a concern for biological applications. Herein, we compared the ability of polyethyleneglycol (PEG)-coated Pd tetrabenzoporphyrin (PdTBP)-based dendritic nanoprobes of three successive generations to sensitize singlet oxygen. It was found that the size of the dendrimer has practically no effect on the singlet oxygen sensitization efficiency in spite of the strong attenuation of the triplet quenching rate with an increase in the dendrimer generation. This unexpected result is due to the fact that the lifetime of the PdTBP triplet state in the absence of oxygen increases with dendritic generation, thus compensating for the concomitant decrease in the rate of quenching. Nevertheless, in spite of their ability to sensitize singlet oxygen, the phosphorescent probes were found to be non-phototoxic when compared with the commonly used photodynamic drug Photofrin in a standard cell-survival assay. The lack of phototoxicity is presumably due to the inability of PEGylated probes to associate with cell surfaces and/or penetrate cellular membranes. In contrast, conventional photosensitizers bind to cell components and act by generating singlet oxygen inside or in the immediate vicinity of cellular organelles. Therefore, PEGylated dendritic probes are safe to use for tissue oxygen measurements as long as the light doses are less than or equal to those commonly employed in photodynamic therapy. PMID:21409208

  7. Primary mechanisms of photosensitization by furocoumarins

    International Nuclear Information System (INIS)

    Grossweiner, L.I.

    1981-01-01

    A proper understanding of the PUVA therapy action mechanism requires the synthesis of concepts developed at the level of molecules, single cells and whole organisms. Although progress has been made in identifying key factors within each level of organization, the interrelationships remain obscure. Important unanswered questions at the molecular and cellular levels include: (1) Which excited states of the furocoumarin in molecule (triplet or excited singlet) are involved in the formation of DNA monoadducts, and the conversion of monoadducts to cross-links. (2) How does the spectrum of the incident radiation affect the distribution of the initial photochemical products from the PUVA sensitizers. (3) What are the relative contributions of furocoumarin-DMA monoadducts, furocoumarin-DNA cross-links and singlet oxygen to mutagenesis and lethality in cells, at the furocoumarin and UV-A dose levels corresponging to PUVA therapy. Additional information about these key aspects of furocoumarin photosensitization should lead to a more definitive relationship of the cellular level events to the endpoints observed with PUVA therapy, and suggest directions for potential improvements in the current clinical procedures

  8. Normobaric pulmonary oxygen toxicity : experimental studies on the mechanism of the protective role of endotoxin and the role of surfactant.

    NARCIS (Netherlands)

    J. Klein (Jan)

    1991-01-01

    textabstractAdministration of above-ambient oxygen tensions, necessary for treatment of severe hypoxemia caused by respiratory failure or acute lung injury, is potentially toxic for the lungs. This thesis is based on six articles dealing with this topic: one review article and five articles

  9. The effect of positive-end expiratory pressure on oxygenation during high frequency jet ventilation and conventional mechanical ventilation in the rabbit model of acute lung injury.

    Science.gov (United States)

    Bang, Jae Ouk; Ha, Seung Il; Choi, In-Cheol

    2012-10-01

    The use of positive end expiratory pressure (PEEP) in patients with acute lung injury (ALI) improves arterial oxygenation by alleviating pulmonary shunting, helping the respiratory muscles to decrease the work of breathing, decreasing the rate of infiltrated and atelectatic tissues, and increasing functional residual capacity. In a rabbit model of saline lavage-induced ALI, we examined the effects of PEEP on gas exchange, hemodynamics, and oxygenation during high frequency jet ventilation (HFJV), and then compared these parameters with those during conventional mechanical ventilation (CMV). Twelve rabbits underwent repeated saline lavage to create ALI. The animals were divided in 2 groups: 1) Group CMV (n = 6), and 2) Group HFJV (n = 6). In both groups, we applied 2 levels of PEEP (5 cmH(2)O and 10 cmH(2)O) and then measured the arterial blood gas, mixed venous blood gas, and hemodynamic parameters. With administration of PEEP of either 5 cmH(2)O or 10 cmH(2)O, the arterial oxygen content of both groups was increased, although without statistically significant differences between groups. On the contrary, the arterial carbon dioxide content was significantly decreased in the HFJV group, as compared with the CMV group, during the entire experiment. Furthermore, there was significant decreases in mean arterial pressures in both groups with a PEEP of 10 cmH(2)O. The application of PEEP in rabbits with ALI effectively improves oxygenation in either HFJV or CMV.

  10. Plant polyphenol induced cell death in human cancer cells involves mobilization of intracellular copper ions and reactive oxygen species generation: a mechanism for cancer chemopreventive action.

    Science.gov (United States)

    Khan, Husain Yar; Zubair, Haseeb; Faisal, Mohd; Ullah, Mohd Fahad; Farhan, Mohd; Sarkar, Fazlul H; Ahmad, Aamir; Hadi, Sheikh Mumtaz

    2014-03-01

    Anticancer polyphenolic nutraceuticals from fruits, vegetables, and spices are generally recognized as antioxidants, but can be prooxidants in the presence of copper ions. We earlier proposed a mechanism for such activity of polyphenols and now we provide data in multiple cancer cell lines in support of our hypothesis. Through multiple assays, we show that polyphenols luteolin, apigenin, epigallocatechin-3-gallate, and resveratrol are able to inhibit cell proliferation and induce apoptosis in different cancer cell lines. Such cell death is prevented to a significant extent by cuprous chelator neocuproine and reactive oxygen species scavengers. We also show that normal breast epithelial cells, cultured in a medium supplemented with copper, become sensitized to polyphenol-induced growth inhibition. Since the concentration of copper is significantly elevated in cancer cells, our results strengthen the idea that an important anticancer mechanism of plant polyphenols is mediated through intracellular copper mobilization and reactive oxygen species generation leading to cancer cell death. Moreover, this prooxidant chemopreventive mechanism appears to be a mechanism common to several polyphenols with diverse chemical structures and explains the preferential cytotoxicity of these compounds toward cancer cells. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Shedding Light on the Oxygen Reduction Reaction Mechanism in Ether-Based Electrolyte Solutions: A Study Using Operando UV-Vis Spectroscopy.

    Science.gov (United States)

    Hirshberg, Daniel; Sharon, Daniel; Afri, Michal; Lavi, Ronit; Frimer, Aryeh A; Metoki, Noa; Eliaz, Noam; Kwak, Won-Jin; Sun, Yang-Kook; Aurbach, Doron

    2018-03-20

    Using UV-vis spectroscopy in conjunction with various electrochemical techniques, we have developed a new effective operando methodology for investigating the oxygen reduction reactions (ORRs) and their mechanisms in nonaqueous solutions. We can follow the in situ formation and presence of superoxide moieties during ORR as a function of solvent, cations, anions, and additives in the solution. Thus, using operando UV-vis spectroscopy, we found evidence for the formation of superoxide radical anions during oxygen reduction in LiTFSI/diglyme electrolyte solutions. Nitro blue tetrazolium (NBT) was used to indicate the presence of superoxide moieties based on its unique spectral response. Indeed, the spectral response of NBT containing solutions undergoing ORR could provide a direct indication for the level of association of the Li cations with the electrolyte anions.

  12. The mechanism for oxygen reduction in cytochrome c dependent nitric oxide reductase (cNOR) as obtained from a combination of theoretical and experimental results.

    Science.gov (United States)

    Blomberg, Margareta R A; Ädelroth, Pia

    2017-11-01

    Bacterial NO-reductases (NOR) belong to the heme-copper oxidase (HCuO) superfamily, in which most members are O 2 -reducing, proton-pumping enzymes. This study is one in a series aiming to elucidate the reaction mechanisms of the HCuOs, including the mechanisms for cellular energy conservation. One approach towards this goal is to compare the mechanisms for the different types of HCuOs, cytochrome c oxidase (CcO) and NOR, reducing the two substrates O 2 and NO. Specifically in this study, we describe the mechanism for oxygen reduction in cytochrome c dependent NOR (cNOR). Hybrid density functional calculations were performed on large cluster models of the cNOR binuclear active site. Our results are used, together with published experimental information, to construct a free energy profile for the entire catalytic cycle. Although the overall reaction is quite exergonic, we show that during the reduction of molecular oxygen in cNOR, two of the reduction steps are endergonic with high barriers for proton uptake, which is in contrast to oxygen reduction in CcO, where all reduction steps are exergonic. This difference between the two enzymes is suggested to be important for their differing capabilities for energy conservation. An additional result from this study is that at least three of the four reduction steps are initiated by proton transfer to the active site, which is in contrast to CcO, where electrons always arrive before the protons to the active site. The roles of the non-heme metal ion and the redox-active tyrosine in the active site are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Extracorporeal membrane oxygenation for life-threatening asthma refractory to mechanical ventilation: analysis of the Extracorporeal Life Support Organization registry

    OpenAIRE

    Yeo, Hye Ju; Kim, Dohyung; Jeon, Doosoo; Kim, Yun Seong; Rycus, Peter; Cho, Woo Hyun

    2017-01-01

    Background The use of extracorporeal membrane oxygenation (ECMO) in cases of near-fatal asthma (NFA) has increased, but the benefits and potential complications of this therapy have yet to be fully investigated. Methods Cases were extracted from the Extracorporeal Life Support Organization Registry between March 1992 and March 2016. All patients with a diagnosis of asthma (according to the International Classification of Diseases 9th edition), who also received ECMO, were extracted. Exclusion...

  14. Oxygen sensing with an absolute optical sensor based on biluminescence (Conference Presentation)

    Science.gov (United States)

    Salas Redondo, Caterin; Reineke, Sebastian

    2017-06-01

    Organic semiconductors are materials having the benefits of semiconductors together with those of organic molecules. That means, on one hand, these are compounds able to absorb and emit light, as well as conduct electricity to a certain extent, which is enough for the functionality of solid state devices. On the other hand, a remarkable characteristic is that the excitations are typically localized on individual molecules, such that the exchange interactions lead to energetically distinct singlet and triplet states. According to the spectroscopic selection rules in quantum mechanics, only transitions from the singlet excited state are allowed, deactivating radiatively while generating fluorescence emission in the process, whereas transitions from the triplet excited state are not allowed, because its decay involves a spin flip, and therefore, it is theoretically forbidden by electric dipole transitions. Nevertheless, there is a small probability of these forbidden transitions to occur at a low rate, resulting in a slow radiative deactivation known as phosphorescence emission. In this context, the property of an organic molecule able to emit light from both their singlet and triplet excited states is called biluminescence. Although this dual state emission, particularly at room temperature, is difficult to achieve by purely organic molecules, it becomes possible if competitive thermal decay is suppressed effectively, allowing emission from the triplet states (i.e. phosphorescence) in addition to the conventional fluorescence. Here, we have identified biluminescence in simple host:guest systems in which a biluminophore (i.e. organic molecule with biluminescence property) is embedded in an optimum rigid matrix, for example, a combination of PMMA [poly(methyl methacrylate)] as host and NPB [N,N'-di(naphtha-1-yl)-N,N'-diphenyl-benzidine] as biluminophore [Reineke and Baldo, Sci. Rep.]. Such system is unique not only because of the dual state emission, but also the large

  15. An Obesity Paradox of Asian Body Mass Index after Cardiac Surgery: Arterial Oxygenations in Duration of Mechanic Ventilation

    Directory of Open Access Journals (Sweden)

    Chiu-Hsia Chang

    2013-01-01

    Full Text Available Background. Numerous studies have documented an obesity paradox that overweight of Caucasian patients has better prognosis after cardiac surgery. This study is to examine Asian patients’ BMI to see whether an obesity paradox exists in DMV after cardiac surgery. Methods. A retrospective study consisted of 428 patients after cardiac surgery from January 2006 to December 2010 in the medical center of Taiwan. The Asian BMI was divided into 3 groups: under-normal weight patients (; , overweight patients (BMI 24 to <27; , and obese patients (; . Multivariable analysis and paired were used to compare all variables. Results. Overweight patients were significantly associated with the shortest DMV. Under-normal weight patients had significantly better oxygenations of AaDO2 and P/F ratio in the DMV; however, they correlated with the longest DMV, older age, more female, lower LVSV, higher BUN, more dialysis-dependent, and poorer outcomes, namely, 1-year mortality, HAP, reintubation, tracheotomy, and LOS. Conclusions. Asian overweight patients after cardiac surgery have better prognosis. Under-normal weight patients have higher risk factors, longer DMV, and poorer outcomes; even though they have better arterial oxygenations, they seem to need better arterial oxygenations for successful weaning ventilator.

  16. Investigations on the mechanism of oxygen-dependent plant processes: ethylene biosynthesis and cyanide-resistant respiration

    International Nuclear Information System (INIS)

    Stegink, S.J.

    1985-01-01

    Two oxygen-dependent plant processes were investigated. A cell-free preparation from pea (Pisum sativum L., cv. Alaska) was used to study ethylene biosynthesis from 1-aminocyclopropane-1-carboxylic acid. Mitochondrial cyanide-resistant respiration was investigated in studies with 14 C-butyl gallate and other respiratory effectors. Ethylene biosynthesis was not due to a specific enzyme, or oxygen radicals. Rather, hydrogen peroxide, generated at low levels, coupled with endogenous manganese produced ethylene. 14 C-butyl gallate bound specifically to mitochondria from cyanide-sensitive and -resistant higher plants and Neurospora crassa mitochondria. The amount of gallate bound was similar for all higher plant mitochondria. Rat liver mitochondria bound very little 14 C-butyl gallate. Plant mitochondria in which cyanide-resistance was induced bound as much 14 C-butyl gallate as before induction. However mitochondria from recently harvested white potato tubers did not bind the gallate. The observations suggest that an engaging factor couples with a gallate binding site in the mitochondrial membrane. With skunk cabbage spadix mitochondria the I 5 0 for antimycin A inhibition of oxygen uptake was decreased by salicylhydroxamic acid pretreatment; this was also true for reverse order additions. No shift was observed with mung bean hypocotyl or Jerusalem artichoke tuber mitochondria

  17. Investigation on the mechanism of non-photocatalytically TiO2 -induced reactive oxygen species and its significance on cell cycle and morphology.

    Science.gov (United States)

    Gali, Nirmal Kumar; Ning, Zhi; Daoud, Walid; Brimblecombe, Peter

    2016-10-01

    Titanium dioxide (TiO2 ) nanoparticles are widely used in daily human life, and were reported to elicit biological effects such as oxidative stress either generating reactive oxygen species (ROS) or causing cell necrosis without generating ROS, whose underlying molecular mechanisms are not yet known. In this study, the role of dissolved oxygen in TiO2 catalytic activity in dark environment, and long-term cytotoxic effects of TiO2 exposure were investigated. To determine the effect of dissolved oxygen, the anatase-TiO2 nanoparticle suspension was prepared both in deoxygenated and regular MilliQ water, and a ~ 9-fold higher ROS in regular MilliQ samples was observed compared to deoxygenated samples while in the dark, which suggested dissolved oxygen as the driving agent behind the TiO2 catalytic reaction. On the other hand, the differential cell viability and endogenous ROS activity was demonstrated through a sensitive macrophage-based assay, on a dose- and time-dependent manner. Both the cell number and endogenous ROS activity increased with increase in time till 48 h, followed by a reduction at 72 h exposure period. Long-term exposures to these nanoparticles even at low concentrations were found detrimental to cells, where late apoptosis until 48 h and necrosis at 72 h leading to cell death were noted. Late apoptotic events and cell membrane cytoskeletal actin rearrangement observed were hypothesized to be induced by particle-mediated cellular ROS. This in addition to radical generation ability of TiO2 in the dark will help further in better understanding of the toxicity mechanism in cells beyond ROS generation. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  18. Strong Electroweak Phase Transitions in the Standard Model with a Singlet

    CERN Document Server

    Espinosa, Jose R; Riva, Francesco

    2012-01-01

    It is well known that the electroweak phase transition (EWPhT) in extensions of the Standard Model with one real scalar singlet can be first-order for realistic values of the Higgs mass. We revisit this scenario with the most general renormalizable scalar potential systematically identifying all regions in parameter space that develop, due to tree-level dynamics, a potential barrier at the critical temperature that is strong enough to avoid sphaleron wash-out of the baryon asymmetry. Such strong EWPhTs allow for a simple mean-field approximation and an analytic treatment of the free-energy that leads to very good theoretical control and understanding of the different mechanisms that can make the transition strong. We identify a new realization of such mechanism, based on a flat direction developing at the critical temperature, which could operate in other models. Finally, we discuss in detail some special cases of the model performing a numerical calculation of the one-loop free-energy that improves over the ...

  19. Spin-singlet quantum Hall states and Jack polynomials with a prescribed symmetry

    International Nuclear Information System (INIS)

    Estienne, Benoit; Bernevig, B. Andrei

    2012-01-01

    We show that a large class of bosonic spin-singlet Fractional Quantum Hall model wavefunctions and their quasihole excitations can be written in terms of Jack polynomials with a prescribed symmetry. Our approach describes new spin-singlet quantum Hall states at filling fraction ν=(2k)/(2r-1) and generalizes the (k,r) spin-polarized Jack polynomial states. The NASS and Halperin spin-singlet states emerge as specific cases of our construction. The polynomials express many-body states which contain configurations obtained from a root partition through a generalized squeezing procedure involving spin and orbital degrees of freedom. The corresponding generalized Pauli principle for root partitions is obtained, allowing for counting of the quasihole states. We also extract the central charge and quasihole scaling dimension, and propose a conjecture for the underlying CFT of the (k,r) spin-singlet Jack states.

  20. A two-component dark matter model with real singlet scalars ...

    Indian Academy of Sciences (India)

    2016-01-05

    component dark matter model with real singlet scalars confronting GeV -ray excess from galactic centre and Fermi bubble. Debasish Majumdar Kamakshya Prasad Modak Subhendu Rakshit. Special: Cosmology Volume 86 Issue ...

  1. Study of the effect of heat treatments and the addition of oxygen on the microstructure and mechanical properties of Ti-15Mo alloy used as biomaterials

    International Nuclear Information System (INIS)

    Martins Junior, J.R.S.; Araujo, R.O.; Nogueira, R.A.; Grandini, C.R.; Claro, A.P.R.A.

    2010-01-01

    The Ti-15Mo alloy has its mechanical properties strongly modified by heat treatments and the addition of interstitial elements such as oxygen, for example. In this sense, the objective of this paper is to evaluate the effect of heat treatment and the introduction of oxygen on the microstructure and mechanical properties of Ti-15% pMo alloy. The samples used in this work consist of Ti containing 15% in weight of molybdenum, which were characterized by density measurements, X-ray diffraction, optical and scanning electron microscopy, microhardness and mechanical spectroscopy. The diffraction patterns were analyzed by Rietveld method, where it was possible to obtain the lattice parameters and the amount (in %) of each phase present in the microstructure. The results of optical and scanning electron microscopy are consistent with the X-ray diffraction, showing a predominance of structures of the beta type. The elasticity modulus obtained was about 90 GPa, indicating that this is a promising alloy for use in dental implants. (author)

  2. Electrochemical conversion of solid Nb2O5 to Nb in sodium chloride melt as proof of oxygen ionisation mechanism of electrodeoxidation

    International Nuclear Information System (INIS)

    Sri Maha Vishnu, D.; Sanil, N.; Mohandas, K.S.

    2016-01-01

    The direct electrochemical reduction of a solid metal oxide (MO x ) to metal (M) in calcium chloride melt (FFC Cambridge process) has been proposed to take place via. oxygen ionisation mechanism, MO x + 2xe − → M + xO 2− . However, generation of calcium metal and reduction of the oxide with it too becomes possible under the applied potential condition (3.1 V) of an FFC cell. The unique chemistry of calcium chloride melt, upon cathodic polarisation, makes it difficult to distinguish between the reduction by electrons and calcium metal. Hence in order to confirm the oxygen ionisation theory of electro-deoxidation, electrochemical deoxidation experiments were carried out with sintered Nb 2 O 5 pellet electrodes in molten sodium chloride at 1173 K. The pellets were found reduced to Nb metal. Sodiothermic reduction of Nb 2 O 5 is thermodynamically not feasible (Nb 2 O 5 + 10Na → 5Na 2 O + 2Nb, ΔG° 1173K = 102.1 kJ) and hence the observed reduction of the oxide is attributed to electrons. This study, for the first time, gives reliable experimental evidence to the oxygen ionisation mechanism of electro-reduction of solid oxides in the FFC process. The experimental results also prove that the electro-reduction of oxides can occur in melts, which otherwise were considered unsuitable from thermodynamic considerations. - Highlights: • In NaCl melt: Negligible O 2− ion solubility & Na reduction of Nb 2 O 5 to Nb – absent. • Nb 2 O 5 could be electrochemically reduced to spongy Nb in NaCl melt at 1173 K. • Mechanism: Nb 2 O 5 → Na−Nb−O compounds + suboxides of Nb → Na x NbO y → Nb. • Metallothermic reduction of oxide in melt - not mandatory for electrodeoxidation. • In FFC Cambridge process: Metallothermic reduction is not essential but desirable.

  3. The nature of singlet excitons in oligoacene molecular crystals

    KAUST Repository

    Yamagata, H.

    2011-01-01

    A theory for polarized absorption in crystalline oligoacenes is presented, which includes Frenkel exciton coupling, the coupling between Frenkel and charge-transfer (CT) excitons, and the coupling of all neutral and ionic excited states to the dominant ring-breathing vibrational mode. For tetracene, spectra calculated using all Frenkel couplings among the five lowest energy molecular singlet states predict a Davydov splitting (DS) of the lowest energy (0-0) vibronic band of only -32cm-1, far smaller than the measured value of 631cm-1 and of the wrong sign-a negative sign indicating that the polarizations of the lower and upper Davydov components are reversed from experiment. Inclusion of Frenkel-CT coupling dramatically improves the agreement with experiment, yielding a 0-0 DS of 601cm-1 and a nearly quantitative reproduction of the relative spectral intensities of the 0-n vibronic components. Our analysis also shows that CT mixing increases with the size of the oligoacenes. We discuss the implications of these results on exciton dissociation and transport. © 2011 American Institute of Physics.

  4. Sustained molecular oxygen activation by solid iron doped silicon carbide under microwave irradiation: Mechanism and application to norfloxacin degradation.

    Science.gov (United States)

    Li, Hongbo; Chen, Jing; Hou, Huijie; Pan, Hong; Ma, Xiaoxue; Yang, Jiakuan; Wang, Linling; Crittenden, John C

    2017-12-01

    Sustained molecular oxygen activation by iron doped silicon carbide (Fe/SiC) was investigated under microwave (MW) irradiation. The catalytic performance of Fe/SiC for norfloxacin (NOR) degradation was also studied. Rapid mineralization in neutral solution was observed with a pseudo-first-order rate constant of 0.2239 min -1 under 540 W of MW irradiation for 20 min. Increasing Fe/SiC rod and MW power significantly enhanced the degradation and mineralization rate with higher yield of reactive oxygen species (ROS). Fe shell corrosion and subsequent Fe 0/II oxidation by molecular oxygen with MW activation was the key factor for NOR degradation through two-electron-transfer by Fe 0 under acidic conditions and single-electron-transfer by Fe II under neutral-alkaline solution. Removal rate of NOR was significantly affected by solution pH, showing higher degradation rates at both acidic and alkaline conditions. The highest removal efficiencies and rates at alkaline pH values were ascribed to the contribution of bound Fe II species on the Fe shell surface due to the hydroxylation of Fe/SiC. ·OH was the main oxidizing specie for NOR degradation, confirmed by density functional theory (DFT) calculations and radical scavenger tests. DFT calculations were conducted on the reaction/activation energies of the transition/final states of NOR/degradation products, combined with intermediate identification with high performance liquid chromatography coupled with a triple-quadruple mass spectrometer (HPLC-MS/MS), the piperazinyl ring was the most reactive site for ·OH attack, followed by further ring-opening and stepwise oxidation. In this study, Fe/SiC were proved to be an excellent catalyst for the treatment of fluoroquinolone antibiotics with MW activation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Ethical dilemma: offering short-term extracorporeal membrane oxygenation support for terminally ill children who are not candidates for long-term mechanical circulatory support or heart transplantation.

    Science.gov (United States)

    Shankar, Venkat; Costello, John P; Peer, Syed M; Klugman, Darren; Nath, Dilip S

    2014-04-01

    The use of extracorporeal membrane oxygenation (ECMO) in terminally ill pediatric patients who are not candidates for long-term mechanical circulatory support or heart transplantation requires careful deliberation. We present the case of a 16-year-old female with a relapse of acute lymphoid leukemia and acute-on-chronic cardiomyopathy who received short-term ECMO therapy. In addition, we highlight several ethical considerations that were crucial to this patient's family-centered care and demonstrate that this therapy can be accomplished in a manner that respects patient autonomy and family wishes.

  6. Mechanical properties and biocompatibility in alloy Ti-Ta system containing oxygen; Propriedades mecanicas e biocompatibilidades em ligas do sistema Ti-Ta contendo oxigenio

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz, S.L.M.; Grandini, C.R., E-mail: samlea@fc.unesp.b [Universidade Estadual Paulista (UNESP), Bauru, SP (Brazil). Lab. de Anelasticidade e Biomateriais; Claro, A.P.R.A. [Universidade Estadual Paulista Julio de Mesquisa Filho (DMT/UNESP), Guaratingueta, SP (Brazil). Fac. de Engenharia. Dept. de Materiais e Tecnologia

    2010-07-01

    Due to the excellent properties such as corrosion resistance, good mechanical strength/density, good performance at high temperatures, Ti is very useful in the chemical industry and aerospace. Currently, their use has expanded to the field of biomaterials, due to its excellent biocompatibility and reduced elasticity modulus, favouring the production of orthopaedic and dental prostheses. Promising alloys are the Ti-Ta system and researches have been directed to describe and understand the behavior of this system. In this paper, samples of Ti-Ta alloys containing 8 and 16% (wt%) containing interstitial oxygen were prepared and characterized by density, xray diffraction, hardness, elasticity modulus measurements and in vitro cytotoxicity tests. (author)

  7. Dynamics of Singlet Fission and Electron Injection in Self-Assembled Acene Monolayers on Titanium Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Justin C [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pace, Natalie A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Arias, Dylan H [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Christensen, Steven T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Granger, Devin B. [University of Kentucky; Anthony, John E. [University of Kentucky

    2018-02-26

    We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition of an alumina layer slows down electron injection, allowing the formation of triplets from singlet fission in 40 ps. However, the triplets do not inject electrons, which is likely due to a lack of sufficient driving force for triplet dissociation. These results point to the critical balance required between efficient singlet fission and appropriate energetics for interfacial charge transfer.

  8. Blue-light dependent reactive oxygen species formation by Arabidopsis cryptochrome may define a novel evolutionarily conserved signaling mechanism.

    Science.gov (United States)

    Consentino, Laurent; Lambert, Stefan; Martino, Carlos; Jourdan, Nathalie; Bouchet, Pierre-Etienne; Witczak, Jacques; Castello, Pablo; El-Esawi, Mohamed; Corbineau, Francoise; d'Harlingue, Alain; Ahmad, Margaret

    2015-06-01

    Cryptochromes are widespread blue-light absorbing flavoproteins with important signaling roles. In plants they mediate de-etiolation, developmental and stress responses resulting from interaction with downstream signaling partners such as transcription factors and components of the proteasome. Recently, it has been shown that Arabidopsis cry1 activation by blue light also results in direct enzymatic conversion of molecular oxygen (O2 ) to reactive oxygen species (ROS) and hydrogen peroxide (H2 O2 ) in vitro. Here we explored whether direct enzymatic synthesis of ROS by Arabidopsis cry1 can play a physiological role in vivo. ROS formation resulting from cry1 expression was measured by fluorescence assay in insect cell cultures and in Arabidopsis protoplasts from cryptochrome mutant seedlings. Cell death was determined by colorimetric assay. We found that ROS formation results from cry1 activation and induces cell death in insect cell cultures. In plant protoplasts, cryptochrome activation results in rapid increase in ROS formation and cell death. We conclude that ROS formation by cryptochromes may indeed be of physiological relevance and could represent a novel paradigm for cryptochrome signaling. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

  9. Dual-functional Memory and Threshold Resistive Switching Based on the Push-Pull Mechanism of Oxygen Ions

    KAUST Repository

    Huang, Yi-Jen

    2016-04-07

    The combination of nonvolatile memory switching and volatile threshold switching functions of transition metal oxides in crossbar memory arrays is of great potential for replacing charge-based flash memory in very-large-scale integration. Here, we show that the resistive switching material structure, (amorphous TiOx)/(Ag nanoparticles)/(polycrystalline TiOx), fabricated on the textured-FTO substrate with ITO as the top electrode exhibits both the memory switching and threshold switching functions. When the device is used for resistive switching, it is forming-free for resistive memory applications with low operation voltage (<±1 V) and self-compliance to current up to 50 μA. When it is used for threshold switching, the low threshold current is beneficial for improving the device selectivity. The variation of oxygen distribution measured by energy dispersive X-ray spectroscopy and scanning transmission electron microscopy indicates the formation or rupture of conducting filaments in the device at different resistance states. It is therefore suggested that the push and pull actions of oxygen ions in the amorphous TiOx and polycrystalline TiOx films during the voltage sweep account for the memory switching and threshold switching properties in the device.

  10. Oxygenic photosynthesis as a protection mechanism for cyanobacteria against iron-encrustation in environments with high Fe2+ concentrations

    NARCIS (Netherlands)

    Ionescu, D.; Buchmann, B.; Heim, C.; Häusler, S.; de Beer, D.; Polerecky, L.

    2014-01-01

    If O2 is available at circumneutral pH, Fe2+ is rapidly oxidized to Fe3+, which precipitates as FeO(OH). Neutrophilic iron oxidizing bacteria have evolved mechanisms to prevent self-encrustation in iron. Hitherto, no mechanism has been proposed for cyanobacteria from Fe2+-rich environments; these

  11. Carbon-14 studies on the role of oxygen-containing compounds in the reaction mechanism of the Fischer-Tropsch synthesis

    International Nuclear Information System (INIS)

    Aksoy, H.A.

    1975-01-01

    In this work the behaviour of organic oxygen compounds has been studied in the reaction mechanism of Fischer-Tropsch synthesis using the tracer method. As an oxygen carrying tracer materials i-propanole (2- 14 C), acetone (2- 14 C) and ethanole (1- 14 C) have been added to the synthesis gas. The synthesis experiments are performed under standard conditions: The synthesis products are separated in suitable fractions and then studied by gas- and radio-gaschromatography. As a result the C-number distributions of the synthesis products are obtained as a function of concentration (weight %, mol %) and radioactivity (activity %). On this basis the relative molar activities have been calculated for certain compounds and fractions. Adding i-propanole- 14 C a great part of the tracer compound is transformed to acetone- 14 C, however adding acetone- 14 C to the synthesis gas a large amount of i-propanole- 14 C is produced. The main hydrocarbon reaction product from i-propanol and acetone is propane. Besides propane also propene is produced with equal molar radioactivity. This indicates that the formation of adsorbed oxygen compounds, as they may also be produced by chemisorption from alcohols or carbonyle compounds, is the first step in the formation of hydrocarbons by hydrogenolytic separation of oxygen. Comparing the results obtained with ethanole- 14 C and i-propanole- 14 C as a tacer material, for ethane an essentially lower molar activity is obtained when adding ethanole- 14 C compared with propane when adding i-propanole- 14 C. This corresponds with a particularly low desorption probability at the C 2 -hydrocarbon level. (orig./HK) [de

  12. Arterial Levels of Oxygen Stimulate Intimal Hyperplasia in Human Saphenous Veins via a ROS-Dependent Mechanism

    Science.gov (United States)

    Joddar, Binata; Firstenberg, Michael S.; Reen, Rashmeet K.; Varadharaj, Saradhadevi; Khan, Mahmood; Childers, Rachel C.; Zweier, Jay L.; Gooch, Keith J.

    2015-01-01

    Saphenous veins used as arterial grafts are exposed to arterial levels of oxygen partial pressure (pO2), which are much greater than what they experience in their native environment. The object of this study is to determine the impact of exposing human saphenous veins to arterial pO2. Saphenous veins and left internal mammary arteries from consenting patients undergoing coronary artery bypass grafting were cultured ex vivo for 2 weeks in the presence of arterial or venous pO2 using an established organ culture model. Saphenous veins cultured with arterial pO2 developed intimal hyperplasia as evidenced by 2.8-fold greater intimal area and 5.8-fold increase in cell proliferation compared to those freshly isolated. Saphenous veins cultured at venous pO2 or internal mammary arteries cultured at arterial pO2 did not develop intimal hyperplasia. Intimal hyperplasia was accompanied by two markers of elevated reactive oxygen species (ROS): increased dihydroethidium associated fluorescence (4-fold, ppO2 is suggested by the observation that chronic exposure to tiron, a ROS scavenger, during the two-week culture period, blocked intimal hyperplasia. Electron paramagnetic resonance based oximetry revealed that the pO2 in the wall of the vessel tracked that of the atmosphere with a ~30 mmHg offset, thus the cells in the vessel wall were directly exposed to variations in pO2. Monolayer cultures of smooth muscle cells isolated from saphenous veins exhibited increased proliferation when exposed to arterial pO2 relative to those cultured at venous pO2. This increased proliferation was blocked by tiron. Taken together, these data suggest that exposure of human SV to arterial pO2 stimulates IH via a ROS-dependent pathway. PMID:25799140

  13. Noninvasive Mechanical Ventilation in Helicopter Emergency Medical Services Saves Time and Oxygen and Improves Patient and Mission Safety: A Pilot Study.

    Science.gov (United States)

    Garrote, Jose Ignacio; Aylagas, Diego; Gutierrez, Jose M; Sinisterra, Juan A; Gowran, Brian Mc; Medina, Alberto; Díaz-Tendero, Javier; Gómez-Calcerrada, Pablo; Crespo, Ricardo

    2015-01-01

    Noninvasive mechanical ventilation (NIMV) is used increasingly in patients with severe respiratory distress and has clear benefits over standard medical therapy (SMT) in terms of patient safety. NIMV is particularly useful in cardiogenic acute pulmonary edema and in exacerbations of chronic obstructive pulmonary disease, both of which are frequent reasons for an emergency medical services dispatch. Early use of NIMV avoids complications in these patients in many cases. To date, the use of noninvasive positive-pressure ventilation in the air medical environment has been minimally researched. We evaluated NIMV versus SMT in the helicopter emergency medical services environment in patients with cardiogenic acute pulmonary edema and exacerbated chronic obstructive pulmonary disease. The parameters assessed were stabilization time, tolerance, safety, clinical response, and oxygen consumption. Bilevel noninvasive positive-pressure ventilation was the ventilatory mode used for all patients. The technique of NIMV in medical air transport is useful, easy to operate, and safe. It offers increased patient safety, reducing the need for invasive mechanical ventilation and its complications; better intervention times (35.8 minutes [NIMV] vs. 57.65 minutes [SMT], P < .05); improvement in aircraft operability; and a reduction in oxygen consumption (6.2 L/min vs. 9.8 L/min, P < .05), contributing to mission operability and safety. Copyright © 2015 Air Medical Journal Associates. Published by Elsevier Inc. All rights reserved.

  14. Effects of fermionic singlet neutrinos on high- and low-energy observables

    International Nuclear Information System (INIS)

    Weiland, C.

    2013-01-01

    In this doctoral thesis, we study both low- and high-energy observables related to massive neutrinos. Neutrino oscillations have provided indisputable evidence in favour of non-zero neutrino masses and mixings. However, the original formulation of the standard model cannot account for these observations, which calls for the introduction of new physics. Among many possibilities, we focus here on the inverse seesaw, a neutrino mass generation mechanism in which the standard model is extended with fermionic gauge singlets. This model offers an attractive alternative to the usual seesaw realisations since it can potentially have natural Yukawa couplings (O(1)) while keeping the new physics scale at energies within the reach of the LHC. Among the many possible effects, this scenario can lead to deviations from lepton flavour universality. We have investigated these signatures and found that the ratios R K and R π provide new, additional constraints on the inverse seesaw. We have also considered the embedding of the inverse seesaw in supersymmetric models. This leads to increased rates for various lepton flavour violating processes, due to enhanced contributions from penguin diagrams mediated by the Higgs and Z 0 bosons. Finally, we also found that the new invisible decay channels associated with the sterile neutrinos present in the super-symmetric inverse seesaw could significantly weaken the constraints on the mass and couplings of a light CP-odd Higgs boson. (author)

  15. Nonuniversal anomaly-free U(1) model with three Higgs doublets and one singlet scalar field

    Science.gov (United States)

    Mantilla, S. F.; Martinez, R.

    2017-11-01

    The flavor problem, neutrino physics, and the fermion mass hierarchy are important motivations to extend the Standard Model to the TeV scale. A new family nonuniversal extension is presented with three Higgs doublets, one Higgs singlet, and one scalar dark matter candidate. Exotic fermions are included in order to cancel chiral anomalies and to allow family nonuniversal U(1 ) X charges. By implementing an additional Z2 symmetry, the Yukawa coupling terms are suited in such a way that the fermion mass hierarchy is obtained without fine-tuning. The neutrino sector includes Majorana fermions to implement the inverse seesaw mechanism. The effective mass matrix for Standard Model neutrinos is fitted to current neutrino oscillation data to check the consistency of the model with experimental evidence, obtaining that the normal-ordering scheme is preferred over the inverse ones, and the values of the neutrino Yukawa coupling constants are shown. Finally, the h →τ μ lepton-flavor-violation process is addressed with the rotation matrices of the C P -even scalars, left- and right-handed charged leptons, yielding definite regions where the model is consistent with CMS reports of BR (h →τ μ ).

  16. Topological spin-singlet superconductors with underlying sublattice structure

    Science.gov (United States)

    Dutreix, C.

    2017-07-01

    Majorana boundary quasiparticles may naturally emerge in a spin-singlet superconductor with Rashba spin-orbit interactions when a Zeeman magnetic field breaks time-reversal symmetry. Their existence and robustness against adiabatic changes is deeply related, via a bulk-edge correspondence, to topological properties of the band structure. The present paper shows that the spin-orbit may be responsible for topological transitions when the superconducting system has an underlying sublattice structure, as it appears in a dimerized Peierls chain, graphene, and phosphorene. These systems, which belong to the Bogoliubov-de Gennes class D, are found to have an extra symmetry that plays the role of the parity. It enables the characterization of the topology of the particle-hole symmetric band structure in terms of band inversions. The topological phase diagrams this leads to are then obtained analytically and exactly. They reveal that, because of the underlying sublattice structure, the existence of topological superconducting phases requires a minimum doping fixed by the strength of the Rashba spin orbit. Majorana boundary quasiparticles are finally predicted to emerge when the Fermi level lies in the vicinity of the bottom (top) of the conduction (valence) band in semiconductors such as the dimerized Peierls chain and phosphorene. In a two-dimensional topological superconductor based on (stretched) graphene, which is semimetallic, Majorana quasiparticles cannot emerge at zero and low doping, that is, when the Fermi level is close to the Dirac points. Nevertheless, they are likely to appear in the vicinity of the van Hove singularities.

  17. Accretion onto Carbon-Oxygen White Dwarfs as a possible mechanism for growth to the Chandrasekhar Limit

    Science.gov (United States)

    Starrfield, Sumner; Bose, Maitrayee; Iliadis, Christian; Hix, William R.; José, Jordi; Hernanz, Margarita

    2017-08-01

    We have continued our studies of accretion onto white dwarfs by following the evolution of thermonuclear runaways (TNRs) on Carbon Oxygen (CO) white dwarfs. We have varied the mass of the white dwarf and the composition of the accreted material. We use the results of the multi-dimensional studies of TNRs in white dwarfs, accreting only Solar matter, which show that sufficient core material is dredged-up by the TNR and then ejected by the explosion to agree with the observations of the ejecta abundances. We have also found that the initial 12C abundance is inversely proportional to the amount of material accreted prior to the TNR. Therefore, we first accrete Solar material and follow the evolution until a TNR occurs. Because the 12C abundance is significantly smaller then if we had initially mixed the accreting gas with the carbon-oxygen core, more matter takes part in the explosion than if we had begun the evolution with the mixed composition. We then instantaneously switch the composition to a mixture with either 25% core material or 50% core material (plus accreted material) and follow the resulting evolution of the TNR. We use our 1D, Lagrangian, hydrodynamic code: NOVA. We report on the results of these new simulations and compare the ejecta abundances to those measured in pre-solar grains that are thought to arise from classical nova explosions. These results will also be compared to recent results with SHIVA (Josè and Hernanz). We find that there are some white dwarf masses where significantly less mass is ejected than accreted during the Classical Nova event and, therefore, the white dwarf is growing in mass as a result of the accretion and in spite of the resulting explosion.This work was supported in part by NASA under the Astrophysics Theory Program grant 14-ATP14-0007 and the U.S. DOE under Contract No. DE-FG02- 97ER41041. SS acknowledges partial support from NASA, NSF, and HST grants to ASU and WRH is supported by the U.S. Department of Energy, Office

  18. Mechanical strain stimulates vasculogenesis and expression of angiogenesis guidance molecules of embryonic stem cells through elevation of intracellular calcium, reactive oxygen species and nitric oxide generation.

    Science.gov (United States)

    Sharifpanah, Fatemeh; Behr, Sascha; Wartenberg, Maria; Sauer, Heinrich

    2016-12-01

    Differentiation of embryonic stem (ES) cells may be regulated by mechanical strain. Herein, signaling molecules underlying mechanical stimulation of vasculogenesis and expression of angiogenesis guidance cues were investigated in ES cell-derived embryoid bodies. Treatment of embryoid bodies with 10% static mechanical strain using a Flexercell strain system significantly increased CD31-positive vascular structures and the angiogenesis guidance molecules plexinB1, ephrin B2, neuropilin1 (NRP1), semaphorin 4D (sem4D) and robo4 as well as vascular endothelial growth factor (VEGF), fibroblast growth factor-2 (FGF-2) and platelet-derived growth factor-BB (PDGF-BB) as evaluated by Western blot and real time RT-PCR. In contrast ephrin type 4 receptor B (EphB4) expression was down-regulated upon mechanical strain, indicating an arterial-type differentiation. Robo1 protein expression was modestly increased with no change in mRNA expression. Mechanical strain increased intracellular calcium as well as reactive oxygen species (ROS) and nitric oxide (NO). Mechanical strain-induced vasculogenesis was abolished by the NOS inhibitor L-NAME, the NADPH oxidase inhibitor VAS2870, upon chelation of intracellular calcium by BAPTA as well as upon siRNA inactivation of ephrin B2, NRP1 and robo4. BAPTA blunted the strain-induced expression of angiogenic growth factors, the increase in NO and ROS as well as the expression of NRP1, sem4D and plexinB1, whereas ephrin B2, EphB4 as well as robo1 and robo4 expression were not impaired. Mechanical strain stimulates vasculogenesis of ES cells by the intracellular messengers ROS, NO and calcium as well as by upregulation of angiogenesis guidance molecules and the angiogenic growth factors VEGF, FGF-2 and PDGF-BB. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Antimicrobial strategies centered around reactive oxygen species - bactericidal antibiotics, photodynamic therapy and beyond

    Science.gov (United States)

    Vatansever, Fatma; de Melo, Wanessa C.M.A.; Avci, Pinar; Vecchio, Daniela; Sadasivam, Magesh; Gupta, Asheesh; Chandran, Rakkiyappan; Karimi, Mahdi; Parizotto, Nivaldo A; Yin, Rui; Tegos, George P; Hamblin, Michael R

    2013-01-01

    Reactive oxygen species (ROS) can attack a diverse range of targets to exert antimicrobial activity, which accounts for their versatility in mediating host defense against a broad range of pathogens. Most ROS are formed by the partial reduction of molecular oxygen. Four major ROS are recognized comprising: superoxide (O2•−), hydrogen peroxide (H2O2), hydroxyl radical (•OH), and singlet oxygen (1O2), but they display very different kinetics and levels of activity. The effects of O2•− and H2O2 are less acute than those of •OH and 1O2, since the former are much less reactive and can be detoxified by endogenous antioxidants (both enzymatic and non-enzymatic) that are induced by oxidative stress. In contrast, no enzyme can detoxify •OH or 1O2, making them extremely toxic and acutely lethal. The present review will highlight the various methods of ROS formation and their mechanism of action. Antioxidant defenses against ROS in microbial cells and the use of ROS by antimicrobial host defense systems are covered. Antimicrobial approaches primarily utilizing ROS comprise both bactericidal antibiotics, and non-pharmacological methods such as photodynamic therapy, titanium dioxide photocatalysis, cold plasma and medicinal honey. A brief final section covers, reactive nitrogen species, and related therapeutics, such as acidified nitrite and nitric oxide releasing nanoparticles. PMID:23802986

  20. Degradation Kinetics and Mechanism of Lithospermic Acid under Low Oxygen Condition Using Quantitative 1H NMR with HPLC-MS.

    Science.gov (United States)

    Pan, Jianyang; Gong, Xingchu; Qu, Haibin

    2016-01-01

    A novel quantitative 1H NMR (Q-NMR) combined with HPLC-MS method has been proposed for investigating the degradation process of traditional Chinese medicine (TCM) components. Through this method, in-situ monitoring of dynamics degradation process of lithospermic acid (LA), one of the popular polyphenolic acids in TCM, was realized under low oxygen condition. Additionally, this methodology was proved to be simple, rapid and specific. Degradation kinetic runs have been carried out to systematically investigate the effects of two key environmental factors, initial pH values and temperatures. Eight main degradation products of LA were detected, seven of which were tentatively structural elucidated with the help of both NMR and LC-MS in this work and salvianolic acid A (Sal A) was the primary degradation product of LA. A possible degradation pathway of LA was proposed, subsequently. The results showed that the degradation of LA followed pseudo-first-order kinetics. The apparent degradation kinetic constants increased as the initial pH value of the phosphate buffer increased. Under the given conditions, the rate constants of overall degradation as a function of temperature obeyed the Arrhenius equation. Our results proved that the Q-NMR combined with HPLC-MS method can be one of the most promising techniques for investigating degradation process of active components in TCM.