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Sample records for singlet oxygen damage

  1. 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

  2. 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....

  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. 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...

  5. 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

  6. 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

  7. 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

  8. 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.

  9. 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...

  10. 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)

  11. 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

  12. 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.

  13. 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...

  14. 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...

  15. 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.

  16. 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.

  17. 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

  18. 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

  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 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®.

  1. 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.

  2. 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 ...

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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

  12. 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.

  13. 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...

  14. 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

  15. 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.

  16. 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.

  17. 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

  18. 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...

  19. 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...

  20. 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...

  1. 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

  2. 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...

  3. 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.

  4. 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.

  5. 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%.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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...

  12. 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.

  13. 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.

  14. 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.

  15. 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...

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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...

  4. 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.

  5. 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 ...

  6. 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...

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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...

  15. 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.

  16. 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.

  17. 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

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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

  3. 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...

  4. 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...

  5. 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.

  6. 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.

  7. 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)

  8. 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.

  9. 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.

  10. 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...

  11. 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.

  12. 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.

  13. 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...

  14. 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...

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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

  19. 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...

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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...

  6. 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

  7. 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

  8. Oxygen reperfusion damage in an insect.

    Directory of Open Access Journals (Sweden)

    John R B Lighton

    Full Text Available The deleterious effects of anoxia followed by reperfusion with oxygen in higher animals including mammals are well known. A convenient and genetically well characterized small-animal model that exhibits reproducible, quantifiable oxygen reperfusion damage is currently lacking. Here we describe the dynamics of whole-organism metabolic recovery from anoxia in an insect, Drosophila melanogaster, and report that damage caused by oxygen reperfusion can be quantified in a novel but straightforward way. We monitored CO(2 emission (an index of mitochondrial activity and water vapor output (an index of neuromuscular control of the spiracles, which are valves between the outside air and the insect's tracheal system during entry into, and recovery from, rapid-onset anoxia exposure with durations ranging from 7.5 to 120 minutes. Anoxia caused a brief peak of CO(2 output followed by knock-out. Mitochondrial respiration ceased and the spiracle constrictor muscles relaxed, but then re-contracted, presumably powered by anaerobic processes. Reperfusion to sustained normoxia caused a bimodal re-activation of mitochondrial respiration, and in the case of the spiracle constrictor muscles, slow inactivation followed by re-activation. After long anoxia durations, both the bimodality of mitochondrial reactivation and the recovery of spiracular control were impaired. Repeated reperfusion followed by episodes of anoxia depressed mitochondrial respiratory flux rates and damaged the integrity of the spiracular control system in a dose-dependent fashion. This is the first time that physiological evidence of oxygen reperfusion damage has been described in an insect or any invertebrate. We suggest that some of the traditional approaches of insect respiratory biology, such as quantifying respiratory water loss, may facilitate using D. melanogaster as a convenient, well-characterized experimental model for studying the underlying biology and mechanisms of ischemia and

  9. 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).

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. 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...

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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

  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

    2018-02-27

    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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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

  5. 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.

  6. 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

  7. 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

  8. 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.

  9. 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%.

  10. 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.

  11. 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.

  12. 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.

  13. Cleaning of Fire Damaged Watercolor and Textiles Using Atomic Oxygen

    Science.gov (United States)

    Rutledge, Sharon K.; Banks, Bruce A.; Chichernea, Virgil A.; Haytas, Christy A.

    2000-01-01

    A noncontact technique is described that uses atomic oxygen generated under low pressure in the presence of nitrogen to remove soot from the surface of a test watercolor panel and strips of cotton, wool and silk. The process, which involves surface oxidation, permits control of the amount of surface material removed. The effectiveness of soot removal from test panels of six basic watercolors (alizarin crimson, burnt sienna, lemon yellow, yellow ochre, cerulean blue and ultramarine blue) and strips of colored cotton, wool and silk was measured using reflectance spectroscopy. The atomic oxygen removed soot effectively from the treated areas and enabled partial recovery of charred watercolors. However, overexposure can result in removal of sizing, bleaching, and weakening of the structure. With the proper precautions, atomic oxygen treatment appears to have great potential to salvage heavily smoke damaged artworks which were previously considered unrestorable.

  14. 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.

  15. 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.

  16. 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

  17. 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...

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Photoexcited riboflavin induces oxidative damage to human serum albumin

    Science.gov (United States)

    Hirakawa, Kazutaka; Yoshioka, Takuto

    2015-08-01

    Photoexcited riboflavin induced damage of human serum albumin (HSA), a water soluble protein, resulting in the diminishment of fluorescence from the tryptophan residue. Because riboflavin hardly photosensitized singlet oxygen generation and sodium azide, a singlet oxygen quencher, did not inhibit protein damage, electron transfer-mediated oxidation of HSA was speculated. Fluorescence lifetime of riboflavin was not affected by HSA, suggesting that the excited triplet state of riboflavin is responsible for protein damage through electron transfer. In addition, the preventive effect of xanthone derivatives, triplet quenchers, on photosensitized protein damage could be evaluated using this photosensitized reaction system of riboflavin and HSA.

  6. 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.

  7. 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.

  8. Oxygen diffusion and recovery of damage in irradiated polystyrene

    Science.gov (United States)

    Holm, U.; Horstmann, D.; Schacht, S.

    1999-05-01

    The diffusion of oxygen in non-irradiated and irradiated polystyrene based plastic scintillators SCSN38 has been measured making use of a fluorescence quenching effect. Fluorescence light from electron or light excitation of dyes is reduced when oxygen is present in the sample. The reduction is characteristic for the dye and proportional to the partial pressure. Oxygen annealing of color centers of samples stored and irradiated in vacuum enhances the light yield. A diffusion model describes the results very well and results in a diffusion constant D=(1.00 ± 0.10)×10 -7 cm 2 s -1 at 23°C.

  9. 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.

  10. Post-irradiation modification of oxygen-dependent and independent damage by catalase in barley seeds

    International Nuclear Information System (INIS)

    Sah, N.K.; Kesavan, P.C.

    1987-01-01

    If H 2 O 2 is one of the major mediators of the 'oxygen effect' in biological systems then catalase, which enzymically decomposes H 2 O 2 should have a significant influence on radiation damage, particularly under oxygenated conditions. The post-irradiation (300 Gy gamma rays) effect of catalase was, therefore, assessed on barley seeds of about 4% moisture content under oxygenated and oxygen-free conditions at varying temperatures. Catalase affords concentration-dependent radioprotection under oxygenated condition at both 25 0 C and 4 0 C. The level of protection at 4 0 C is less than at 25 0 C. This is obviously due to a decrease in catalase activity at low temperature. Under oxygen-free conditions, catalase enhances radiation damage at 4 0 C while at 25 0 C it it has no effect. This has been substantiated by data on the frequency of chromosomal aberrations and on peroxidase activity. Sodium azide, a catalase inhibitor, was found to eliminate the radioprotective action of catalase. The study supports the view that the 'oxygen effect' is mediated largely through peroxides in irradiated biological systems. However, the observations made particularly at 4 0 C under oxygen-free condition seem to involve physicochemical reactions. (author)

  11. The neuroprotective effect of hyperbaric oxygen treatment on laser-induced retinal damage in rats

    Science.gov (United States)

    Vishnevskia-Dai, Victoria; Belokopytov, Mark; Dubinsky, Galina; Nachum, Gal; Avni, Isaac; Belkin, Michael; Rosner, Mordechai

    2005-04-01

    Retinal damage induced by mechanical trauma, ischemia or laser photocoagulation increases considerably by secondary degeneration processes. The spread of damage may be ameliorated by neuroprotection that is aimed at reducing the extent of the secondary degeneration and promote healing processes. Hyperbaric oxygen (HBO) treatment consists of inspiration of oxygen at higher than one absolute atmospheric pressure. Improved neural function was observed in patients with acute brain trauma or ischemia treated with HBO. This study was designed to evaluate the neuroprotective effect of hyperbaric oxygen (HBO) on laser induced retinal damage in a rat model. Standard argon laser lesions were created in 25 pigmented rats divided into three groups: Ten rats were treated immediately after the irradiation with HBO three times during the first 24 hr followed by 12 consecutive daily treatments. Five rats received a shorter treatment regimen of 10 consecutive HBO treatments. The control group (10 rats) underwent the laser damage with no additional treatment. The retinal lesions were evaluated 20 days after the injury. All outcome measures were improved by the longer HBO treatment (Ptreatment was less effective, showing an increase only in nuclei density at the central area of lesion (Pretinal damage in a rat model. In the range of HBO exposures studied, longer exposure provides more neuroprotection. These results encourage further evaluation of the potential therapeutic use of hyperbaric oxygen in diseases and injuries of the retina.

  12. 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...

  13. Creating rat model for hypoxic brain damage in neonates by oxygen deprivation.

    Science.gov (United States)

    Zhang, Qiaoli; Ding, Yingxue; Yao, Yanqing; Yu, Yang; Yang, Lijun; Cui, Hong

    2013-01-01

    Current study explores the feasibility of using a non-surgical method of oxygen deprivation to create Hypoxic brain damage in neonatal rats for medical studies. 7-day-old Sprague Dowley (SD) rats were kept in a container with low oxygen level (8%) for 1.5h. A second group had bilateral cephalic artery ligation before the 1.5h-low oxygen treatment, a method similar to the popular Rice method, to expose the brain to both hypoxic and ischemic situations. Short term neural functions and brain water weights were evaluated 1 day after the hypoxic treatment. Brain pathology and histology were also examined at 1 day and 3 days after the hypoxic treatment. Both groups showed impaired neural functions and increased brain water weight compared to the controls. Histology studies also revealed injuries in the subcortex, hippocampus and lateral ventricle in the brains from both groups. There is no significant difference in the degree of brain damages observed in the two groups. Our work demonstrated that oxygen deprivation alone is sufficient to cause brain damages similar to those seen in Hypoxic-ischemic brain disease (HIBD). Because this method avoids the invasive surgical procedure and therefore reduces the stress and mortality of laboratory animals during the experiment, we recommend it to be the favorable method for creating rat models for HIBD studies.

  14. Creating rat model for hypoxic brain damage in neonates by oxygen deprivation.

    Directory of Open Access Journals (Sweden)

    Qiaoli Zhang

    Full Text Available Current study explores the feasibility of using a non-surgical method of oxygen deprivation to create Hypoxic brain damage in neonatal rats for medical studies. 7-day-old Sprague Dowley (SD rats were kept in a container with low oxygen level (8% for 1.5h. A second group had bilateral cephalic artery ligation before the 1.5h-low oxygen treatment, a method similar to the popular Rice method, to expose the brain to both hypoxic and ischemic situations. Short term neural functions and brain water weights were evaluated 1 day after the hypoxic treatment. Brain pathology and histology were also examined at 1 day and 3 days after the hypoxic treatment. Both groups showed impaired neural functions and increased brain water weight compared to the controls. Histology studies also revealed injuries in the subcortex, hippocampus and lateral ventricle in the brains from both groups. There is no significant difference in the degree of brain damages observed in the two groups. Our work demonstrated that oxygen deprivation alone is sufficient to cause brain damages similar to those seen in Hypoxic-ischemic brain disease (HIBD. Because this method avoids the invasive surgical procedure and therefore reduces the stress and mortality of laboratory animals during the experiment, we recommend it to be the favorable method for creating rat models for HIBD studies.

  15. 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

  16. 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

  17. 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.

  18. Oxidatively generated DNA damage after Cu(II) catalysis of dopamine and related catecholamine neurotransmitters and neurotoxins: Role of reactive oxygen species.

    Science.gov (United States)

    Spencer, Wendy A; Jeyabalan, Jeyaprakash; Kichambre, Sunita; Gupta, Ramesh C

    2011-01-01

    There is increasing evidence supporting a causal role for oxidatively damaged DNA in neurodegeneration during the natural aging process and in neurodegenerative diseases such as Parkinson and Alzheimer. The presence of redox-active catecholamine neurotransmitters coupled with the localization of catalytic copper to DNA suggests a plausible role for these agents in the induction of oxidatively generated DNA damage. In this study we have investigated the role of Cu(II)-catalyzed oxidation of several catecholamine neurotransmitters and related neurotoxins in inducing oxidatively generated DNA damage. Autoxidation of all catechol neurotransmitters and related congeners tested resulted in the formation of nearly a dozen oxidation DNA products resulting in a decomposition pattern that was essentially identical for all agents tested. The presence of Cu(II), and to a lesser extent Fe(III), had no effect on the decomposition pattern but substantially enhanced the DNA product levels by up to 75-fold, with dopamine producing the highest levels of unidentified oxidation DNA products (383±46 adducts/10(6) nucleotides), nearly 3-fold greater than 8-oxo-7,8-dihydro-2'-deoxyguanosine (122±19 adducts/10(6) nucleotides) under the same conditions. The addition of sodium azide, 2,2,6,6-tetramethyl-4-piperidone, tiron, catalase, bathocuproine, or methional to the dopamine/Cu(II) reaction mixture resulted in a substantial decrease (>90%) in oxidation DNA product levels, indicating a role for singlet oxygen, superoxide, H(2)O(2), Cu(I), and Cu(I)OOH in their formation. Whereas the addition of N-tert-butyl-α-phenylnitrone significantly decreased (67%) dopamine-mediated oxidatively damaged DNA, three other hydroxyl radical scavengers, ascorbic acid, sodium benzoate, and mannitol, had little to no effect on these oxidation DNA product levels, suggesting that free hydroxyl radicals may have limited involvement in this dopamine/Cu(II)-mediated oxidatively generated DNA damage. These

  19. 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....

  20. 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

  1. The oxygen-rich postnatal environment induces cardiomyocyte cell-cycle arrest through DNA damage response.

    Science.gov (United States)

    Puente, Bao N; Kimura, Wataru; Muralidhar, Shalini A; Moon, Jesung; Amatruda, James F; Phelps, Kate L; Grinsfelder, David; Rothermel, Beverly A; Chen, Rui; Garcia, Joseph A; Santos, Celio X; Thet, SuWannee; Mori, Eiichiro; Kinter, Michael T; Rindler, Paul M; Zacchigna, Serena; Mukherjee, Shibani; Chen, David J; Mahmoud, Ahmed I; Giacca, Mauro; Rabinovitch, Peter S; Aroumougame, Asaithamby; Shah, Ajay M; Szweda, Luke I; Sadek, Hesham A

    2014-04-24

    The mammalian heart has a remarkable regenerative capacity for a short period of time after birth, after which the majority of cardiomyocytes permanently exit cell cycle. We sought to determine the primary postnatal event that results in cardiomyocyte cell-cycle arrest. We hypothesized that transition to the oxygen-rich postnatal environment is the upstream signal that results in cell-cycle arrest of cardiomyocytes. Here, we show that reactive oxygen species (ROS), oxidative DNA damage, and DNA damage response (DDR) markers significantly increase in the heart during the first postnatal week. Intriguingly, postnatal hypoxemia, ROS scavenging, or inhibition of DDR all prolong the postnatal proliferative window of cardiomyocytes, whereas hyperoxemia and ROS generators shorten it. These findings uncover a protective mechanism that mediates cardiomyocyte cell-cycle arrest in exchange for utilization of oxygen-dependent aerobic metabolism. Reduction of mitochondrial-dependent oxidative stress should be an important component of cardiomyocyte proliferation-based therapeutic approaches. Copyright © 2014 Elsevier Inc. All rights reserved.

  2. 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.

  3. Atomic Oxygen Treatment as a Method of Recovering Smoke Damaged Paintings

    Science.gov (United States)

    Rutledge, Sharon K.; Banks, Bruce A.; Forkapa, Mark; Stueber, Thomas; Sechkar, Edward; Malinowski, Kevin

    1998-01-01

    Smoke damage, as a result of a fire, can be difficult to remove from some types of painting media without causing swelling, leaching or pigment movement or removal. A non-contact technique has been developed which can remove soot from the surface of a painting by use of a gently flowing gas containing atomic oxygen. The atomic oxygen chemically reacts with the soot on the surface creating gasses such as carbon monoxide and carbon dioxide which can be removed through the use of an exhaust system. The reaction is limited to the surface so that the process can be timed to stop when the paint layer is reached. Atomic oxygen is a primary component of the low Earth orbital environment, but can be generated on Earth through various methods. This paper will discuss the results of atomic oxygen treatment of soot exposed acrylic gesso, ink on paper, and a varnished oil painting. Reflectance measurements were used to characterize the surfaces before and after treatment.

  4. Atomic Oxygen Treatment as a Method of Recovering Smoke Damaged Paintings. Revised

    Science.gov (United States)

    Rutledge, Sharon K.; Banks, Bruce A.; Forkapa, Mark; Stueber, Thomas; Sechkar, Edward; Malinowski, Kevin

    1999-01-01

    A noncontact technique is described that uses atomic oxygen, generated under low pressure in the presence of nitrogen, to remove soot and charred varnish from the surface of a painting. The process, which involves surface oxidation, permits control of the amount of surface material removed. The effectiveness of the process was evaluated by reflectance measurements from selected areas made during the removal of soot from acrylic gesso, ink on paper, and varnished oil paint substrates. For the latter substrate, treatment also involved the removal of damaged varnish and paint binder from the surface.

  5. 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.

  6. Furfural induces reactive oxygen species accumulation and cellular damage in Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    Slininger Patricia J

    2010-01-01

    Full Text Available Abstract Background Biofuels offer a viable alternative to petroleum-based fuel. However, current methods are not sufficient and the technology required in order to use lignocellulosic biomass as a fermentation substrate faces several challenges. One challenge is the need for a robust fermentative microorganism that can tolerate the inhibitors present during lignocellulosic fermentation. These inhibitors include the furan aldehyde, furfural, which is released as a byproduct of pentose dehydration during the weak acid pretreatment of lignocellulose. In order to survive in the presence of furfural, yeast cells need not only to reduce furfural to the less toxic furan methanol, but also to protect themselves and repair any damage caused by the furfural. Since furfural tolerance in yeast requires a functional pentose phosphate pathway (PPP, and the PPP is associated with reactive oxygen species (ROS tolerance, we decided to investigate whether or not furfural induces ROS and its related cellular damage in yeast. Results We demonstrated that furfural induces the accumulation of ROS in Saccharomyces cerevisiae. In addition, furfural was shown to cause cellular damage that is consistent with ROS accumulation in cells which includes damage to mitochondria and vacuole membranes, the actin cytoskeleton and nuclear chromatin. The furfural-induced damage is less severe when yeast are grown in a furfural concentration (25 mM that allows for eventual growth after an extended lag compared to a concentration of furfural (50 mM that prevents growth. Conclusion These data suggest that when yeast cells encounter the inhibitor furfural, they not only need to reduce furfural into furan methanol but also to protect themselves from the cellular effects of furfural and repair any damage caused. The reduced cellular damage seen at 25 mM furfural compared to 50 mM furfural may be linked to the observation that at 25 mM furfural yeast were able to exit the furfural

  7. Atomic Oxygen Treatment Technique for Removal of Smoke Damage from Paintings

    Science.gov (United States)

    Rutledge, S. K.; Banks, B. A.

    1997-01-01

    Soot deposits that can accumulate on surfaces of a painting during a fire can be difficult to clean from some types of paintings without damaging the underlying paint layers. A non-contact technique has been developed which can remove the soot by allowing a gas containing atomic oxygen to flow over the surface and chemically react with the soot to form carbon monoxide and carbon dioxide. The reaction is limited to the surface, so the underlying paint is not touched. The process can be controlled so that the cleaning can be stopped once the paint surface is reached. This paper describes the smoke exposure and cleaning of untreated canvas, acrylic gesso, and sections of an oil painting using this technique. The samples were characterized by optical microscopy and reflectance spectroscopy.

  8. Cysteine protects rabbit spermatozoa against reactive oxygen species-induced damages.

    Science.gov (United States)

    Zhu, Zhendong; Ren, Zhanjun; Fan, Xiaoteng; Pan, Yang; Lv, Shan; Pan, Chuanying; Lei, Anmin; Zeng, Wenxian

    2017-01-01

    The process of cryopreservation results in over-production of reactive oxygen species, which is extremely detrimental to spermatozoa. The aim of this study was to investigate whether addition of cysteine to freezing extender would facilitate the cryosurvival of rabbit spermatozoa, and if so, how cysteine protects spermatozoa from cryodamages. Freshly ejaculated semen was diluted with Tris-citrate-glucose extender supplemented with different concentrations of cysteine. The motility, intact acrosomes, membrane integrity, mitochondrial potentials, 8-hydroxyguanosine level and sperm-zona pellucida binding capacity were examined. Furthermore, glutathione peroxidase (GPx) activity, glutathione content (GSH), and level of reactive oxygen species (ROS) and hydrogen peroxide of spermatozoa were analyzed. The values of motility, intact acrosomes, membrane integrity, mitochondrial potentials and sperm-zona pellucida binding capacity of the frozen-thawed spermatozoa in the treatment of cysteine were significantly higher than those of the control. Addition of cysteine to extenders improved the GPx activity and GSH content of spermatozoa, while lowered the ROS, DNA oxidative alterations and lipid peroxidation level, which makes spermatozoa avoid ROS to attack DNA, the plasma membrane and mitochondria. In conclusion, cysteine protects spermatozoa against ROS-induced damages during cryopreservation and post-thaw incubation. Addition of cysteine is recommended to facilitate the improvement of semen preservation for the rabbit breeding industry.

  9. Regulation of radiation protective agents on cell damage induced by reactive oxygen species

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jeong Hee; Lee, Si Eun; Ju, Eun Mi; Gao, Eu Feng [Kyung Hee University, Seoul (Korea)

    2002-04-01

    In this study, we developed candidates of new radio-protective agents and elucidated the regulation mechanism of these candidates on cell damage induced by reactive oxygen species. The methanol extracts and ethylacetate fractions of NP-1, NP-5, NP-7, NP-11, NP-12 and NP-14 showed higher radical scavenging activity. The extracts of NP-7, NP-12 and NP-14 showed strong protective effect against oxidative damage induced by UV and H{sub 2}O{sub 2}. The most of samples enhanced SOD, CAT and GPX activity in V79-4 cells. The protective effect of samples on H{sub 2}O{sub 2}-induced apoptosis was observed with microscope and flow cytometer. Cells exposed to H{sub 2}O{sub 2} exhibit distinct morphological features of programmed cell death, such as nuclear fragmentation and increase in the percentage of cells with a sub-G1 DNA content. However, cells which was pretreated with samples significantly reduced the characteristics of apoptotic cells. Their morphological observation and DNA profiles were similar to those of the control cells. NP-14 which had excellent antioxidant activity restored G2/M arrest induced by oxidative stress. These data suggested that natural medicinal plants protected H{sub 2}O{sub 2}-induced apoptosis. 42 refs., 29 figs., 11 tabs. (Author)

  10. Low Doses of Oxygen Ion Irradiation Cause Acute Damage to Hematopoietic Cells in Mice.

    Directory of Open Access Journals (Sweden)

    Jianhui Chang

    Full Text Available One of the major health risks to astronauts is radiation on long-duration space missions. Space radiation from sun and galactic cosmic rays consists primarily of 85% protons, 14% helium nuclei and 1% high-energy high-charge (HZE particles, such as oxygen (16O, carbon, silicon, and iron ions. HZE particles exhibit dense linear tracks of ionization associated with clustered DNA damage and often high relative biological effectiveness (RBE. Therefore, new knowledge of risks from HZE particle exposures must be obtained. In the present study, we investigated the acute effects of low doses of 16O irradiation on the hematopoietic system. Specifically, we exposed C57BL/6J mice to 0.1, 0.25 and 1.0 Gy whole body 16O (600 MeV/n irradiation and examined the effects on peripheral blood (PB cells, and bone marrow (BM hematopoietic stem cells (HSCs and hematopoietic progenitor cells (HPCs at two weeks after the exposure. The results showed that the numbers of white blood cells, lymphocytes, monocytes, neutrophils and platelets were significantly decreased in PB after exposure to 1.0 Gy, but not to 0.1 or 0.25 Gy. However, both the frequency and number of HPCs and HSCs were reduced in a radiation dose-dependent manner in comparison to un-irradiated controls. Furthermore, HPCs and HSCs from irradiated mice exhibited a significant reduction in clonogenic function determined by the colony-forming and cobblestone area-forming cell assays. These acute adverse effects of 16O irradiation on HSCs coincided with an increased production of reactive oxygen species (ROS, enhanced cell cycle entry of quiescent HSCs, and increased DNA damage. However, none of the 16O exposures induced apoptosis in HSCs. These data suggest that exposure to low doses of 16O irradiation induces acute BM injury in a dose-dependent manner primarily via increasing ROS production, cell cycling, and DNA damage in HSCs. This finding may aid in developing novel strategies in the protection of the

  11. 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

  12. Mobile phone radiation induces reactive oxygen species production and DNA damage in human spermatozoa in vitro.

    Directory of Open Access Journals (Sweden)

    Geoffry N De Iuliis

    Full Text Available BACKGROUND: In recent times there has been some controversy over the impact of electromagnetic radiation on human health. The significance of mobile phone radiation on male reproduction is a key element of this debate since several studies have suggested a relationship between mobile phone use and semen quality. The potential mechanisms involved have not been established, however, human spermatozoa are known to be particularly vulnerable to oxidative stress by virtue of the abundant availability of substrates for free radical attack and the lack of cytoplasmic space to accommodate antioxidant enzymes. Moreover, the induction of oxidative stress in these cells not only perturbs their capacity for fertilization but also contributes to sperm DNA damage. The latter has, in turn, been linked with poor fertility, an increased incidence of miscarriage and morbidity in the offspring, including childhood cancer. In light of these associations, we have analyzed the influence of RF-EMR on the cell biology of human spermatozoa in vitro. PRINCIPAL FINDINGS: Purified human spermatozoa were exposed to radio-frequency electromagnetic radiation (RF-EMR tuned to 1.8 GHz and covering a range of specific absorption rates (SAR from 0.4 W/kg to 27.5 W/kg. In step with increasing SAR, motility and vitality were significantly reduced after RF-EMR exposure, while the mitochondrial generation of reactive oxygen species and DNA fragmentation were significantly elevated (P<0.001. Furthermore, we also observed highly significant relationships between SAR, the oxidative DNA damage bio-marker, 8-OH-dG, and DNA fragmentation after RF-EMR exposure. CONCLUSIONS: RF-EMR in both the power density and frequency range of mobile phones enhances mitochondrial reactive oxygen species generation by human spermatozoa, decreasing the motility and vitality of these cells while stimulating DNA base adduct formation and, ultimately DNA fragmentation. These findings have clear implications

  13. Robust DNA Damage Response and Elevated Reactive Oxygen Species in TINF2-Mutated Dyskeratosis Congenita Cells.

    Science.gov (United States)

    Pereboeva, Larisa; Hubbard, Meredith; Goldman, Frederick D; Westin, Erik R

    2016-01-01

    Dyskeratosis Congenita (DC) is an inherited multisystem premature aging disorder with characteristic skin and mucosal findings as well as a predisposition to cancer and bone marrow failure. DC arises due to gene mutations associated with the telomerase complex or telomere maintenance, resulting in critically shortened telomeres. The pathogenesis of DC, as well as several congenital bone marrow failure (BMF) syndromes, converges on the DNA damage response (DDR) pathway and subsequent elevation of reactive oxygen species (ROS). Historically, DC patients have had poor outcomes following bone marrow transplantation (BMT), perhaps as a consequence of an underlying DNA hypersensitivity to cytotoxic agents. Previously, we demonstrated an activated DDR and increased ROS, augmented by chemotherapy and radiation, in somatic cells isolated from DC patients with a mutation in the RNA component of telomerase, TERC. The current study was undertaken to determine whether previous findings related to ROS and DDR in TERC patients' cells could be extended to other DC mutations. Of particular interest was whether an antioxidant approach could counter increased ROS and decrease DC pathologies. To test this, we examined lymphocytes from DC patients from different DC mutations (TERT, TINF2, and TERC) for the presence of an active DDR and increased ROS. All DC mutations led to increased steady-state p53 (2-fold to 10-fold) and ROS (1.5-fold to 2-fold). Upon exposure to ionizing radiation (XRT), DC cells increased in both DDR and ROS to a significant degree. Exposing DC cells to hydrogen peroxide also revealed that DC cells maintain a significant oxidant burden compared to controls (1.5-fold to 3-fold). DC cell culture supplemented with N-acetylcysteine, or alternatively grown in low oxygen, afforded significant proliferative benefits (proliferation: maximum 2-fold increase; NAC: 5-fold p53 decrease; low oxygen: maximum 3.5-fold p53 decrease). Together, our data supports a mechanism

  14. Robust DNA Damage Response and Elevated Reactive Oxygen Species in TINF2-Mutated Dyskeratosis Congenita Cells.

    Directory of Open Access Journals (Sweden)

    Larisa Pereboeva

    Full Text Available Dyskeratosis Congenita (DC is an inherited multisystem premature aging disorder with characteristic skin and mucosal findings as well as a predisposition to cancer and bone marrow failure. DC arises due to gene mutations associated with the telomerase complex or telomere maintenance, resulting in critically shortened telomeres. The pathogenesis of DC, as well as several congenital bone marrow failure (BMF syndromes, converges on the DNA damage response (DDR pathway and subsequent elevation of reactive oxygen species (ROS. Historically, DC patients have had poor outcomes following bone marrow transplantation (BMT, perhaps as a consequence of an underlying DNA hypersensitivity to cytotoxic agents. Previously, we demonstrated an activated DDR and increased ROS, augmented by chemotherapy and radiation, in somatic cells isolated from DC patients with a mutation in the RNA component of telomerase, TERC. The current study was undertaken to determine whether previous findings related to ROS and DDR in TERC patients' cells could be extended to other DC mutations. Of particular interest was whether an antioxidant approach could counter increased ROS and decrease DC pathologies. To test this, we examined lymphocytes from DC patients from different DC mutations (TERT, TINF2, and TERC for the presence of an active DDR and increased ROS. All DC mutations led to increased steady-state p53 (2-fold to 10-fold and ROS (1.5-fold to 2-fold. Upon exposure to ionizing radiation (XRT, DC cells increased in both DDR and ROS to a significant degree. Exposing DC cells to hydrogen peroxide also revealed that DC cells maintain a significant oxidant burden compared to controls (1.5-fold to 3-fold. DC cell culture supplemented with N-acetylcysteine, or alternatively grown in low oxygen, afforded significant proliferative benefits (proliferation: maximum 2-fold increase; NAC: 5-fold p53 decrease; low oxygen: maximum 3.5-fold p53 decrease. Together, our data supports a

  15. Radiation-induced DNA damage in tumors and normal tissues. II. Influence of dose, residual DNA damage and physiological factors in oxygenated cells

    International Nuclear Information System (INIS)

    Zhang, H.; Wheeler, K.T.

    1994-01-01

    Detection and quantification of hypoxic cells in solid tumors is important for many experimental and clinical situations. Several laboratories, including ours, have suggested that assays which measure radiation-induced DNA strand breaks and DNA-protein crosslinks (DPCs) might be used to detect or quantify hypoxic cells in tumors and normal tissues. Recently, we demonstrated the feasibility of using an alkaline elution assay that measures strand breaks and DPCs to detect and/or quantify hypoxic cells in tissues. For this approach to be valid, DPCs must not be formed to any great extent in irradiated oxygenated cells, and the formation and repair of strand breaks and DPCs in oxygenated cells must not be modified appreciably by physiological factors (e.g., temperature, pH and nutrient depletion) that are often found in solid tumors. To address these issues, two sets of experiments were performed. In one set of experiments, oxygenated 9L cells in tissue culture, subcutaneous 9L tumors and rat cerebella were irradiated with doses of 15 or 50 Gy and allowed to repair until the residual strand break damage was low enough to detect DPCs. In another set of experiments, oxygenated exponentially growing or plateau-phase 9L cells in tissue culture were irradiated with a dose of 15 Gy at 37 or 20 degrees C, while the cells were maintained at a pH of either 6.6 or 7.3. DNA-protein crosslinks were formed in oxygenated cells about 100 times less efficiently than in hypoxic cells. In addition, temperature, pH, nutrient depletion and growth phase did not appreciably alter the formation and repair of strand breaks or the formation of DPCs in oxygenated 9L cells. These results support the use of this DNA damage assay for the detection and quantification of hypoxic cells in solid tumors. 27 refs., 5 tabs

  16. Zinc oxide nanoparticle induced autophagic cell death and mitochondrial damage via reactive oxygen species generation.

    Science.gov (United States)

    Yu, Kyeong-Nam; Yoon, Tae-Jong; Minai-Tehrani, Arash; Kim, Ji-Eun; Park, Soo Jin; Jeong, Min Sook; Ha, Shin-Woo; Lee, Jin-Kyu; Kim, Jun Sung; Cho, Myung-Haing

    2013-06-01

    Zinc oxide nanoparticles (ZnO-np) are used in an increasing number of industrial products such as paint, coating and cosmetics, and in other biological applications. There have been many suggestions of a ZnO-np toxicity paradigm but the underlying molecular mechanisms about the toxicity of ZnO-np remain unclear. This study was done to determine the potential toxicity of ZnO-np and to assess the toxicity mechanism in normal skin cells. Synthesized ZnO-np generated reactive oxygen species (ROS), as determined by electron spin resonance. After uptake into cells, ZnO-np induced ROS in a concentration- and time-dependent manner. To demonstrate ZnO-np toxicity mechanism related to ROS, we detected abnormal autophagic vacuoles accumulation and mitochondria dysfunction after ZnO-np treatment. Furthermore mitochondria membrane potential and adenosine-5'-triphosphate (ATP) production are decreased for culture with ZnO-np. We conclude that ZnO-np leads to cell death through autophagic vacuole accumulation and mitochondria damage in normal skin cells via ROS induction. Accordingly, ZnO-np may cause toxicity and the results highlight and need for careful regulation of ZnO-np production and use. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Neuroprotective effects of cactus polysaccharide on oxygen and glucose deprivation induced damage in rat brain slices.

    Science.gov (United States)

    Huang, Xianju; Li, Qin; Zhang, Yingpei; Lü, Qing; Guo, Lianjun; Huang, Lin; He, Zhi

    2008-06-01

    1. The neuroprotective effect of cactus polysaccharide (CP) on oxygen and glucose deprivation (OGD) and reoxygenation (REO)-induced damage in the cortical and hippocampal slices of rat brain was investigated. 2. Cell viability was evaluated by using the 2, 3, 5-triphenyl tetrazolium chloride (TTC) method. The fluorescence of propidium iodide (PI) staining was used for quantification of cellular survival, and lactate dehydrogenase (LDH) activity in incubation medium was assessed by LDH assay to evaluate the degree of injury. 3. The OGD ischemic condition significantly decreased cellular viability and increased LDH release in the incubation medium. CP (0.2 mg/l approximately 2 mg/l) protected brain slices from OGD injury in a dosage dependent manner as demonstrated by increased A 490 value of TTC, decreased PI intensity and LDH release. At the above concentration, CP also prevented the increase of nitric oxide (NO) content and inducible nitric oxide synthase (iNOS) activity induced by OGD. 4. CP can protect the brain slices (cortical and hippocampus) against injury induced by OGD. Its neuroprotective effect may be partly mediated by the NO/iNOS system induced by OGD insult.

  18. Green synthesized silver nanoparticles destroy multidrug resistant bacteria via reactive oxygen species mediated membrane damage

    Directory of Open Access Journals (Sweden)

    Balaram Das

    2017-09-01

    Full Text Available The growing need of antimicrobial agent for novel therapies against multi-drug resistant bacteria has drawn researchers to green nanotechnology. Especially, eco-friendly biosynthesis of silver nanoparticles (Ag NPs has shown its interesting impact against bacterial infection in laboratory research. In this study, a simple method was developed to form Ag NPs at room temperature, bio-reduction of silver ions from silver nitrate salt by leaf extract from Ocimum gratissimum. The Ag NPs appear to be capped with plant proteins, but are otherwise highly crystalline and pure. The Ag NPs have a zeta potential of −15 mV, a hydrodynamic diameter of 31 nm with polydispersity index of 0.65, and dry sizes of 18 ± 3 nm and 16 ± 2 nm, based on scanning and transmission electron microscopy respectively. The minimum inhibitory concentration (MIC of the Ag NPs against a multi-drug resistant Escherichia coli was 4 μg/mL and the minimum bactericidal concentration (MBC was 8 μg/mL, while the MIC and MBC against a resistant strain of Staphylococcus aureus were slightly higher at 8 μg/mL and 16 μg/mL respectively. Further, the Ag NPs inhibited biofilm formation by both Escherichia coli and S. aureus at concentrations similar to the MIC for each strain. Treatment of E. coli and S. aureus with Ag NPs resulted in damage to the surface of the cells and the production of reactive oxygen species. Both mechanisms likely contribute to bacterial cell death. In summary, this new method appears promising for green biosynthesis of pure Ag NPs with potent antimicrobial activity.

  19. Protein nitration, lipid peroxidation and DNA damage at high altitude in acclimatized lowlanders and native highlanders: relation with oxygen consumption.

    Science.gov (United States)

    Sinha, Sanchari; Dutta, Arkadeb; Singh, Som Nath; Ray, Uday Sankar

    2010-04-30

    Reactive oxygen and nitrogen species have been reported to be increased due to hypobaric hypoxia. It was hypothesized that lowlanders are more susceptible to protein nitration, lipid peroxidation and DNA damage at high altitude than highlanders and formation of these biomarkers may have strong correlation with oxygen consumption. Male volunteers were randomly selected and categorized into 3 groups, i.e. lowlanders at sea level (LL-SL, n=10), lowlanders at an altitude of 4560 m (LL-HA, n=10) and highlanders (HAN, n=10). Volunteers performed maximal aerobic exercise. Resting and post-exercise blood samples were taken at sea level and high altitude. Both resting and maximum oxygen consumption showed positive correlation with stress markers. LL-HA showed increased 3-nitrotyrosine and lipid hydroperoxide than LL-SL at rest. 3-Nitrotyrosine and lipid hydroperoxide increased after exercise in 3 groups, but percentage increase was higher in HAN than LL-SL and LL-HA. LL-SL and HAN showed significant DNA damage after exercise. Results indicate that resting oxygen consumption is positively correlated with nitrosative and oxidative stress markers irrespective of environmental condition and adaptation levels. Lowlanders have shown higher susceptibility to hypoxic insult than highlanders at rest, but when subjected to exercise test, they showed better tolerance to hypoxia than highlanders. (c) 2010 Elsevier B.V. All rights reserved.

  20. 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.

  1. 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

  2. Evaluation of N-acetylcysteine and methylprednisolone as therapies for oxygen and acrolein-induced lung damage

    Energy Technology Data Exchange (ETDEWEB)

    Critchley, J.A.J.H. (Univ. of Edinburgh (England)); Beeley, J.M.; Clark, R.J.; Buchanan, J.D. (Royal Naval Hospital Hoslar, Gosport (England)); Summerfield, M.; Bell, S. (Admiralty Research Establishment, Alverstoke (England)); Spurlock, M.S.; Edginton, J.A.G. (Chemical Defence Establishment, Porton Down (England))

    1990-04-01

    Reactive oxidizing species are implicated in the etiology of a range of inhalational pulmonary injuries. Consequently, various free radical scavengers have been tested as potential prophylactic agents. The sulfydryl compound, N-acetylcysteine (NAC) is the only such compound clinically available for use in realistic dosages, and it is well established as an effective antidote for the hepatic and renal toxicity of paracetamol. Another approach in pulmonary injury prophylaxis is methylprednisolone therapy. The authors evaluated NAC and methylprednisolone in two rats models of inhalation injury: 40-hr exposure to >97% oxygen at 1.1 bar and 15-min exposure to acrolein vapor (210 ppm). The increases in lung wet/dry weight ratios, seen with both oxygen and acrolein toxicity were reduced with both treatments. However, with oxygen, NAC therapy was associated with considerably increased mortality and histological changes. Furthermore, IP NAC administration resulted in large volumes of ascitic fluid. With acrolein, IV, NAC had no significant effect on mortality or pulmonary histological damage. Methylprednisolone had no beneficial effects on either the mortality or histological damage observed in either toxicity model. They caution against the ad hoc use of NAC in the management of inhalational pulmonary injury.

  3. Vorinostat induces reactive oxygen species and DNA damage in acute myeloid leukemia cells.

    Directory of Open Access Journals (Sweden)

    Luca A Petruccelli

    Full Text Available Histone deacetylase inhibitors (HDACi are promising anti-cancer agents, however, their mechanisms of action remain unclear. In acute myeloid leukemia (AML cells, HDACi have been reported to arrest growth and induce apoptosis. In this study, we elucidate details of the DNA damage induced by the HDACi vorinostat in AML cells. At clinically relevant concentrations, vorinostat induces double-strand breaks and oxidative DNA damage in AML cell lines. Additionally, AML patient blasts treated with vorinostat display increased DNA damage, followed by an increase in caspase-3/7 activity and a reduction in cell viability. Vorinostat-induced DNA damage is followed by a G2-M arrest and eventually apoptosis. We found that pre-treatment with the antioxidant N-acetyl cysteine (NAC reduces vorinostat-induced DNA double strand breaks, G2-M arrest and apoptosis. These data implicate DNA damage as an important mechanism in vorinostat-induced growth arrest and apoptosis in both AML cell lines and patient-derived blasts. This supports the continued study and development of vorinostat in AMLs that may be sensitive to DNA-damaging agents and as a combination therapy with ionizing radiation and/or other DNA damaging agents.

  4. Vorinostat Induces Reactive Oxygen Species and DNA Damage in Acute Myeloid Leukemia Cells

    Science.gov (United States)

    Pettersson, Filippa; Retrouvey, Hélène; Skoulikas, Sophia; Miller, Wilson H.

    2011-01-01

    Histone deacetylase inhibitors (HDACi) are promising anti-cancer agents, however, their mechanisms of action remain unclear. In acute myeloid leukemia (AML) cells, HDACi have been reported to arrest growth and induce apoptosis. In this study, we elucidate details of the DNA damage induced by the HDACi vorinostat in AML cells. At clinically relevant concentrations, vorinostat induces double-strand breaks and oxidative DNA damage in AML cell lines. Additionally, AML patient blasts treated with vorinostat display increased DNA damage, followed by an increase in caspase-3/7 activity and a reduction in cell viability. Vorinostat-induced DNA damage is followed by a G2-M arrest and eventually apoptosis. We found that pre-treatment with the antioxidant N-acetyl cysteine (NAC) reduces vorinostat-induced DNA double strand breaks, G2-M arrest and apoptosis. These data implicate DNA damage as an important mechanism in vorinostat-induced growth arrest and apoptosis in both AML cell lines and patient-derived blasts. This supports the continued study and development of vorinostat in AMLs that may be sensitive to DNA-damaging agents and as a combination therapy with ionizing radiation and/or other DNA damaging agents. PMID:21695163

  5. Attenuating brain inflammation, ischemia, and oxidative damage by hyperbaric oxygen in diabetic rats after heat stroke

    Directory of Open Access Journals (Sweden)

    Kai-Li Lee

    2013-08-01

    Conclusion: Our results suggest that, in diabetic animals, HBO2 therapy may improve outcomes of HS in part by reducing heat-induced activated inflammation and ischemic and oxidative damage in the hypothalamus and other brain regions.

  6. Influence of pH, Oxygen, and Humic Substances on Ability of Sunlight To Damage Fecal Coliforms in Waste Stabilization Pond Water

    OpenAIRE

    Curtis, Thomas P.; Mara, D. Duncan; Silva, Salomao A.

    1992-01-01

    Simple beaker experiments established that light damages fecal coliforms in waste stabilization ponds by an oxygen-mediated exogenous photosensitization. Wavelengths of up to 700 nm were able to damage bacteria. The ability of wavelengths of >425 nm to damage fecal coliforms was dependent on the presence of dissolved sensitizers. The sensitizers were ubiquitous in raw sewage, unaffected by sewage treatment, not derivatives of bacteriochlorophyll or chlorophyll, absorbed well in UV light, and ...

  7. 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)

  8. 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.

  9. Generation of Oxygen Free Radicals by Proflavine: Implication in Protein Degradation

    Directory of Open Access Journals (Sweden)

    Mansour K.M. Gatasheh

    2017-07-01

    Full Text Available Proflavine, an acridine dye, is a known DNA intercalating agent. In the present study, we show that proflavine alone on photoillumination can generate reactive oxygen species (ROS. These proflavine-derived ROS cause damage to proteins, and this effect is enhanced when the divalent metal ion Cu (II is included in the reaction. Bathocuproine, a specific Cu (I sequestering agent, when present in the reaction mixture containing Cu (II, was found to inhibit the protein degradation, showing that Cu (I is an essential intermediate in the reaction. The effect of several scavengers of ROS such as superoxide dismutase, sodium azide, potassium iodide, and thiourea were examined on the protein damaging reaction. Potassium iodide was found to be the most effective in inhibiting protein damage followed by sodium azide and thiourea. Our results indicate the involvement of superoxide, singlet oxygen, triplet oxygen, and hydroxyl radicals in proflavine-induced damage to proteins.

  10. Lung and Diaphragm Damage at Varying Oxygen Levels and Ventilator Modes Pst Hemorrhagic

    Science.gov (United States)

    2011-12-20

    positive end-expiratory pressure = 1 cm H2O, peak inspiratory pressure = 8 cm H2O, and inspired tidal volume = 4.0 mL. Hemodynamics (systolic...intensities are detected and differentiated based on cell type. For example, Q4 is the cell count for 179 neutrophils that have positive fluorescence for...37132007000600008 [pii] Vento, M., Moro, M., Escrig, R., Arruza, L., Villar, G., Izquierdo, I., . . . Asensi, M. A. (2009). Preterm Resuscitation With Low Oxygen

  11. Protection against post-irradiation oxygen-dependent damage in barley seeds by catalase and hydrogen peroxide: probable radiation chemistry

    International Nuclear Information System (INIS)

    Singh, S.P.; Kesavan, P.C.

    1990-01-01

    Influence of varying concentration of catalase and H 2 O 2 administered individually and in combination treatment during post-hydration on the oxygen-dependent and -independent pathways of damage was assessed in dry barley seeds irradiated in vacuo with 350 Gy of 60 Co gammarays. Both catalase (100 to 500 units/ml) and H 2 O 2 (0.001 to 0.1 mM) afforded significant radioprotection against the post-irradiation O 2 -dependent damage. However, a combination treatment (300 units/ml of catalase and 0.01 mM of H 2 O 2 ) afforded significantl y more protection than either of the additives individually. None of the concentrations of catalase exerted any effect on the O 2 -independent pathway, whereas H 2 O 2 at higher concentrations (1 and 10 mM) significantly potentiated both the O 2 -dependent as well as the -independent components of radiation damage. These observations are better explicable in terms of radiation chemistry. (author). 16 refs., 3 tabs

  12. Laser phototherapy triggers the production of reactive oxygen species in oral epithelial cells without inducing DNA damage.

    Science.gov (United States)

    Dillenburg, Caroline Siviero; Almeida, Luciana Oliveira; Martins, Manoela Domingues; Squarize, Cristiane Helena; Castilho, Rogerio Moraes

    2014-04-01

    Laser phototherapy (LPT) is widely used in clinical practice to accelerate healing. Although the use of LPT has advantages, the molecular mechanisms involved in the process of accelerated healing and the safety concerns associated with LPT are still poorly understood. We investigated the physiological effects of LPT irradiation on the production and accumulation of reactive oxygen species (ROS), genomic instability, and deoxyribose nucleic acid (DNA) damage in human epithelial cells. In contrast to a high energy density (20  J/cm²), laser administered at a low energy density (4  J/cm²) resulted in the accumulation of ROS. Interestingly, 4  J/cm² of LPT did not induce DNA damage, genomic instability, or nuclear influx of the BRCA1 DNA damage repair protein, a known genome protective molecule that actively participates in DNA repair. Our results suggest that administration of low energy densities of LPT induces the accumulation of safe levels of ROS, which may explain the accelerated healing results observed in patients. These findings indicate that epithelial cells have an endowed molecular circuitry that responds to LPT by physiologically inducing accumulation of ROS, which triggers accelerated healing. Importantly, our results suggest that low energy densities of LPT can serve as a safe therapy to accelerate epithelial healing.

  13. Zinc protects sperm from being damaged by reactive oxygen species in assisted reproduction techniques.

    Science.gov (United States)

    Wu, Jinxiang; Wu, Shiqiang; Xie, Yuanzhi; Wang, Zhengyao; Wu, Ruiyun; Cai, Junfeng; Luo, Xiangmin; Huang, Suzhen; You, Liuxia

    2015-04-01

    The aim of this study was to explore the effect of zinc on hydrogen peroxide-induced sperm damage in assisted reproduction techniques. First, sperms were selected from semen samples of 20 healthy men prepared by density gradient centrifugation. Selected sperm were treated with either 0.001% H(2)O(2), 12.5 nM ZnCL(2), 0.001% H(2)O(2) + 12.5 nM ZnCL(2) or 0.9% NaCl(2) (control). After this treatment, the motility, viability, membrane integrity and DNA fragmentation of sperms in each group were analysed by Goodline sperm detection system, optical microscopy and sperm DNA fragmentation assay. Poorer motility, vitality, membrane integrity and more DNA damage were found in sperms treated by H(2)O(2), compared with control. When sperms were treated with both H(2)O(2) and zinc, however, all indicators were improved compared with H(2)O(2) alone. There was a close association between oxidative stimulation and sperm injury; zinc could inhibit hydrogen peroxide-induced damage of sperm in assisted reproductive technology. However, the presence of zinc in culture medium can decrease the sperm quality without addition of peroxide. Copyright © 2014 Reproductive Healthcare Ltd. Published by Elsevier Ltd. All rights reserved.

  14. A role for nuclear translocation of tripeptidyl-peptidase II in reactive oxygen species-dependent DNA damage responses

    International Nuclear Information System (INIS)

    Preta, Giulio; Klark, Rainier de; Glas, Rickard

    2009-01-01

    Responses to DNA damage are influenced by cellular metabolism through the continuous production of reactive oxygen species (ROS), of which most are by-products of mitochondrial respiration. ROS have a strong influence on signaling pathways during responses to DNA damage, by relatively unclear mechanisms. Previous reports have shown conflicting data on a possible role for tripeptidyl-peptidase II (TPPII), a large cytosolic peptidase, within the DNA damage response. Here we show that TPPII translocated into the nucleus in a p160-ROCK-dependent fashion in response to γ-irradiation, and that nuclear expression of TPPII was present in most γ-irradiated transformed cell lines. We used a panel of nine cell lines of diverse tissue origin, including four lymphoma cell lines (T, B and Hodgkins lymphoma), a melanoma, a sarcoma, a colon and two breast carcinomas, where seven out of nine cell lines showed nuclear TPPII expression after γ-irradiation. Further, this required cellular production of ROS; treatment with either N-acetyl-Cysteine (anti-oxidant) or Rotenone (inhibitor of mitochondrial respiration) inhibited nuclear accumulation of TPPII. The local density of cells was important for nuclear accumulation of TPPII at early time-points following γ-irradiation (at 1-4 h), indicating a bystander effect. Further, we showed that the peptide-based inhibitor Z-Gly-Leu-Ala-OH, but not its analogue Z-Gly-(D)-Leu-Ala-OH, excluded TPPII from the nucleus. This correlated with reduced nuclear expression of p53 as well as caspase-3 and -9 activation in γ-irradiated lymphoma cells. Our data suggest a role for TPPII in ROS-dependent DNA damage responses, through alteration of its localization from the cytosol into the nucleus.

  15. A role for nuclear translocation of tripeptidyl-peptidase II in reactive oxygen species-dependent DNA damage responses

    Energy Technology Data Exchange (ETDEWEB)

    Preta, Giulio; Klark, Rainier de [Center for Molecular Medicine (CMM), Department of Medicine, Karolinska Institutet, Karolinska University Hospital, 171 76 Stockholm (Sweden); Glas, Rickard, E-mail: rickard.glas@ki.se [Center for Molecular Medicine (CMM), Department of Medicine, Karolinska Institutet, Karolinska University Hospital, 171 76 Stockholm (Sweden)

    2009-11-27

    Responses to DNA damage are influenced by cellular metabolism through the continuous production of reactive oxygen species (ROS), of which most are by-products of mitochondrial respiration. ROS have a strong influence on signaling pathways during responses to DNA damage, by relatively unclear mechanisms. Previous reports have shown conflicting data on a possible role for tripeptidyl-peptidase II (TPPII), a large cytosolic peptidase, within the DNA damage response. Here we show that TPPII translocated into the nucleus in a p160-ROCK-dependent fashion in response to {gamma}-irradiation, and that nuclear expression of TPPII was present in most {gamma}-irradiated transformed cell lines. We used a panel of nine cell lines of diverse tissue origin, including four lymphoma cell lines (T, B and Hodgkins lymphoma), a melanoma, a sarcoma, a colon and two breast carcinomas, where seven out of nine cell lines showed nuclear TPPII expression after {gamma}-irradiation. Further, this required cellular production of ROS; treatment with either N-acetyl-Cysteine (anti-oxidant) or Rotenone (inhibitor of mitochondrial respiration) inhibited nuclear accumulation of TPPII. The local density of cells was important for nuclear accumulation of TPPII at early time-points following {gamma}-irradiation (at 1-4 h), indicating a bystander effect. Further, we showed that the peptide-based inhibitor Z-Gly-Leu-Ala-OH, but not its analogue Z-Gly-(D)-Leu-Ala-OH, excluded TPPII from the nucleus. This correlated with reduced nuclear expression of p53 as well as caspase-3 and -9 activation in {gamma}-irradiated lymphoma cells. Our data suggest a role for TPPII in ROS-dependent DNA damage responses, through alteration of its localization from the cytosol into the nucleus.

  16. The influence of oxygen on the induction of radiation damage in DNA in mammalian cells after sensitization by intracellular glutathione depletion

    International Nuclear Information System (INIS)

    Schans, G.P. van der; Vos, O.; Roos-Verheij, W.S.D.; Lohman, P.H.M.

    1986-05-01

    Treatment of mammalian cells with buthionine sulphoximine (BSO) or diethyl maleate (DEM) results in a decrease in the intracellular GSH (glutathione) and NPSH (non-protein-bound SH) levels. The effect of depletion of GSH and NPSH on radiosensitivity was studied in relation to the concentration of oxygen during irradiation. Single- and double-strand DNA breaks (ssb and dsb) and cell killing were used as criteria for radiation damage. Under aerobic conditions, BSO and DEM treatment gave a small sensitization of 10-20% for the 3 types of radiation damage. Also under severely hypoxic conditions (0.01 μM oxygen in the medium) the sensitizing effect of both compounds on the induction of ssb and dsb and on cell killing was small (0-30%). At somewhat higher concentrations of oxygen (0.5-10 μM) however, the sensitization amounted to about 90% for the induction of ssb and dsb and about 50% for cell killing. These results strengthen the widely accepted idea that intracellular SH-compounds compete with oxygen and other electron-affinic radiosensitizers with respect to reaction with radiation-induced damage, thus preventing the fixation of DNA damages by oxygen. These results imply that the extent to which SH-compounds affect the radiosensitivity of cells in vivo depends strongly on the local concentration of oxygen. (Auth.)

  17. Senescence, Stress, and Reactive Oxygen Species

    Directory of Open Access Journals (Sweden)

    Ivan Jajic

    2015-07-01

    Full Text Available Generation of reactive oxygen species (ROS is one of the earliest responses of plant cells to various biotic and abiotic stresses. ROS are capable of inducing cellular damage by oxidation of proteins, inactivation of enzymes, alterations in the gene expression, and decomposition of biomembranes. On the other hand, they also have a signaling role and changes in production of ROS can act as signals that change the transcription of genes that favor the acclimation of plants to abiotic stresses. Among the ROS, it is believed that H2O2 causes the largest changes in the levels of gene expression in plants. A wide range of plant responses has been found to be triggered by H2O2 such as acclimation to drought, photooxidative stress, and induction of senescence. Our knowledge on signaling roles of singlet oxygen (1O2 has been limited by its short lifetime, but recent experiments with a flu mutant demonstrated that singlet oxygen does not act primarily as a toxin but rather as a signal that activates several stress-response pathways. In this review we summarize the latest progress on the signaling roles of ROS during senescence and abiotic stresses and we give a short overview of the methods that can be used for their assessment.

  18. Senescence, Stress, and Reactive Oxygen Species

    Science.gov (United States)

    Jajic, Ivan; Sarna, Tadeusz; Strzalka, Kazimierz

    2015-01-01

    Generation of reactive oxygen species (ROS) is one of the earliest responses of plant cells to various biotic and abiotic stresses. ROS are capable of inducing cellular damage by oxidation of proteins, inactivation of enzymes, alterations in the gene expression, and decomposition of biomembranes. On the other hand, they also have a signaling role and changes in production of ROS can act as signals that change the transcription of genes that favor the acclimation of plants to abiotic stresses. Among the ROS, it is believed that H2O2 causes the largest changes in the levels of gene expression in plants. A wide range of plant responses has been found to be triggered by H2O2 such as acclimation to drought, photooxidative stress, and induction of senescence. Our knowledge on signaling roles of singlet oxygen (1O2) has been limited by its short lifetime, but recent experiments with a flu mutant demonstrated that singlet oxygen does not act primarily as a toxin but rather as a signal that activates several stress-response pathways. In this review we summarize the latest progress on the signaling roles of ROS during senescence and abiotic stresses and we give a short overview of the methods that can be used for their assessment. PMID:27135335

  19. Radiation damage studies on NaBi(WO4)2 single crystals through oxygen related defects

    International Nuclear Information System (INIS)

    Singh, S.G.; Tyagi, M.; Desai, D.G.; Singh, A.K.; Gadkari, S.C.

    2010-01-01

    Single crystals of NaBi(WO 4 ) 2 grown under different conditions were studied for their radiation hardness to high gamma radiation doses (10 5 and 10 6 Gy) employing high dose rates (∼2 Gy/s). Annealing studies in oxygen as well as in vacuum were carried out and a relation between oxygen defects and irradiation induced damages has been proposed. Induced absorption spectra of irradiated and annealed samples were calculated and 5 individual peaks around 3.1, 2.8, 2.6, 2 and 1.7 eV related to different defect centers have been identified. Recovery of the transmission characteristics after the heavy irradiation was monitored at room temperatures (20±2 o C) and the corresponding lifetime has been found to be about 50 days. The thermoluminescence glow curve has been recorded and the activation energy of the defect centers was calculated as 0.9 eV using an initial rising method.

  20. A redox hydrogel protects hydrogenase from high-potential deactivation and oxygen damage

    Science.gov (United States)

    Plumeré, Nicolas; Rüdiger, Olaf; Oughli, Alaa Alsheikh; Williams, Rhodri; Vivekananthan, Jeevanthi; Pöller, Sascha; Schuhmann, Wolfgang; Lubitz, Wolfgang

    2014-09-01

    Hydrogenases are nature's efficient catalysts for both the generation of energy via oxidation of molecular hydrogen and the production of hydrogen via the reduction of protons. However, their O2 sensitivity and deactivation at high potential limit their applications in practical devices, such as fuel cells. Here, we show that the integration of an O2-sensitive hydrogenase into a specifically designed viologen-based redox polymer protects the enzyme from O2 damage and high-potential deactivation. Electron transfer between the polymer-bound viologen moieties controls the potential applied to the active site of the hydrogenase and thus insulates the enzyme from excessive oxidative stress. Under catalytic turnover, electrons provided from the hydrogen oxidation reaction induce viologen-catalysed O2 reduction at the polymer surface, thus providing self-activated protection from O2. The advantages of this tandem protection are demonstrated using a single-compartment biofuel cell based on an O2-sensitive hydrogenase and H2/O2 mixed feed under anode-limiting conditions.

  1. Inhibition of oxygen-dependent radiation-induced damage by the nitroxide superoxide dismutase mimic, tempol

    Energy Technology Data Exchange (ETDEWEB)

    Mitchell, J.B.; DeGraff, W.; Kaufman, D.; Krishna, M.C.; Samuni, A.; Finkelstein, E.; Ahn, M.S.; Hahn, S.M.; Gamson, J.; Russo, A. (Radiobiology Section, National Cancer Institute, National Institutes of Health, Bethesda, MD (United States))

    1991-08-15

    Stable nitroxide radicals have been previously shown to function as superoxide dismutase (SOD)2 mimics and to protect mammalian cells against superoxide and hydrogen peroxide-mediated oxidative stress. These unique characteristics suggested that nitroxides, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (Tempol), might protect mammalian cells against ionizing radiation. Treating Chinese hamster cells under aerobic conditions with 5, 10, 50, and 100 mM Tempol 10 min prior to X-rays resulted in radiation protection factors of 1.25, 1.30, 2.1, and 2.5, respectively. However, the reduced form of Tempol afforded no protection. Tempol treatment under hypoxic conditions did not provide radioprotection. Aerobic X-ray protection by Tempol could not be attributed to the induction of intracellular hypoxia, increase in intracellular glutathione, or induction of intracellular SOD mRNA. Tempol thus represents a new class of non-thiol-containing radiation protectors, which may be useful in elucidating the mechanism(s) of radiation-induced cellular damage and may have broad applications in protecting against oxidative stress.

  2. Production of gamma induced reactive oxygen species and damage of DNA molecule in HaCaT cells under euoxic and hypoxic condition

    International Nuclear Information System (INIS)

    Joseph, P.; Bhat, N.N.; Copplestone, D.; Narayana, Y.

    2014-01-01

    The paper deals with the study of gamma radiation induced reactive oxygen species (ROS) generation in normal human keratinocytes (HaCaT) cells and quantification of subsequent damages induced on DNA molecules. The DNA damages induced in cells after gamma irradiation has been analyzed using Alkaline comet assay. The ROS produced in the cells were quantified by measuring fluorescence after loading the cells with 2', 7' dichlorofluorescin diacetate, a dye that is oxidized into a highly fluorescent form in the presence of peroxides. Studies reveal that in HaCaT cells radical generation occurs when exposed to ionizing radiation and it increases with dose. The induced DNA damages also increases with dose and ROS generation. The study clearly shows the importance of ROS in DNA damage induction and the cells possessing elevated levels of DNA damage after radiation exposure is due to the effect of increased levels of intracellular ROS. (author)

  3. 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.

  4. 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 ...

  5. Laser-induced damage threshold of ZrO2 thin films prepared at different oxygen partial pressures by electron-beam evaporation

    International Nuclear Information System (INIS)

    Zhang Dongping; Shao Jianda; Zhao Yuanan; Fan Shuhai; Hong Ruijing; Fan Zhengxiu

    2005-01-01

    ZrO 2 films were deposited by electron-beam evaporation with the oxygen partial pressure varying from 3x10 -3 Pa to 11x10 -3 Pa. The phase structure of the samples was characterized by x-ray diffraction (XRD). The thermal absorption of the films was measured by the surface thermal lensing technique. A spectrophotometer was employed to measure the refractive indices of the samples. The laser-induced damage threshold (LIDT) was assessed using a 1064 nm Nd: yttritium-aluminum-garnet pulsed laser at pulse width of 12 ns. The influence of oxygen partial pressure on the microstructure and LIDT of ZrO 2 films was investigated. XRD data revealed that the films changed from polycrystalline to amorphous as the oxygen partial pressure increased. The variation of refractive index at 550 nm wavelength indicated that the packing density of the films decreased gradually with increasing oxygen partial pressure. The absorptance of the samples decreased monotonically from 125.2 to 84.5 ppm with increasing oxygen partial pressure. The damage threshold values increased from 18.5 to 26.7 J/cm 2 for oxygen partial pressures varying from 3x10 -3 Pa to 9x10 -3 Pa, but decreased to 17.3 J/cm 2 in the case of 11x10 -3 Pa

  6. 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

  7. Radiation-induced damage in E. coli B: The effect of superoxide radicals and molecular oxygen. Progress report, December 1, 1978--November 30, 1979

    International Nuclear Information System (INIS)

    Samuni, A.; Czapski, G.

    The roles of superoxide radicals and of molecular oxygen in the radiodamage of E. coli B suspended in dilute phosphate buffer were studied. The presence of high concentrations of polyethylene glycol in the γ-irradiated cell suspensions, had no effect on bacterial radiosensitivity. This indicates that the damage was primarily endogenous, i.e. originated intracellularly. Saturation of the cell suspensions with N 2 O doubled the radiosensitivity, thus indicating that OH radicals are responsible for the majority of the damage (indirect radiation effect). The presence of oxygen either in the absence or presence of N 2 O brought about roughly a three-fold increase in the radiosensitivity. Since in the presence of N 2 O all e - /sub aq/ are scavenged by the nitrous oxide rather than by oxygen, this shows that superoxide radicals play no role in the bacterial radiodamage. Our results substantiate the attribution of the oxygen effect to a direct interaction of O 2 with the hydroxyl-radical-damaged sites on vital biomolecules, and exclude any significant contribution of e - /sub aq/ and superoxide radicals to the cellular radiodamage

  8. 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...

  9. Cordyceps sinensis Oral Liquid Inhibits Damage Induced by Oxygen and Glucose Deprivation in SH-SY5Y Cells.

    Science.gov (United States)

    Zou, Ying-Xin; Liu, Yu-Xiang; Ruan, Ming-Hua; Zhou, Yi; Wang, Jia-Chun; Chu, Zhi-Yong

    2016-01-01

    Cordyceps sinensis has been used in traditional Chinese medicine for thousands of years. It has been demonstrated to have a variety of biological activities, and an extract of it has been demonstrated to possess a protective effect in occlusion-induced focal cerebral ischemia of the middle cerebral artery in rats. It could be explored as an agent for treatment of ischemic stroke, and the mechanisms need to be studied further. The study intended to investigate the protective effects of the Cordyceps sinensis oral liquid (CSOL) against damage induced by oxygen and glucose deprivation (OGD) in SH-SY5Y cells. DESIGN • The research team designed an in vitro study. The study occurred at the Naval Medical Research Institute in Shanghai, China. SH-SY5Y cells were exposed to CSOL in doses of 0.01, 0.03, 0.10, 0.30, and 1.00 mg/mL, creating 5 intervention groups. The OGD condition was induced by transfer of the cells from high-glucose Dulbecco's Modified Eagle's medium (DMEM) in a box gassed with air containing 5% CO2 to glucose-free DMEM in a box gassed with 94% N2, 5% CO2, and 1% O2. Like the cells for the interventions groups, the cells for a model group were cultured with high-glucose DMEM and were transferred to the OGD, but they received no dose of COSL. Cells in a control group were cultured with high-glucose DMEM, were not transferred to the OGD condition, and did not receive any dose of COSL. Cell viability was assayed using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) method. The apoptosis and the mitochondrial membrane potential (MMP) were detected by flow cytometry, and the protein expression of caspase-3 was observed by western blot. After exposure to OGD, the cell viability of cells treated with 0.01, 0.03, 0.10, 0.30, and 1.00 mg/mL of CSOL increased in a dose-effect relationship. Compared with the cells in the model group, the treatment of CSOL at all the experimental concentrations significantly inhibited both the cell apoptosis

  10. Reactive oxygen species mediate soft corals-derived sinuleptolide-induced antiproliferation and DNA damage in oral cancer cells

    Directory of Open Access Journals (Sweden)

    Chang YT

    2017-07-01

    Full Text Available Yung-Ting Chang,1,2,* Chiung-Yao Huang,3,* Jen-Yang Tang,4,5 Chih-Chuang Liaw,1,3 Ruei-Nian Li,6 Jing-Ru Liu,6 Jyh-Horng Sheu,1,3,7,8 Hsueh-Wei Chang6,9–12 1Doctoral Degree Program in Marine Biotechnology, National Sun Yat-sen University, Kaohsiung, Taiwan; 2Doctoral Degree Program in Marine Biotechnology, Academia Sinica, Taipei, Taiwan; 3Department of Marine Biotechnology and Resources, National Sun Yat-sen University, Kaohsiung, Taiwan; 4Department of Radiation Oncology, Faculty of Medicine, College of Medicine, Kaohsiung Medical University, Kaohsiung, Taiwan; 5Department of Radiation Oncology, Kaohsiung Municipal Ta-Tung Hospital, Kaohsiung, Taiwan; 6Department of Biomedical Science and Environmental Biology, Kaohsiung Medical University, Kaohsiung, Taiwan; 7Department of Medical Research, China Medical University Hospital, China Medical University, Taichung, Taiwan; 8Frontier Center for Ocean Science and Technology, National Sun Yat-sen University, Kaohsiung, Taiwan; 9Institute of Medical Science and Technology, National Sun Yat-sen University, Kaohsiung, Taiwan; 10Cancer Center, Kaohsiung Medical University Hospital; Kaohsiung Medical University, Kaohsiung, Taiwan; 11Department of Medical Research, Kaohsiung Medical University Hospital, Kaohsiung, Taiwan; 12Research Center for Natural Products and Drug Development, Kaohsiung Medical University, Kaohsiung, Taiwan *These authors contributed equally to this work Abstract: We previously reported that the soft coral-derived bioactive substance, sinuleptolide, can inhibit the proliferation of oral cancer cells in association with oxidative stress. The functional role of oxidative stress in the cell-killing effect of sinuleptolide on oral cancer cells was not investigated as yet. To address this question, we introduced the reactive oxygen species (ROS scavenger (N-acetylcysteine [NAC] in a pretreatment to evaluate the sinuleptolide-induced changes to cell viability, morphology, intracellular

  11. ETV6/RUNX1 Induces Reactive Oxygen Species and Drives the Accumulation of DNA Damage in B Cells

    Directory of Open Access Journals (Sweden)

    Hans-Peter Kantner

    2013-11-01

    Full Text Available The t(12;21(p13;q22 chromosomal translocation is the most frequent translocation in childhood B cell precursor-acute lymphoblastic leukemia and results in the expression of an ETV6/RUNX1 fusion protein. The frequency of ETV6/RUNX1 fusions in newborns clearly exceeds the leukemia rate revealing that additional events occur in ETV6/RUNX1-positive cells for leukemic transformation. Hitherto, the mechanisms triggering these second hits remain largely elusive. Thus, we generated a novel ETV6/RUNX1 transgenic mouse model where the expression of the fusion protein is restricted to CD19+ B cells. These animals harbor regular B cell development and lack gross abnormalities. We established stable pro-B cell lines carrying the ETV6/RUNX1 transgene that allowed us to investigate whether ETV6/RUNX1 itself favors the acquisition of second hits. Remarkably, these pro-B cell lines as well as primary bone marrow cells derived from ETV6/RUNX1 transgenic animals display elevated levels of reactive oxygen species (ROS as tested with ETV6/RUNX1 transgenic dihydroethidium staining. In line, intracellular phospho-histone H2AX flow cytometry and comet assay revealed increased DNA damage indicating that ETV6/RUNX1 expression enhances ROS. On the basis of our data, we propose the following model: the expression of ETV6/RUNX1 creates a preleukemic clone and leads to increased ROS levels. These elevated ROS favor the accumulation of secondary hits by increasing genetic instability and doublestrand breaks, thus allowing preleukemic clones to develop into fully transformed leukemic cells.

  12. PKCδ sensitizes neuroblastoma cells to L-buthionine-sulfoximine and etoposide inducing reactive oxygen species overproduction and DNA damage.

    Directory of Open Access Journals (Sweden)

    Barbara Marengo

    Full Text Available Neuroblastoma is a type of pediatric cancer. The sensitivity of neuroblastoma (NB cancer cells to chemotherapy and radiation is inhibited by the presence of antioxidants, such as glutathione (GSH, which is crucial in counteracting the endogenous production of reactive oxygen species (ROS. We have previously demonstrated that cells depleted of GSH undergo apoptosis via oxidative stress and Protein kinase C (PKC δ activation. In the present study, we transfected PKCδ in NB cells resistant to oxidative death induced by L-buthionine-S,R-sulfoximine (BSO, a GSH-depleting agent. Cell responses, in terms of ROS production, apoptosis and DNA damage were evaluated. Moreover, PKCδ activation was monitored by analyzing the phosphorylation status of threonine 505 residue, carrying out PKC activity assay and investigating the subcellular localization of the kinase. The cell responses obtained in BSO-resistant cells were also compared with those obtained in BSO-sensitive cells subjected to the same experimental protocol. Our results demonstrate, for the first time, that PKCδ induces DNA oxidation and ROS overproduction leading to apoptosis of BSO-resistant NB cells and potentiates the cytotoxic effects induced by BSO in sensitive cells. Moreover, PKCδ overexpression enhances the sensitivity of NB cells to etoposide, a well-characterised drug, commonly used in neuroblastoma therapy. Altogether our data provide evidence of a pro-oxidant role of PKCδ that might be exploited to design new therapeutic strategies aimed at selective killing of cancer cells and overcoming drug resistance. However, it becomes evident that a more detailed understanding of ROS-mediated signaling in cancer cells is necessary for the development of redox-modulated therapeutic approaches.

  13. Essential oil of Artemisia scoparia inhibits plant growth by generating reactive oxygen species and causing oxidative damage.

    Science.gov (United States)

    Singh, Harminder Pal; Kaur, Shalinder; Mittal, Sunil; Batish, Daizy Rani; Kohli, Ravinder Kumar

    2009-02-01

    We investigated the chemical composition and phytotoxicity of the essential oil extracted from leaves of Artemisia scoparia Waldst. et Kit. (red stem wormwood, Asteraceae). GC/GC-MS analyses revealed 33 chemical constituents representing 99.83% of the oil. The oil, in general, was rich in monoterpenes that constitute 71.6%, with beta-myrcene (29.27%) as the major constituent followed by (+)-limonene (13.3%), (Z)-beta-ocimene (13.37%), and gamma-terpinene (9.51%). The oil and beta-myrcene were evaluated in a dose-response bioassay under laboratory conditions for phytotoxicity against three weeds-Avena fatua, Cyperus rotundus, and Phalaris minor. A significant reduction in germination, seedling growth, and dry matter accumulation was observed in the test weeds. At the lowest treatment of 0.07 mg/ml Artemisia oil, germination was reduced by 39%, 19%, and 10.6% in C. rotundus, P. minor, and A. fatua, respectively. However, the inhibitory effect of beta-myrcene was less. In general, a dose-dependent effect was observed and the growth declined with increasing concentration. Among the three weeds, the inhibitory effect was greatest on C. rotundus, so it was selected for further studies. We explored the explanation for observed growth inhibition in terms of reactive oxygen species (ROS: lipid peroxidation, membrane integrity, and amounts of conjugated dienes and hydrogen peroxide)-induced oxidative stress. Exposure of C. rotundus to Artemisia oil or beta-myrcene enhanced solute leakage, indicating membrane disintegration. There were increased levels of malondialdehyde and hydrogen peroxide, indicating lipid peroxidation and induction of oxidative stress. We conclude that Artemisia oil inhibits plant root growth through generation of ROS-induced oxidative damage.

  14. 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

  15. 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

  16. Radiation-induced damage in T4 bacteriophage: the effect of superoxid radicals and molecular oxygen. Progress report, December 1, 1977--November 30, 1978

    International Nuclear Information System (INIS)

    Samuni, A.; Chevion, M.; Halpern, Y.S.; Ilan, Y.A.; Czapski, G.

    1978-01-01

    The sensitivity of T4 bacteriophage towards γ irradiation has been studied in phosphate buffer suspensions. The spectrum of the water radicals was controlled by a careful choice of the appropriate saturating gas and the addition of radical scavengers. Thus, it was possible to distinguish between the effects of molecular oxygen and the superoxide radicals formed through its reactions. About 90 percent of the damage was caused by the water radicals formed in the bulk suspensions. These probably affected the phage proteins; only the remainder of the damage involved the viral DNA. The oxygen enhancement ratio observed was not connected in any way with the formation of the superoxide radicals. The results confirmed that the OH radicals are the reactive species, while e - /sub aq/ as well as the superoxide radical do not contribute to the radiodamage

  17. 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.

  18. 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.)

  19. Recovery of human lymphocytes damaged with. gamma. -radiation or enzymatically produced oxygen radicals: different effects of poly(ADP-ribosyl)polymerase inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Marini, M.; Zunica, G. (Ist. di Istologia ed Embriologia Generale, Bologna (Italy)); Tamba, M. (Consiglio Nazionale delle Ricerche, Bologna (Italy). Lab. di Fotochimica e Radiazioni d' Alta Energia); Cossarizza, A.; Monti, D.; Franceschi, C. (Ist. di Patologia Generale, Modena (Italy))

    1990-08-01

    Quiescent human lymphocytes were damaged in two different ways, both producing toxic oxygen radicals: xanthine oxidase plus hypoxanthine (XOD/HYP), or {gamma}-rays. Under conditions where DNA synthesis was reduced to 10-20% of control, inhibitors of poly(ADP-ribosyl)polymerase (ADPRP, an enzyme that becomes activated in the presence of DNA strand breaks) allowed lymphocytes to recover completely when the damage was caused by XOD/HYP, but they did not affect DNA synthesis of irradiated cells. However, a protective effect of ADPRP inhibitors was observed with irradiated lymphocytes receiving doses {ge}50Gy. Unscheduled DNA synthesis was significantly increased when lymphocytes were damaged by high radiation doses in the presence of ADPRP inhibitors. (author).

  20. Effects of oxygen and moisture content on the radiation damage in barley seeds irradiated with fast neutrons and gamma rays

    International Nuclear Information System (INIS)

    Ahnstroem, G.

    1968-01-01

    In gamma-irradiated barley seeds the effect of moisture content seems to modify the oxygen effect. If gamma-irradiated seeds (4% H 2 O content) are soaked in oxygen-free water before being transferred to oxygenated water, the oxygen-sensitive centres decay. The decay rate is a function of temperature and is shown to be most likely due to how fast the target molecules are hydrated. When low moisture content seeds were irradiated with fast neutrons in the SNIF, a moisture content effect was also obtained. However, contrary to what was found with gamma-irradiated seeds, no effect of oxygen was obtained. This excludes the possibility that gamma-contamination caused the moisture content effect. A model explaining the difference between the effect of neutrons and gamma-rays, respectively, is discussed. (author). 13 refs, 1 fig., 2 tabs

  1. Hypoxia-induced cell damage is reduced by mild hypothermia and postconditioning with catalase in-vitro: application of an enzyme based oxygen deficiency system.

    Science.gov (United States)

    Zitta, Karina; Meybohm, Patrick; Bein, Berthold; Rodde, Cornelia; Steinfath, Markus; Scholz, Jens; Albrecht, Martin

    2010-02-25

    Mild hypothermia and pharmacological postconditioning are widespread therapeutical treatment options that positively influence the clinical outcome after tissue hypoxia. In the study presented, a two-enzyme based in-vitro oxygen deficiency model in combination with cultured HT-1080 fibrosarcoma cells was employed to mimic the in-vivo situation of hypoxia and to evaluate the influence of mild hypothermia and postconditioning with catalase on hypoxia-mediated cell damage. Using the in-vitro oxygen deficiency model, partial pressure of oxygen was rapidly reduced to levels below 5mmHg in the culture media and cells responded with an increased expression of hypoxia inducible factor-1 on protein level. Hypoxia resulted in significant cell rounding and retraction of cytoplasmic cell extensions. Evaluation of cytotoxicity revealed a 3.5-fold increase in lactate dehydrogenase levels which was accompanied by 40-fold elevated levels of hydrogen peroxide. The hypoxia-induced increase of lactate dehydrogenase was 2.5-fold reduced in the hypothermia group, although morphological correlates of cytotoxicity were still visible. Hypothermia did not significantly influence hydrogen peroxide concentrations in the culture media. Pharmacological postconditioning with catalase however dose-dependently decreased hypoxia-induced lactate dehydrogenase release. This cytoprotective effect was accompanied by a dose-dependent, up to 50-fold reduction of hydrogen peroxide concentrations and retention of normal cell morphology. We suggest that the described in-vitro oxygen deficiency model is a convenient and simple culture system for the investigation of cellular and subcellular events associated with oxygen deficiency. Moreover, our in-vitro results imply that catalase postconditioning may be a promising approach to attenuate hypoxia-induced and hydrogen peroxide-mediated cell and tissue damage.

  2. The effect of camphorquinone (CQ) and CQ-related photosensitizers on the generation of reactive oxygen species and the production of oxidative DNA damage.

    Science.gov (United States)

    Pagoria, Dustin; Lee, Abert; Geurtsen, Werner

    2005-07-01

    Recent evidence suggests that following visible-light (VL) irradiation, CQ and the CQ-related photosensitizers benzil (BZ), benzophenone (BP), and 9-fluorenone (9-F) generate initiating radicals that may indiscriminately react with molecular oxygen forming reactive oxygen species (ROS). The purpose of this investigation was to determine whether VL-irradiated CQ, BZ, BP, and 9-F cause DNA damage due to the generation of ROS in vitro. ROS formation by CQ and CQ-related photosensitizers+/-dimethyl-p-toluidine (DMT) was investigated in a cell-free system with VL irradiation. DNA damage was determined using PhiX-174 RF I supercoiled double-stranded plasmid DNA and ROS quantified with 4-((9-acridinecarbonyl)amino)-2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO-9-AC), a fluorogenic ROS-sensitive probe. VL-irradiated CQ, BZ, BP, and 9-F (+/-DMT) produced significant DNA damage at 0.1, 0.5, and 1.0 mM and in a concentration-dependent manner (p<0.05). TEMPO-9-AC revealed that all investigated VL-irradiated photosensitizers produced significant amounts of ROS with BZ in the presence of DMT generating the most ROS after 30, 60, and 90 min. VL-irradiated CQ, BZ, BP, and 9-F +/-DMT continued to generate significant amounts of ROS 90 min after VL irradiation. As a result, future investigations should evaluate the effect of VL-irradiated photosensitizers in cells and possible protective effects provided by antioxidants.

  3. 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

  4. Effects of iron salts and haemosiderin from a thalassaemia patient on oxygen radical damage as measured in the comet assay

    NARCIS (Netherlands)

    Anderson, D.; Yardley-Jones, A.; Hambly, R.J.; Vives-Bauza, C.; Smykatz-Kloss, V.; Chua-anusorn, W.; Webb, J.

    2000-01-01

    Thalassaemia is a group of genetic diseases where haemoglobin synthesis is impaired. This chronic anaemia leads to increased dietary iron absorption, which develops into iron overload pathology. Treatment through regular transfusions increases oxygen capacity but also provides iron through the red

  5. 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.

  6. 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...

  7. Effects of exercise-induced muscle damage on resting metabolic rate, sub-maximal running and post-exercise oxygen consumption.

    Science.gov (United States)

    Burt, Dean Gareth; Lamb, Kevin; Nicholas, Ceri; Twist, Craig

    2014-01-01

    Exercise-induced muscle damage (EIMD), described as the acute weakness of the musculature after unaccustomed eccentric exercise, increases oxidative metabolism at rest and during endurance exercise. However, it is not known whether oxygen uptake during recovery from endurance exercise is increased when experiencing symptoms of EIMD. Therefore, the purpose of this study was to investigate the effects of EIMD on physiological and metabolic responses before, during and after sub-maximal running. After a 12 h fast, eight healthy male participants completed baseline measurements comprising resting metabolic rate (RMR), indirect markers of EIMD, 10 min of sub-maximal running and 30 min of recovery to ascertain excess post-exercise oxygen consumption (EPOC). Measurements were then repeated at 24 and 48 h after 100 Smith-machine squats. Data analysis revealed significant (PEPOC were increased in the two days after squatting exercise (PEPOC. Individuals engaging in unaccustomed resistance exercise that results in muscle damage should be mindful of the increases in resting energy expenditure and increased metabolic demand to exercise in the days that follow.

  8. Involvement of Cytochrome P450 in Reactive Oxygen Species Formation and Cancer.

    Science.gov (United States)

    Hrycay, Eugene G; Bandiera, Stelvio M

    2015-01-01

    This review examines the involvement of cytochrome P450 (CYP) enzymes in the formation of reactive oxygen species in biological systems and discusses the possible involvement of reactive oxygen species and CYP enzymes in cancer. Reactive oxygen species are formed in biological systems as byproducts of the reduction of molecular oxygen and include the superoxide radical anion (∙O2-), hydrogen peroxide (H2O2), hydroxyl radical (∙OH), hydroperoxyl radical (HOO∙), singlet oxygen ((1)O2), and peroxyl radical (ROO∙). Two endogenous sources of reactive oxygen species are the mammalian CYP-dependent microsomal electron transport system and the mitochondrial electron transport chain. CYP enzymes catalyze the oxygenation of an organic substrate and the simultaneous reduction of molecular oxygen. If the transfer of oxygen to a substrate is not tightly controlled, uncoupling occurs and leads to the formation of reactive oxygen species. Reactive oxygen species are capable of causing oxidative damage to cellular membranes and macromolecules that can lead to the development of human diseases such as cancer. In normal cells, intracellular levels of reactive oxygen species are maintained in balance with intracellular biochemical antioxidants to prevent cellular damage. Oxidative stress occurs when this critical balance is disrupted. Topics covered in this review include the role of reactive oxygen species in intracellular cell signaling and the relationship between CYP enzymes and cancer. Outlines of CYP expression in neoplastic tissues, CYP enzyme polymorphism and cancer risk, CYP enzymes in cancer therapy and the metabolic activation of chemical procarcinogens by CYP enzymes are also provided. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Potentiating effects of oxygen in lungs damaged by methylcyclopentadienyl manganese tricarbonyl, cadmium chloride, oleic acid, and antitumor drugs

    Energy Technology Data Exchange (ETDEWEB)

    Hakkinen, P.J.; Morse, C.C.; Martin, F.M.; Dalbey, W.E.; Haschek, W.M.; Witschi, H.R.

    1983-01-01

    The intraperitoneal administration of methylcyclopentadienyl manganese tricarbonyl (MMT) and cyclophosphamide, exposure to an aerosol of cadmium chloride, intravenous administration of oleic acid, and intratracheal instillation of bleomycin to young female BALB/c mice or CD/CR rats result in acute lung injury. Pulmonary morphology and lung collagen content were examined in animals treated with these chemicals alone or in combination with an elevated oxygen concentration (80%) in the inspired air. In mice, the development of fibrosis could be significantly enhanced if animals treated with MMT, cadmium chloride, cyclophosphamide, or bleomycin were exposed to 80% oxygen immediately following exposure to these agents. In rats only cyclophosphamide- and bleomycin-induced acute lung injury was potentiated by hyperoxia, resulting in significant enhancement of lung collagen content. The pathogenesis responsible for this differential species response of pulmonary injury to hyperoxia remains to be investigated.

  10. THE PROTECTIVE ROLE OF VITAMIN E AGAINST OXYGEN FREE RADICAL AND DNA DAMAGE IN CHILDREN WITH β-THALASSEMIA MAJOR

    International Nuclear Information System (INIS)

    NASSAR, E.M.

    2008-01-01

    The present study aimed to determine the benefits of vitamin E as antioxidant supplement in β thalassemia children who are at risk of iron overload due to multiple blood transfusion and oxidative stress. Antioxidant markers, oxidative products, hematological parameters and biomarkers of cell damage were studied in 24 transfusion-dependent β -thalassemia children before and after treatment with vitamin E at a dose of 10 mg/kg /day for a period of four weeks. Plasma thiobarbituric acid reactive species (TBARS) and urinary 8-hydroxy-2 ' -deoxyguanosine (8-OHdG) were analyzed as oxidative markers, whereas the plasma vitamin E and the activities of the antioxidant enzymes glutathione peroxidase (GSH-Px), superoxide dismutase(SOD) and catalase were measured to show the antioxidant status of thalassemic children. All these parameters were also studied in 15 non-anemic healthy controls .The results showed that all the patients had increased signs of iron overload and cell damage that were obvious from the increase in serum iron, ferritin, alanine transaminases (ALT), aspartate transaminases (AST) and both total and direct bilirubin .The level of plasma vitamin E in the thalassemia patients were found to be significantly lower as compared to normal subjects (1.3 ± 0.7 and 3.14 ± 1.5 mg % , respectively). The activities of antioxidants enzymes, glutathione peroxidase and catalase in untreated β-thalassemic patients were found to be significantly (P<0.001) less than that of the normal subjects. However, SOD level was significantly increased. Markers of free radical injury such as TBARS , urinary 8-OHdG levels in thalassemic children were significantly higher than control levels . All these changes in the antioxidant status as well as the hematological parameters, iron overload and cell damage markers in β-thalassemia patients showed significant improvement after vitamin E supplementation. Vitamin E levels showed significant positive correlations with each of Hb, GSH

  11. Effects of cryopreservation on sperm viability, synthesis of reactive oxygen species, and DNA damage of bovine sperm.

    Science.gov (United States)

    Gürler, H; Malama, E; Heppelmann, M; Calisici, O; Leiding, C; Kastelic, J P; Bollwein, H

    2016-07-15

    The objective was to examine if there are relationships between alterations in sperm viability, reactive oxygen species (ROS) synthesis, and DNA integrity induced by cryopreservation of bovine sperm. Four ejaculates were collected from each of six bulls. Each ejaculate was diluted and divided into two aliquots; one was incubated for 24 hours at 37 °C, and the other frozen, thawed, and incubated for 24 hours at 37 °C. Analyses of quality of sperm were performed after 0, 3, 6, 12, and 24 hours of incubation. Progressive motile sperm was determined with computer assisted sperm analysis. Percentages of plasma membrane- and acrosome-intact sperm, sperm with a high mitochondrial membrane potential, sperm showing a high degree of DNA fragmentation (%DFI), and their reactive oxygen species content were assessed with dichlorofluorescein-diacetate, dihydrorhodamine, diaminofluorescein diacetate, and mitochondrial superoxide indicator using flow cytometry. Although all other sperm parameters showed alterations (P  0.05, 0.91 ± 0.23) in nonfrozen sperm. Cryopreservation induced changes of all sperm parameters (P reactive oxygen species. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. 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

  13. An Ethanol Extract Derived from Bonnemaisonia hamifera Scavenges Ultraviolet B (UVB) Radiation-Induced Reactive Oxygen Species and Attenuates UVB-Induced Cell Damage in Human Keratinocytes

    Science.gov (United States)

    Piao, Mei Jing; Hyun, Yu Jae; Cho, Suk Ju; Kang, Hee Kyoung; Yoo, Eun Sook; Koh, Young Sang; Lee, Nam Ho; Ko, Mi Hee; Hyun, Jin Won

    2012-01-01

    The present study investigated the photoprotective properties of an ethanol extract derived from the red alga Bonnemaisonia hamifera against ultraviolet B (UVB)-induced cell damage in human HaCaT keratinocytes. The Bonnemaisonia hamifera ethanol extract (BHE) scavenged the superoxide anion generated by the xanthine/xanthine oxidase system and the hydroxyl radical generated by the Fenton reaction (FeSO4 + H2O2), both of which were detected by using electron spin resonance spectrometry. In addition, BHE exhibited scavenging activity against the 1,1-diphenyl-2-picrylhydrazyl radical and intracellular reactive oxygen species (ROS) that were induced by either hydrogen peroxide or UVB radiation. BHE reduced UVB-induced apoptosis, as shown by decreased apoptotic body formation and DNA fragmentation. BHE also attenuated DNA damage and the elevated levels of 8-isoprostane and protein carbonyls resulting from UVB-mediated oxidative stress. Furthermore, BHE absorbed electromagnetic radiation in the UVB range (280–320 nm). These results suggest that BHE protects human HaCaT keratinocytes against UVB-induced oxidative damage by scavenging ROS and absorbing UVB photons, thereby reducing injury to cellular components. PMID:23242204

  14. 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

  15. 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.

  16. Constants of the Alper and Howard-Flanders oxygen equation for damage to bacterial membrane, deduced from observations on the radiation-induced penicillin-sensitive lesion.

    Science.gov (United States)

    Obioha, F I; Gillies, N E; Cullen, B M; Walker, H C; Alper, T

    1984-05-01

    Energy deposited in the bacterial envelope of E. coli B/r induces lesions which are lethally attacked by penicillin in concentration insufficient to affect unirradiated bacteria. The critical lesions are probably in the membrane moiety. Bacteria were irradiated in the presence of 100 per cent oxygen, oxygen-free nitrogen and mixtures of 1.01, 0.59, 0.3, 0.1 and 0.06 per cent oxygen in nitrogen. Changes in sensitivity with pO2 conformed with the Alper and Howard-Flanders equation, for bacteria treated after irradiation by penicillin as well as for the untreated ones. The values of m were respectively 4.8 and 3.3; the values of K were identical, within experimental error, i.e. 4.4 mmHg. Sensitivity to induction of the penicillin-sensitive lesion was calculated from the difference in the reciprocals of D0 values proper to untreated and treated bacteria, for every gas used. The value of m could not be directly calculated because the effect of penicillin on anoxically irradiated bacteria was not detectable. For that reason, a transformation of the oxygen equation was used which allowed estimates to be made of both m and K, provided the results conformed with the equation. Within experimental error they did so conform. The calculated values of m and K for induction of the penicillin-sensitive lesion were respectively 8 and 5.9 mmHg, but it is shown that the oxygen enhancement ratio was probably underestimated and the K value overestimated. On the assumptions that these values of m and K are specific for radiation damage to bacterial membrane, and that radiation-induced killing is attributable to lethal lesions in the membrane as well as the DNA, the results demonstrate that any interaction of oxygen with sites of energy deposition in the DNA must play a very much smaller role in radiosensitization than does interaction with sites of energy deposition in the membrane.

  17. 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.)

  18. 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.)

  19. Reactive oxygen species and high-nitrogen compound in the mechanism of protection and damage in white blood cells in pulmonary tuberculosis.

    Science.gov (United States)

    Sabadash, E V; Skorniakov, S N; Paviov, V A; Novikov, B I; Ershova, A V; Egorov, E A

    2016-01-01

    The aim of the study was to determine changes in the level of reactive oxygen species (ROS) and high-nitrogen compounds (HNC) of white blood cells of patients with various forms of pulmonary tuberculosis, and attempt to identify the pathogenic importance marked disturbances in protection mechanisms and damaged by the disease. A prospective study of 92 people, who were divided into 4 groups: I - 25 patients with newly diagnosed infiltrative tuberculosis and localization process within the same lobe of the lung, II - 42 patients with newly diagnosed pulmonary tuberculosis with a limited process (tuberculoma), III - 15 patients with fibrosis - cavernosis pulmonary tuberculosis with disease duration of less than 2 years old and group IV - healthy people - 10. It has been found that chronic TB infection suppresses the phagocytes activity of leukocytes in any form of study of its development. However, in more severe forms of tuberculosis with a predominance of exudative tissue reactions (infiltrative) levels of these metabolites in the white blood cells increases and they become damaging significance. With limited forms of pulmonary tuberculosis - tuberculoma - levels of these metabolites (especially ICA) in white blood cells is reduced, which may have a protective value. The obtained results allow to claim that in the diagnosis and assessment of the nature of the tuberculosis process may be used definition of functional and metabolic characteristics of blood leukocytes and plasma (phagocytosis, peroxide, total lipid, BURST TEST, AFC, ICA and their derivatives), as well as the number of amino acids, taurine and arginine in plasma and leukocytes.

  20. 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; ...

  1. Influence of oxygen on the repair of direct radiation damage to DNA by thiols in model systems

    International Nuclear Information System (INIS)

    Becker, D.; Summerfield, S.; Gillich, S.; Sevilla, M.D.

    1994-01-01

    Here the reactions of thiols with DNA primary radical intermediates formed after γ-irradiation of frozen (77K) anoxic and oxic solutions of DNA/thiol mixtures are investigated. Through analysis of the experimental composite spectra at each annealing temperature, the relative concentrations of individual radicals present are estimated and reaction sequences inferred. In all samples the primary DNA radical anions and cations (DNA · + and DNA · - ) are suggested to be the predominant radicals at low temperatures. In anoxic samples, TH · (5,6-dihydrothym-5-yl radical), RSSR · - and, in glutathione samples, · GSH [γ-glu-NHC(CH 2 SH) CO-gly] radicals are observed as the temperature is increased. The presence of oxygen efficiently suppresses the formation of RSSR · - and · GSH; instead, in oxic samples, O 2 · - , DNAOO · , RSOO · and RSO · are observed at higher temperatures. The photolytic conversion of RSOO · to RSO 2 · is used to verify the presence of RSOO · in γ-irradiated DNA/thiol systems and confirm that the computer analysis employed yields reasonable estimates of the relative DNAOO · and RSOO · concentrations. (Author)

  2. 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.

  3. 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.

  4. Reactive oxygen species damage drives cardiac and mitochondrial dysfunction following acute nano-titanium dioxide inhalation exposure.

    Science.gov (United States)

    Nichols, Cody E; Shepherd, Danielle L; Hathaway, Quincy A; Durr, Andrya J; Thapa, Dharendra; Abukabda, Alaeddin; Yi, Jinghai; Nurkiewicz, Timothy R; Hollander, John M

    2018-02-01

    Nanotechnology offers innovation in products from cosmetics to drug delivery, leading to increased engineered nanomaterial (ENM) exposure. Unfortunately, health impacts of ENM are not fully realized. Titanium dioxide (TiO 2 ) is among the most widely produced ENM due to its use in numerous applications. Extrapulmonary effects following pulmonary exposure have been identified and may involve reactive oxygen species (ROS). The goal of this study was to determine the extent of ROS involvement on cardiac function and the mitochondrion following nano-TiO 2 exposure. To address this question, we utilized a transgenic mouse model with overexpression of a novel mitochondrially-targeted antioxidant enzyme (phospholipid hydroperoxide glutathione peroxidase; mPHGPx) which provides protection against oxidative stress to lipid membranes. MPHGPx mice and littermate controls were exposed to nano-TiO 2 aerosols (Evonik, P25) to provide a calculated pulmonary deposition of 11 µg/mouse. Twenty-four hours following exposure, we observed diastolic dysfunction as evidenced by E/A ratios greater than 2 and increased radial strain during diastole in wild-type mice (p nano-TiO 2 exposure. To investigate the cellular mechanisms associated with the observed cardiac dysfunction, we focused our attention on the mitochondrion. We observed a significant increase in ROS production (p nano-TiO 2 exposure which were attenuated in mPHGPx transgenic mice. In summary, nano-TiO 2 inhalation exposure is associated with cardiac diastolic dysfunction and mitochondrial functional alterations, which can be mitigated by the overexpression of mPHGPx, suggesting ROS contribution in the development of contractile and bioenergetic dysfunction.

  5. Long-Term Sodium Ferulate Supplementation Scavenges Oxygen Radicals and Reverses Liver Damage Induced by Iron Overloading

    Directory of Open Access Journals (Sweden)

    Yang Qiao

    2016-09-01

    Full Text Available Ferulic acid is a polyphenolic compound contained in various types of fruits and wheat bran. As a salt of the active ingredient, sodium ferulate (SF has potent free radical scavenging activity and can effectively scavenge ROS. In this study, we examined the effect of SF on iron-overloaded mice in comparison to a standard antioxidant, taurine (TAU. We determined the protective role of SF against liver injury by examining liver-to-body ratio (%, transaminase and hepatocyte apoptosis in rats supplied with 10% dextrose intraperitoneal injection. In addition, antioxidative enzymes activities, ROS formation, mitochondrial swelling, and mitochondrial membrane potential (MMP were all evaluated to clarify the mechanism of protective effect of SF associated with oxidative stress. After 15 weeks of SF treatment, we found a significant reduction in liver-to-body weight radio and elevation in both transaminase and hepatocyte apoptosis associated with iron-injected to levels comparable to those achieved with TAU. Both SF and TAU significantly attenuated the impaired liver function associated with iron-overloaded in mice, whereas neither showed any significant effect on the iron uptake. Furthermore, treatment with either SF or TAU in iron-overloaded mice attenuated oxidative stress, associated with elevated oxidant enzymes activities, decreased ROS production, prevented mitochondrial swelling and dissipation of MMP and then inhibited hepatic apoptosis. Taken together, the current study shows that, SF alleviated oxidative stress and liver damage associated with iron-overload conditions compared to the standard ROS scavenger (TAU, and potentially could encourage higher consumption and utilization as healthy and sustainable ingredients by the food and drink.

  6. Attenuation of partial unilateral ureteral obstruction – induced renal damage with hyperbaric oxygen therapy in a rat model

    Directory of Open Access Journals (Sweden)

    Eyup Burak Sancak

    Full Text Available ABSTRACT Objective: The objective of the present study was to evaluate the effectiveness of HBO therapy on biochemical parameters, renal morphology and renal scintigraphy in rats undergoing chronic unilateral partial ureteral obstruction (UPUO. Material and methods: Thirty-five rats were divided into five equal groups: Control group; Sham group; HBO group; UPUO group and UPUO/HBO group. The effects of HBO therapy were examined using biochemical parameters and histopathological changes. After calculating the score for each histopathological change, the total histopathological score was obtained by adding all the scores. In addition, dynamic renal scintigraphy findings were evaluated. Results: Serum parameters indicating inflammation, serum tumor necrosis factor- alpha, ischemia modified-albumin, IMA/albumin ratio and Pentraxin-3 levels, were observed to be high in the UPUO group and low in the UPUO/HBO treatment group. Similarly, in the treatment group, the reduction in malondialdehyde, total oxidant status and oxidative stress index levels and increase in total antioxidant capacity values were observed to be statistically significant compared to the UPUO group (p<0.001, p=0.007, p<0.001, p=0.001, respectively. The total score and apoptosis index significantly decreased after administration of HBO treatment. Dynamic 99mTc-MAG3 renal scintigraphy also showed convincing evidence regarding the protective nature of HBO against kidney injury. In the UPUO/HBO therapy group, the percentage contribution of each operated kidney increased significantly compared to the UPUO group (41.73% versus 32.72%. Conclusion: The findings of this study indicate that HBO therapy had a reno-protective effect by reducing inflammation and oxidative stress, and preserving renal function after renal tissue damage due to induction of UPUO.

  7. Oxidatively generated base damage to cellular DNA

    Energy Technology Data Exchange (ETDEWEB)

    Cadet, Jean [Laboratoire ' Lesions des Acides Nucleiques' , SCIB-UMR-E no.3 - CEA/UJF, Institut nano-sciences et Cryogenie, CEA/Grenoble, F-38054 Grenoble Cedex 9 (France); Departement de Medecine Nucleaire et Radiobiologie, Faculte de medecine de des sciences de la sante, Universite de Sherbrooke, Sherbrooke, Quebec, J1H 5N4 (Canada); Douki, Thierry; Ravanat, Jean-Luc [Laboratoire ' Lesions des Acides Nucleiques' , SCIB-UMR-E no.3 - CEA/UJF, Institut nano-sciences et Cryogenie, CEA/Grenoble, F-38054 Grenoble Cedex 9 (France)

    2010-07-01

    Search for the formation of oxidatively base damage in cellular DNA has been a matter of debate for more than 40 years due to the lack of accurate methods for the measurement of the lesions. HPLC associated with either tandem mass spectrometry (MS/MS) or electrochemical detector (ECD) together with optimized DNA extraction conditions constitutes a relevant analytical approach. This has allowed the accurate measurement of oxidatively generated single and clustered base damage in cellular DNA following exposure to acute oxidative stress conditions mediated by ionizing radiation. UVA light and one-electron oxidants. In this review the formation of 11 single base lesions that is accounted for by reactions of singlet oxygen, hydroxyl radical or high intensity UVC laser pulses with nucleobases is discussed on the basis of the mechanisms available from model studies. In addition several clustered lesions were found to be generated in cellular DNA as the result of one initial radical hit on either a vicinal base or the 2-deoxyribose. Information on nucleo-base modifications that are formed upon addition of reactive aldehydes arising from the breakdown of lipid hydroperoxides is also provided. (authors)

  8. Effects of signal transducer and activator of transcription 3 RNAi on content of reactive oxygen species and DNA damage in glioma cell

    International Nuclear Information System (INIS)

    Gao Ling; Li Fengsheng; Dong Bo; Liu Lihui; Liu Qingjie; Chen Xiaohua; Mao Bingzhi

    2011-01-01

    Objective: To investigate the effects of signal transducer and activator of transcription 3 (STAT3) RNAi on the content of reactive oxygen species (ROS) and the DNA damage in glioma cells. Methods: Glioma cells of the line U251 cells were cultured and transfected with STAT3 RNAi plasmid (pSilencer2.1-STAT3, STAT3 group) and pSilencer2.1-GFP (GFP control group) respectively. Part of the U251 cells were irradiated with γ-rays of 60 Co as positive control group of smear phenomenon. The levels of ROS and malondialdehyde (MDA) in the cells were detected 24, 48, and 72 h later by flow cytometry and fluorescence chamoluminescence analyzer, respectively. The DNA damage in the transfected U251 cells was examined by using single cell gel electrophoresis assay, and the cell cycle distribution was examined using FACS PI staining 12, 24, and 36 h later. Results: At 24 h after the transfection, the ROS level of the siSTAT3-transfected cells was 8.91 times that of the control group (F=89.296, P<0.05), and returned to the normal level 48 h later. There were not significant differences in the MDA level of the cells 24, 48, and 72 h later between the siSTAT3 group and siGFP group. Compared with the 8 Gy irradiation positive group with obvious smear phenomenon, smear phenomenon was shown in part of the cells in the siSTAT3 group 6 h later, became less 12 h later, and disappeared completely 24 h later. Compared with the control group,lag of S stage rate was 17.22% and the lag of G 2 /M stage rate was 6.4% 12 h later in the siSTAT-transfected group,and the G 0 /G 1 stage lag rate was 18.44% 24 h later, and the lag of S stage rate was 17.99% 36 h later. Conclusions: Inhibition of STAT3 results in the change of oxido reduction status in glioma cells, as well as damage and reparation of DNA. (authors)

  9. Solid-state 17O nuclear magnetic resonance spectroscopy without isotopic enrichment: direct detection of bridging oxygen in radiation damaged zircon.

    Science.gov (United States)

    Ashbrook, Sharon E; Farnan, IanIan

    2004-09-01

    Protocols are presented for obtaining natural abundance (17)O magic angle spinning and static NMR spectra in the solid state. Rotor-assisted population transfer (RAPT), Carr-Purcell-Meiboom-Gill (CPMG) echo trains and cross-polarisation (CP) are all used to obtain spectra of sites with large as well as small electric field gradients in proton and non-proton containing inorganic materials. Spectra are of sufficient quality to obtain the typical NMR parameters by standard fitting of the spectra. The protocol is then applied to identifying the changes that accompany radioactive decay in zircon (ZrSiO(4)) where enrichment is impossible. The (17)O NMR spectra of a partially metamict zircon sample clearly show evidence of bridging oxygens being produced as a consequence of radiation damage. The spectra have been acquired at moderate magnetic fields over periods typically of 60 h (1 weekend) and it is concluded that a 'routine' overnight (17)O experiment of 15 h at high field (e.g. 21 T) may well be possible.

  10. Sodium Nitrate Induces Reactive Oxygen Species That Lower the Antioxidant Power, Damage the Membrane, and Alter Pathways of Glucose Metabolism in Human Erythrocytes.

    Science.gov (United States)

    Ansari, Fariheen Aisha; Mahmood, Riaz

    2015-12-09

    Nitrate salts are widely used as food additives and nitrogenous fertilizers and are present as contaminants in drinking water supplies. The effect of different concentrations (1-15 mM) of sodium nitrate (NaNO3) on human erythrocytes was studied under in vitro conditions. Treatment of erythrocytes with NaNO3 resulted in increases in methemoglobin levels, lipid peroxidation, and protein oxidation and a decrease in glutathione content. There were changes in the activities of all major antioxidant defense enzymes, and the pathways of glucose metabolism were also affected. Increased generation of reactive oxygen species (ROS) took place while the antioxidant power was impaired. The osmotic fragility of cells was increased, and membrane-bound enzymes were greatly inhibited. All changes were statistically significant at a probability level of P < 0.05 at all concentrations of NaNO3 except the lowest (1 mM). Thus, NaNO3 generates ROS that cause significant damage to human erythrocytes and interfere in normal cellular pathways.

  11. 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

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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...

  17. 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

  18. 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

  19. 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

  20. The effect of tobacco smoke exposure on the generation of reactive oxygen species and cellular membrane damage using co-culture model of blood brain barrier with astrocytes.

    Science.gov (United States)

    Seo, Seung-Beom; Choe, Eun Sang; Kim, Kwang-Sik; Shim, Soon-Mi

    2017-06-01

    Brain tissue is known to be vulnerable to the exposure by tobacco smoke. Tobacco smoke can induce generation of reactive oxygen species (ROS), causing inflammatory activity and blood-brain barrier (BBB) impairment. The aim of the present study was to investigate the effect of tobacco smoke on cell cytotoxicity, generation of ROS, and cellular membrane damage in astrocytes and BBB using a co-culture system. Cell viability of U373MG cells was reduced in a dose-dependent manner, ranging from 96.7% to 40.3% by tobacco smoke condensate (TSC). Cell viability of U373MG co-cultured with human brain microvascular endothelial cells (HBMECs) was 104.9% at the IC 50 value of TSC. Trans-epithelial electric resistance values drastically decreased 80% following 12-h incubation. The value was maintained until 48 h and then increased at 72-h incubation (85%). It then decreased to 75% at 120 h. Generation of ROS increased in a dose-dependent manner, ranging from 102.7% to 107.9%, when various concentrations of TSC (4-16 mg/mL) were administered to the U373MG monoculture. When TSC was added into U373MG co-cultured with HBMECs, production of ROS ranged from 101.7% to 102.6%, slightly increasing over 12 h. Maximum exposure-generated ROS of 104.8% was reached at 24 h. Cell cytotoxicity and oxidative stress levels in the U373MG co-culture model system with HBMECs were lower than U373MG monoculture. HBMECs effectively acted as a barrier to protect the astrocytes (U373MG) from toxicity of TSC.

  1. Tobacco Smoke: Involvement of Reactive Oxygen Species and Stable Free Radicals in Mechanisms of Oxidative Damage, Carcinogenesis and Synergistic Effects with Other Respirable Particles

    Directory of Open Access Journals (Sweden)

    Konstantinos Fiotakis

    2009-02-01

    Full Text Available Tobacco smoke contains many toxic, carcinogenic and mutagenic chemicals, as well as stable and unstable free radicals and reactive oxygen species (ROS in the particulate and the gas phase with the potential for biological oxidative damage. Epidemiological evidence established that smoking is one of the most important extrinsic factor of premature morbidity and mortality. The objective of this study was to investigate oxidative and carcinogenic mechanisms of tobacco and synergistic action with other respirable particles in the respiratory system of smokers. Electron Paramagnetic Resonance (EPR and spin- trapping techniques were used to study stable free radicals in the cigarette tar, and unstable superoxide anion (O2·- and hydroxyl (HO· radicals in the smoke Results showed that the semiquinone radical system has the potential for redox recycling and oxidative action. Further, results proved that aqueous cigarette tar (ACT solutions can generate adducts with DNA nucleobases, particularly the mutagenic 8-hydroxy-2’-deoxyguanosine (a biomarker for carcinogenesis.Also, we observed synergistic effects in the generation of HO·, through the Fenton reaction, with environmental respirable particles (asbestos fibres, coal dust, etc. and ambient particulate matter (PM, such as PM10, PM2.5 and diesel exhaust particles (DEP. The highest synergistic effects was observed with the asbestos fibres (freshly grounded, PM2.5 and DEP. Finally, we discuss results from our previous study of conventional cellulose acetate filters and “bio-filters” with hemoglobin impregnated activated carbon, which showed that these filters do not substantially alter the free radical content of smoke in the particulate and in the gaseous phase.

  2. 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.

  3. 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

  4. 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.

  5. 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_{\

  6. 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 ...

  7. 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 ...

  8. 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

  9. 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

  10. 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.)

  11. 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.)

  12. 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.

  13. 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.)

  14. 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

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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 ...

  3. 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.

  4. 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.

  5. 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.

  6. Spectroscopic study on the sonodynamic and sonocatalytic damage of anthraquinone derivants to bovine serum albumin under ultrasonic irradiation

    International Nuclear Information System (INIS)

    Wang Zhiqiu; Gao Jingqun; Wang Jun; Li Ying; Li Kai; Kang Pingli; Zhang Xiangdong

    2012-01-01

    In this work, three anthraquinone derivants (Alizarin: 1,2-dihydroxy-9, 10-anthraquinone, Alizarin–DA: 1,2-dihydroxy-9, 10-anthraquinone-3-aminomethyl-N, N-diacetic acid and Alizarin–DA–Fe: 1,2-dihydroxy-9, 10-anthraquinone-3-aminomethyl-N, N-diacetate-Ferrous(III)) were used to study the sonodynamic and sonocatalytic damage of bovine serum albumin (BSA) molecules according to the hyperchromic effect of UV–vis spectra and quenching effect of intrinsic fluorescence. Meanwhile, some influencing factors such as ultrasonic irradiation time, anthraquinone derivants concentration and ionic strength on the damage of BSA molecules were also considered. The results show that the synergetic effect of anthraquinone derivants and ultrasonic irradiation can efficiently damage the BSA molecules. Finally, some special radical scavengers were used to determine the kind of generated reactive oxygen species (ROS) in the presence of three anthraquinone derivants under ultrasonic irradiation. The results show that the ROS, at least, including singlet oxygen ( 1 O 2 ) and hydroxyl radicals (OH) are generated during the sonodynamic and sonocatalytic processes. It is wished that this paper could offer some valuable references for the application of anthraquinone derivants in sonodynamic therapy (SDT) and sonocatalytic therapy (SCT) for tumor treatment. - Highlights: ► Anthraquinone derivants were used to study the sonodynamic and sonocatalytic damage to BSA. ► The generations of ROS during sonodynamic and sonocatalytic process were estimated. ► Some quenchers were used to determine the kind of the ROS.

  7. 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.

  8. Proposal of a defense application for a chemical oxygen laser

    Science.gov (United States)

    Takehisa, K.

    2015-05-01

    Defense application for a chemical oxygen laser (COL) is explained. Although a COL has not yet been successful in lasing, the oscillator was estimated to produce a giant pulse with the full width at half maximum (FWHM) of ~0.05ms which makes the damage threshold for the mirrors several-order higher than that for a typical solid-state laser with a ~10ns pulse width. Therefore it has a potential to produce MJ class output considering the simple scalability of being a chemical laser. Since within 0.05ms a supersonic aircraft can move only a few centimeters which is roughly equal to the spot size of the focused beam at ~10km away using a large-diameter focusing mirror, a COL has a potential to make a damage to an enemy aircraft by a single shot without beam tracking. But since the extracted beam can propagate up to a few kilometers due to the absorption in the air, it may be suitable to use in space. While a chemical oxygen-iodine laser (COIL) can give a pulsed output with a width of ~2 ms using a high-pressure singlet oxygen generator (SOG). Therefore a pulsed COIL may also not require beam tracking if a target aircraft is approaching. Another advantage for these pulsed high-energy lasers (HELs) is that, in case of propagating in cloud or fog, much less energy is required for a laser for aerosol vaporization (LAV) than that of a LAV for a CW HEL. Considerations to use a COL as a directed energy weapon (DEW) in a point defense system are shown.

  9. 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....

  10. Constants of the Alper and Howard-Flanders oxygen equation for damage to bacterial membrane, deduced from observations on the radiation-induced penicillin-sensitive lesion

    International Nuclear Information System (INIS)

    Obioha, F.I.; Gillies, N.E.; Cullen, B.M.; Walker, H.C.; Alper, T.

    1984-01-01

    E. coli were irradiated in the presence of 100% oxygen, oxygen-free nitrogen and mixtures of 1.01, 0.59, 0.3, 0.1 and 0.06% oxygen in nitrogen. Changes in sensitivity with pO 2 conformed with the Alper and Howard-Flanders equation for bacteria treated after irradiation by penicillin as well as for the untreated ones. Values of m were respectively 4.8 and 3.3; values of K were identical, within experimental error, (4.4 mmHg). Sensitivity to induction of the bacterial membrane penicillin-sensitive lesion was calculated from the difference in the reciprocals of D 0 values proper to untreated and treated bacteria, for every gas used. The value of m could not be directly calculated because the effect of penicillin on anoxically irradiated bacteria was not detectable. For that reason, a transformation of the oxygen equation was used, allowing estimates to be made of both m and K, provided the results conformed with the equation. Within experimental error they did. Calculated values of m and K for induction of the penicillin-sensitive lesion were respectively 8 and 5.9 mmHg, but it is shown that the oxygen enhancement ratio was probably underestimated and the value overestimated. (author)

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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)

  16. 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

  17. Sinoporphyrin sodium, a novel sensitizer, triggers mitochondrial-dependent apoptosis in ECA-109 cells via production of reactive oxygen species

    Directory of Open Access Journals (Sweden)

    Wang H

    2014-06-01

    Full Text Available Haiping Wang,1 Xiaobing Wang,1 Shaoliang Zhang,2 Pan Wang,1 Kun Zhang,1 Quanhong Liu1 1Key Laboratory of Medicinal Resources and Natural Pharmaceutical Chemistry, Ministry of Education, National Engineering Laboratory for Resource Developing of Endangered Chinese Crude Drugs in Northwest of China, College of Life Sciences, Shaanxi Normal University, Xi'an, Shaanxi, 2Qinglong High-Tech Co, Ltd, Yichun, Jiangxi, People's Republic of China Background: Sonodynamic therapy (SDT is a promising method that uses ultrasound to activate certain chemical sensitizers for the treatment of cancer. The purpose of this study was to investigate the sonoactivity of a novel sensitizer, sinoporphyrin sodium (DVDMS, and its sonotoxicity in an esophageal cancer (ECA-109 cell line. Methods: The fluorescence intensity of DVDMS, hematoporphyrin, protoporphyrin IX, and Photofrin II was detected by fluorescence microscopy and flow cytometry. Generation of singlet oxygen was measured using a 1, 3-diphenylisobenzofuran experiment. A 3-(4, 5-dimethylthiazol-2-yl-2, 5-diphenyl tetrazolium bromide assay was used to examine cell viability. Production of reactive oxygen species (ROS and destabilization of the mitochondrial membrane potential were assessed by flow cytometry. Apoptosis was analyzed using Annexin-PE/7-amino-actinomycin D staining. Confocal microscopy was performed to assess mitochondrial damage and identify release of cytochrome C after treatment. Western blots were used to determine expression of oxidative stress-related and apoptosis-associated protein. Ultrastructural changes in the cell were studied by scanning electron microscopy. Results: DVDMS showed higher autofluorescence intensity and singlet oxygen production efficiency compared with other photosensitizers in both cancerous and normal cells. Compared with hematoporphyrin, DVDMS-mediated SDT was more cytotoxic in ECA-109 cells. Abundant intracellular ROS was found in the SDT groups, and the cytotoxicity

  18. Effect of oxygen and misonidazole on radiation damage in biologically active DNA dissolved in a bacterial extract. Influence of cytochrome c

    International Nuclear Information System (INIS)

    Lafleur, M.V.M.; Pluijmackers-Westmijze, E.J.; Loman, H.

    1982-01-01

    The effect of radiation on biologically active DNA, dissolved in a bacterial extract was studied. The results show that oxygen affects DNA inactivation for both double-stranded (RF) and single-stranded phiX174 DNA. Misonidazole induces an increased radiosensitivity in this system as found for single-stranded DNA. These effects disappear with ageing of the extract, but can be recovered by the addition of 10 -6 M cytochrome c. (author)

  19. 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.)

  20. 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.

  1. 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.

  2. Nature of oxygen containing radicals in radiation chemistry and photochemistry of aqueous solutions. Annual progress report, September 1978--July 1979

    International Nuclear Information System (INIS)

    Czapski, G.

    1979-01-01

    The proposed research is a continuation of the work conducted under this contract and is outlined. During this year, the main emphasis will be given to study further the properties of HO 2 and O 2 - and OH, mainly in their role in biological systems. We will continue to study and elucidate how O 2 - reacts in biological systems. The toxicity of O 2 - is quite well established, but the mechanism is still obscure. The Haber Weiss reaction most probably can not account for the toxicity of O 2 - nor for the formation of singlet oxygen, nor of OH. We will study if reduction of Fe 3+ complexes by O 2 - in biological systems does catalyze the Haber Weiss reaction and if OH is formed in this mechanism. The role of oxygen, radiosensitizers in radiation damage of bacteriophages and cells will be further studied, as well as on E. Coli and Enzymes. We will try to elucidate the formation and role of OH, O 2 - and O 2 in these systems as well as the relative contribution of endogenous and exogenous damage, and the role of direct and indirect radiation damage to cells. We intend also to study if SOD (super oxide dismutase) does react only with O 2 - or also with biological peroxides (RO 2 ) and Hydroperoxides (RO 2 H). Further studies of O 2 - and O 2 with various cytochromes, and hemoglobins is planned

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. Reactive oxygen species: role in the development of cancer and various chronic conditions

    Directory of Open Access Journals (Sweden)

    Waris Gulam

    2006-05-01

    Full Text Available Abstract Oxygen derived species such as superoxide radical, hydrogen peroxide, singlet oxygen and hydroxyl radical are well known to be cytotoxic and have been implicated in the etiology of a wide array of human diseases, including cancer. Various carcinogens may also partly exert their effect by generating reactive oxygen species (ROS during their metabolism. Oxidative damage to cellular DNA can lead to mutations and may, therefore, play an important role in the initiation and progression of multistage carcinogenesis. The changes in DNA such as base modification, rearrangement of DNA sequence, miscoding of DNA lesion, gene duplication and the activation of oncogenes may be involved in the initiation of various cancers. Elevated levels of ROS and down regulation of ROS scavengers and antioxidant enzymes are associated with various human diseases including various cancers. ROS are also implicated in diabtes and neurodegenerative diseases. ROS influences central cellular processes such as proliferation a, apoptosis, senescence which are implicated in the development of cancer. Understanding the role of ROS as key mediators in signaling cascades may provide various opportunities for pharmacological intervention.

  9. Reactive oxygen species: role in the development of cancer and various chronic conditions

    Science.gov (United States)

    Waris, Gulam; Ahsan, Haseeb

    2006-01-01

    Oxygen derived species such as superoxide radical, hydrogen peroxide, singlet oxygen and hydroxyl radical are well known to be cytotoxic and have been implicated in the etiology of a wide array of human diseases, including cancer. Various carcinogens may also partly exert their effect by generating reactive oxygen species (ROS) during their metabolism. Oxidative damage to cellular DNA can lead to mutations and may, therefore, play an important role in the initiation and progression of multistage carcinogenesis. The changes in DNA such as base modification, rearrangement of DNA sequence, miscoding of DNA lesion, gene duplication and the activation of oncogenes may be involved in the initiation of various cancers. Elevated levels of ROS and down regulation of ROS scavengers and antioxidant enzymes are associated with various human diseases including various cancers. ROS are also implicated in diabtes and neurodegenerative diseases. ROS influences central cellular processes such as proliferation a, apoptosis, senescence which are implicated in the development of cancer. Understanding the role of ROS as key mediators in signaling cascades may provide various opportunities for pharmacological intervention. PMID:16689993

  10. Photodynamic DNA damage induced by phycocyanin and its repair in Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    M. Pádula

    1999-09-01

    Full Text Available In the present study, we analyzed DNA damage induced by phycocyanin (PHY in the presence of visible light (VL using a set of repair endonucleases purified from Escherichia coli. We demonstrated that the profile of DNA damage induced by PHY is clearly different from that induced by molecules that exert deleterious effects on DNA involving solely singlet oxygen as reactive species. Most of PHY-induced lesions are single strand breaks and, to a lesser extent, base oxidized sites, which are recognized by Nth, Nfo and Fpg enzymes. High pressure liquid chromatography coupled to electrochemical detection revealed that PHY photosensitization did not induce 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo at detectable levels. DNA repair after PHY photosensitization was also investigated. Plasmid DNA damaged by PHY photosensitization was used to transform a series of Saccharomyces cerevisiae DNA repair mutants. The results revealed that plasmid survival was greatly reduced in rad14 mutants, while the ogg1 mutation did not modify the plasmid survival when compared to that in the wild type. Furthermore, plasmid survival in the ogg1 rad14 double mutant was not different from that in the rad14 single mutant. The results reported here indicate that lethal lesions induced by PHY plus VL are repaired differently by prokaryotic and eukaryotic cells. Morever, nucleotide excision repair seems to play a major role in the recognition and repair of these lesions in Saccharomyces cerevisiae.

  11. [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.

  12. Oxidative DNA Adducts Following Cu2+-Mediated Activation of Dihydroxy PCBs: Role of Reactive Oxygen Species1

    Science.gov (United States)

    Spencer, Wendy A.; Lehmler, Hans-Joachim; Robertson, Larry W.; Gupta, Ramesh C.

    2009-01-01

    Polychlorinated biphenyls (PCBs) are toxic industrial chemicals, complete carcinogens and efficacious tumor promoters. However, the mechanism(s) of PCB-mediated carcinogenicity remains largely undefined. One likely pathway by which these agents may play a role in carcinogenesis is the generation of oxidative DNA damage by redox cycling of dihydroxylated PCB metabolites. We have now employed a new 32P-postlabeling system to examine novel oxidative DNA lesions induced by Cu2+-mediated activation of PCB metabolites. 32P-Postlabeling of DNA incubated with various PCB metabolites resulted in over a dozen novel polar oxidative DNA adducts that were chromatographically similar for all active agents. The most potent metabolites tested were the hydroquinones (hydroxyl groups arranged para to each other) yielding polar oxidative adduct levels ranging from 55 to 142 adducts/106 nucleotides. PCB catechols, or ortho-dihydroxy metabolites, were up to 40% less active than their corresponding hydroquinone congeners while mono hydroxylated and quinone metabolites did not produce detectable oxidative damage over that of vehicle. With the exception of 2,4,5-Cl-2′,5′-dihydroxybiphenyl, this oxidative DNA damage appeared to be inversely related to chlorine content: no chlorine ≈ mono- > di- > tri-chlorinated metabolites. Importantly, copper, but not iron, was essential for activation of the PCB metabolites to these polar oxidative DNA adducts since in its absence or in the presence of the Cu+-specific scavenger, bathocuproine, no adducts were detected. Intervention studies with known reactive oxygen species (ROS) modifiers suggested that H2O2, singlet oxygen, hydroxyl radical and superoxide may also be involved in this PCB-mediated oxidative DNA damage. These data indicate a mechanistic role of several ROS, in addition to copper, in PCB-induced DNA damage and provide further support for oxidative DNA damage in PCB-mediated carcinogenesis. PMID:19233261

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Comparative study of the antioxidant and reactive oxygen species scavenging properties in the extracts of the fruits of Terminalia chebula, Terminalia belerica and Emblica officinalis.

    Science.gov (United States)

    Hazra, Bibhabasu; Sarkar, Rhitajit; Biswas, Santanu; Mandal, Nripendranath

    2010-05-13

    Cellular damage caused by reactive oxygen species (ROS) has been implicated in several diseases, and hence natural antioxidants have significant importance in human health. The present study was carried out to evaluate the in vitro antioxidant and reactive oxygen species scavenging activities of Terminalia chebula, Terminalia belerica and Emblica officinalis fruit extracts. The 70% methanol extracts were studied for in vitro total antioxidant activity along with phenolic and flavonoid contents and reducing power. Scavenging ability of the extracts for radicals like DPPH, hydroxyl, superoxide, nitric oxide, hydrogen peroxide, peroxynitrite, singlet oxygen, hypochlorous acid were also performed to determine the potential of the extracts. The ability of the extracts of the fruits in exhibiting their antioxative properties follow the order T. chebula >E. officinalis >T. belerica. The same order is followed in their flavonoid content, whereas in case of phenolic content it becomes E. officinalis >T. belerica >T. chebula. In the studies of free radicals' scavenging, where the activities of the plant extracts were inversely proportional to their IC50 values, T. chebula and E. officinalis were found to be taking leading role with the orders of T. chebula >E. officinalis >T. belerica for superoxide and nitric oxide, and E. officinalis >T. belerica >T. chebula for DPPH and peroxynitrite radicals. Miscellaneous results were observed in the scavenging of other radicals by the plant extracts, viz., T. chebula >T. belerica >E. officinalis for hydroxyl, T. belerica >T. chebula >E. officinalis for singlet oxygen and T. belerica >E. officinalis >T. chebula for hypochlorous acid. In a whole, the studied fruit extracts showed quite good efficacy in their antioxidant and radical scavenging abilities, compared to the standards. The evidences as can be concluded from the study of the 70% methanol extract of the fruits of Terminalia chebula, Terminalia belerica and Emblica officinalis

  1. 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 ...

  2. 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

  3. 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...

  4. 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

  5. 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

  6. 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...

  7. 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

  8. Effects of Laser Printer–Emitted Engineered Nanoparticles on Cytotoxicity, Chemokine Expression, Reactive Oxygen Species, DNA Methylation, and DNA Damage: A Comprehensive in Vitro Analysis in Human Small Airway Epithelial Cells, Macrophages, and Lymphoblasts

    Science.gov (United States)

    Pirela, Sandra V.; Miousse, Isabelle R.; Lu, Xiaoyan; Castranova, Vincent; Thomas, Treye; Qian, Yong; Bello, Dhimiter; Kobzik, Lester; Koturbash, Igor; Demokritou, Philip

    2015-01-01

    Background Engineered nanomaterials (ENMs) incorporated into toner formulations of printing equipment become airborne during consumer use. Although information on the complex physicochemical and toxicological properties of both toner powders and printer-emitted particles (PEPs) continues to grow, most toxicological studies have not used the actual PEPs but rather have primarily used raw toner powders, which are not representative of current exposures experienced at the consumer level during printing. Objectives We assessed the biological responses of a panel of human cell lines to PEPs. Methods Three physiologically relevant cell lines—small airway epithelial cells (SAECs), macrophages (THP-1 cells), and lymphoblasts (TK6 cells)—were exposed to PEPs at a wide range of doses (0.5–100 μg/mL) corresponding to human inhalation exposure durations at the consumer level of 8 hr or more. Following treatment, toxicological parameters reflecting distinct mechanisms were evaluated. Results PEPs caused significant membrane integrity damage, an increase in reactive oxygen species (ROS) production, and an increase in pro-inflammatory cytokine release in different cell lines at doses equivalent to exposure durations from 7.8 to 1,500 hr. Furthermore, there were differences in methylation patterns that, although not statistically significant, demonstrate the potential effects of PEPs on the overall epigenome following exposure. Conclusions The in vitro findings obtained in this study suggest that laser printer–emitted engineered nanoparticles may be deleterious to lung cells and provide preliminary evidence of epigenetic modifications that might translate to pulmonary disorders. Citation Pirela SV, Miousse IR, Lu X, Castranova V, Thomas T, Qian Y, Bello D, Kobzik L, Koturbash I, Demokritou P. 2016. Effects of laser printer–emitted engineered nanoparticles on cytotoxicity, chemokine expression, reactive oxygen species, DNA methylation, and DNA damage: a comprehensive in

  9. Ambient oxygen promotes tumorigenesis.

    Directory of Open Access Journals (Sweden)

    Ho Joong Sung

    2011-05-01

    Full Text Available Oxygen serves as an essential factor for oxidative stress, and it has been shown to be a mutagen in bacteria. While it is well established that ambient oxygen can also cause genomic instability in cultured mammalian cells, its effect on de novo tumorigenesis at the organismal level is unclear. Herein, by decreasing ambient oxygen exposure, we report a ∼50% increase in the median tumor-free survival time of p53-/- mice. In the thymus, reducing oxygen exposure decreased the levels of oxidative DNA damage and RAG recombinase, both of which are known to promote lymphomagenesis in p53-/- mice. Oxygen is further shown to be associated with genomic instability in two additional cancer models involving the APC tumor suppressor gene and chemical carcinogenesis. Together, these observations represent the first report directly testing the effect of ambient oxygen on de novo tumorigenesis and provide important physiologic evidence demonstrating its critical role in increasing genomic instability in vivo.

  10. Schiff bases of putrescine with methylglyoxal protect from cellular damage caused by accumulation of methylglyoxal and reactive oxygen species in Dictyostelium discoideum.

    Science.gov (United States)

    Park, Seong-Jun; Kwak, Min-Kyu; Kang, Sa-Ouk

    2017-05-01

    Polyamines protect protein glycation in cells against the advanced glycation end product precursor methylglyoxal, which is inevitably produced during glycolysis, and the enzymes that detoxify this α-ketoaldehyde have been widely studied. Nonetheless, nonenzymatic methylglyoxal-scavenging molecules have not been sufficiently studied either in vitro or in vivo. Here, we hypothesized reciprocal regulation between polyamines and methylglyoxal modeled in Dictyostelium grown in a high-glucose medium. We based our hypothesis on the reaction between putrescine and methylglyoxal in putrescine-deficient (odc - ) or putrescine-overexpressing (odc oe ) cells. In these strains, growth and cell cycle were found to be dependent on cellular methylglyoxal and putrescine contents. The odc - cells showed growth defects and underwent G1 phase cell cycle arrest, which was efficiently reversed by exogenous putrescine. Cellular methylglyoxal, reactive oxygen species (ROS), and glutathione levels were remarkably changed in odc oe cells and odc̄ cells. These results revealed that putrescine may act as an intracellular scavenger of methylglyoxal and ROS. Herein, we observed interactions of putrescine and methylglyoxal via formation of a Schiff base complex, by UV-vis spectroscopy, and confirmed this adduct by liquid chromatography with mass spectrometry via electrospray ionization. Schiff bases were isolated, analyzed, and predicted to have molecular masses ranging from 124 to 130. We showed that cellular putrescine-methylglyoxal Schiff bases were downregulated in proportion to the levels of endogenous or exogenous putrescine and glutathione in the odc mutants. The putrescine-methylglyoxal Schiff base affected endogenous metabolite levels. This is the first report showing that cellular methylglyoxal functions as a signaling molecule through reciprocal interactions with polyamines by forming Schiff bases. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. 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.

  12. 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 ...

  13. 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.

  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. 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.

  16. 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.

  17. Comparative kinetics of damage to the plasma and mitochondrial membranes by intra-cellularly synthesized and externally-provided photosensitizers using multi-color FACS.

    Science.gov (United States)

    Haupt, Sara; Malik, Zvi; Ehrenberg, Benjamin

    2014-01-01

    Photodynamic therapy (PDT) of cancer involves inflicting lethal damage to the cells of malignant tumors, primarily by singlet oxygen that is generated following light-absorption in a photosensitizer molecule. Dysfunction of cells is manifested in many ways, including peroxidation of cellular components, membrane rupture, depolarization of electric potentials, termination of mitochondrial activity, onset of apoptosis and necrosis and eventually cell lysis. These events do not necessarily occur in linear fashion and different types of damage to cell components occur, most probably, in parallel. In this report we measured the relative rates of damage to two cellular membranes: the plasma membrane and the mitochondrial membrane. We employed photosensitizers of diverse hydrophobicities and used different incubation procedures, which lead to their different intra-cellular localizations. We monitored the damage that was inflicted on these membranes, by employing optical probes of membrane integrity, in a multi-color FACS experiment. The potentiometric indicator JC-1 monitored the electric cross-membrane potential of the mitochondria and the fluorometric indicator Draq7 monitored the rupture of the plasma membrane. We show that the electric depolarization of the mitochondrial membrane and the damage to the enveloping plasma membrane proceed with different kinetics that reflect the molecular character and intracellular location of the sensitizer: PpIX that is synthesized in the cells from ALA causes rapid mitochondrial damage and very slow damage to the plasma membrane, while externally added PpIX has an opposite effect. The hydrophilic sensitizer HypS4 can be taken up by the cells by different incubation conditions, and these affect its intracellular location, and as a consequence either the plasma membrane or the mitochondria is damaged first. A similar correlation was found for additional extracellularly-provided photosensitizers HP and PpIX.

  18. 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.

  19. Spectroscopic study on the sonodynamic and sonocatalytic damage of anthraquinone derivants to bovine serum albumin under ultrasonic irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Wang Zhiqiu; Gao Jingqun [College of Chemistry, Liaoning University, Shenyang 110036 (China); Wang Jun, E-mail: wangjun890@126.com [College of Chemistry, Liaoning University, Shenyang 110036 (China); Li Ying; Li Kai; Kang Pingli; Zhang Xiangdong [College of Chemistry, Liaoning University, Shenyang 110036 (China)

    2012-03-15

    In this work, three anthraquinone derivants (Alizarin: 1,2-dihydroxy-9, 10-anthraquinone, Alizarin-DA: 1,2-dihydroxy-9, 10-anthraquinone-3-aminomethyl-N, N-diacetic acid and Alizarin-DA-Fe: 1,2-dihydroxy-9, 10-anthraquinone-3-aminomethyl-N, N-diacetate-Ferrous(III)) were used to study the sonodynamic and sonocatalytic damage of bovine serum albumin (BSA) molecules according to the hyperchromic effect of UV-vis spectra and quenching effect of intrinsic fluorescence. Meanwhile, some influencing factors such as ultrasonic irradiation time, anthraquinone derivants concentration and ionic strength on the damage of BSA molecules were also considered. The results show that the synergetic effect of anthraquinone derivants and ultrasonic irradiation can efficiently damage the BSA molecules. Finally, some special radical scavengers were used to determine the kind of generated reactive oxygen species (ROS) in the presence of three anthraquinone derivants under ultrasonic irradiation. The results show that the ROS, at least, including singlet oxygen ({sup 1}O{sub 2}) and hydroxyl radicals (OH) are generated during the sonodynamic and sonocatalytic processes. It is wished that this paper could offer some valuable references for the application of anthraquinone derivants in sonodynamic therapy (SDT) and sonocatalytic therapy (SCT) for tumor treatment. - Highlights: Black-Right-Pointing-Pointer Anthraquinone derivants were used to study the sonodynamic and sonocatalytic damage to BSA. Black-Right-Pointing-Pointer The generations of ROS during sonodynamic and sonocatalytic process were estimated. Black-Right-Pointing-Pointer Some quenchers were used to determine the kind of the ROS.

  20. Effects of Laser Printer-Emitted Engineered Nanoparticles on Cytotoxicity, Chemokine Expression, Reactive Oxygen Species, DNA Methylation, and DNA Damage: A Comprehensive in Vitro Analysis in Human Small Airway Epithelial Cells, Macrophages, and Lymphoblasts.

    Science.gov (United States)

    Pirela, Sandra V; Miousse, Isabelle R; Lu, Xiaoyan; Castranova, Vincent; Thomas, Treye; Qian, Yong; Bello, Dhimiter; Kobzik, Lester; Koturbash, Igor; Demokritou, Philip

    2016-02-01

    Engineered nanomaterials (ENMs) incorporated into toner formulations of printing equipment become airborne during consumer use. Although information on the complex physicochemical and toxicological properties of both toner powders and printer-emitted particles (PEPs) continues to grow, most toxicological studies have not used the actual PEPs but rather have primarily used raw toner powders, which are not representative of current exposures experienced at the consumer level during printing. We assessed the biological responses of a panel of human cell lines to PEPs. Three physiologically relevant cell lines--small airway epithelial cells (SAECs), macrophages (THP-1 cells), and lymphoblasts (TK6 cells)--were exposed to PEPs at a wide range of doses (0.5-100 μg/mL) corresponding to human inhalation exposure durations at the consumer level of 8 hr or more. Following treatment, toxicological parameters reflecting distinct mechanisms were evaluated. PEPs caused significant membrane integrity damage, an increase in reactive oxygen species (ROS) production, and an increase in pro-inflammatory cytokine release in different cell lines at doses equivalent to exposure durations from 7.8 to 1,500 hr. Furthermore, there were differences in methylation patterns that, although not statistically significant, demonstrate the potential effects of PEPs on the overall epigenome following exposure. The in vitro findings obtained in this study suggest that laser printer-emitted engineered nanoparticles may be deleterious to lung cells and provide preliminary evidence of epigenetic modifications that might translate to pulmonary disorders.

  1. DNA damage and autophagy

    International Nuclear Information System (INIS)

    Rodriguez-Rocha, Humberto; Garcia-Garcia, Aracely; Panayiotidis, Mihalis I.; Franco, Rodrigo

    2011-01-01

    Both exogenous and endogenous agents are a threat to DNA integrity. Exogenous environmental agents such as ultraviolet (UV) and ionizing radiation, genotoxic chemicals and endogenous byproducts of metabolism including reactive oxygen species can cause alterations in DNA structure (DNA damage). Unrepaired DNA damage has been linked to a variety of human disorders including cancer and neurodegenerative disease. Thus, efficient mechanisms to detect DNA lesions, signal their presence and promote their repair have been evolved in cells. If DNA is effectively repaired, DNA damage response is inactivated and normal cell functioning resumes. In contrast, when DNA lesions cannot be removed, chronic DNA damage triggers specific cell responses such as cell death and senescence. Recently, DNA damage has been shown to induce autophagy, a cellular catabolic process that maintains a balance between synthesis, degradation, and recycling of cellular components. But the exact mechanisms by which DNA damage triggers autophagy are unclear. More importantly, the role of autophagy in the DNA damage response and cellular fate is unknown. In this review we analyze evidence that supports a role for autophagy as an integral part of the DNA damage response.

  2. Origins of Singlet Fission in Solid Pentacene from an ab initio Green's Function Approach

    Science.gov (United States)

    Refaely-Abramson, Sivan; da Jornada, Felipe H.; Louie, Steven G.; Neaton, Jeffrey B.

    2017-12-01

    We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a G W plus Bethe-Salpeter equation approach, we calculate the exciton-biexciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two noninteracting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay process from a bright singlet state requires a final state consisting of two inequivalent nearly degenerate triplets of nonzero, equal and opposite, center-of-mass momenta. For such a process, we predict a singlet lifetime of 30-70 fs, in very good agreement with experimental data, indicating that this process can dominate singlet fission in crystalline pentacene. Our approach is general and provides a framework for predicting and understanding multiexciton interactions in solids.

  3. Diradical character dependences of the first and second hyperpolarizabilities of asymmetric open-shell singlet systems.

    Science.gov (United States)

    Nakano, Masayoshi; Champagne, Benoît

    2013-06-28

    The static first and second hyperpolarizabilities (referred to as β and γ, respectively) of asymmetric open-shell singlet systems have been investigated using the asymmetric two-site diradical model within the valence configuration interaction level of theory in order to reveal the effect of the asymmetric electron distribution on the diradical character and subsequently on β and γ. It is found that the increase of the asymmetric electron distribution causes remarkable changes in the amplitude and the sign of β and γ, and that their variations are intensified with the increase of the diradical character. These results demonstrate that the asymmetric open-shell singlet systems with intermediate diradical characters can exhibit further enhancements of β and γ as compared to conventional asymmetric closed-shell systems and also to symmetric open-shell singlet systems with intermediate diradical characters.

  4. Singlet-to-triplet intermediates and triplet exciton dynamics in pentacene thinfilms

    Science.gov (United States)

    Thorsmolle, Verner; Korber, Michael; Obergfell, Emanuel; Kuhlman, Thomas; Campbell, Ian; Crone, Brian; Taylor, Antoinette; Averitt, Richard; Demsar, Jure

    Singlet-to-triplet fission in organic semiconductors is a spin-conserving multiexciton process in which one spin-zero singlet excitation is converted into two spin-one triplet excitations on an ultrafast timescale. Current scientific interest into this carrier multiplication process is largely driven by prospects of enhancing the efficiency in photovoltaic applications by generating two long-lived triplet excitons by one photon. The fission process is known to involve intermediate states, known as correlated triplet pairs, with an overall singlet character, before being interchanged into uncorrelated triplets. Here we use broadband femtosecond real-time spectroscopy to study the excited state dynamics in pentacene thin films, elucidating the fission process and the role of intermediate triplet states. VKT and AJT acknowledge support by the LDRD program at Los Alamos National Laboratory and the Department of Energy, Grant No. DE-FG02-04ER118. MK, MO and JD acknowledge support by the Alexander von Humboldt Foundation.

  5. Interplay between singlet and triplet excited states in a conformationally locked donor–acceptor dyad

    KAUST Repository

    Filatov, Mikhail A.

    2015-10-13

    The synthesis and photophysical characterization of a palladium(II) porphyrin – anthracene dyad bridged via short and conformationally rigid bicyclo[2.2.2]octadiene spacer were achieved. A spectroscopic investigation of the prepared molecule in solution has been undertaken to study electronic energy transfer in excited singlet and triplet states between the anthracene and porphyrin units. By using steady-state and time-resolved photoluminescence spectroscopy it was shown that excitation of the singlet excited state of the anthracene leads to energy transfer to the lower-lying singlet state of porphyrin. Alternatively, excitation of the porphyrin followed by intersystem crossing to the triplet state leads to very fast energy transfer to the triplet state of anthracene. The rate of this energy transfer has been determined by transient absorption spectroscopy. Comparative studies of the dynamics of triplet excited states of the dyad and reference palladium octaethylporphyrin (PdOEP) have been performed.

  6. Oxygen Therapy

    Science.gov (United States)

    ... oxygen at very high altitudes (like in the mountains or in an airplane) even if you do ... an arterial blood gas (ABG) measurement. The ABG measures your oxygen level directly from your blood and ...

  7. Bortezomib-induced sensitization of malignant human glioma cells to vorinostat-induced apoptosis depends on reactive oxygen species production, mitochondrial dysfunction, Noxa upregulation, Mcl-1 cleavage, and DNA damage.

    Science.gov (United States)

    Premkumar, Daniel R; Jane, Esther P; Agostino, Naomi R; DiDomenico, Joseph D; Pollack, Ian F

    2013-02-01

    Glioblastomas are invasive tumors with poor prognosis despite current therapies. Histone deacetylase inhibitors (HDACIs) represent a class of agents that can modulate gene expression to reduce tumor growth, and we and others have noted some antiglioma activity from HDACIs, such as vorinostat, although insufficient to warrant use as monotherapy. We have recently demonstrated that proteasome inhibitors, such as bortezomib, dramatically sensitized highly resistant glioma cells to apoptosis induction, suggesting that proteasomal inhibition may be a promising combination strategy for glioma therapeutics. In this study, we examined whether bortezomib could enhance response to HDAC inhibition in glioma cells. Although primary cells from glioblastoma multiforme (GBM) patients and established glioma cell lines did not show significant induction of apoptosis with vorinostat treatment alone, the combination of vorinostat plus bortezomib significantly enhanced apoptosis. The enhanced efficacy was due to proapoptotic mitochondrial injury and increased generation of reactive oxygen species. Our results also revealed that combination of bortezomib with vorinostat enhanced apoptosis by increasing Mcl-1 cleavage, Noxa upregulation, Bak and Bax activation, and cytochrome c release. Further downregulation of Mcl-1 using shRNA enhanced cell killing by the bortezomib/vorinostat combination. Vorinostat induced a rapid and sustained phosphorylation of histone H2AX in primary GBM and T98G cells, and this effect was significantly enhanced by co-administration of bortezomib. Vorinostat/bortezomib combination also induced Rad51 downregulation, which plays an important role in the synergistic enhancement of DNA damage and apoptosis. The significantly enhanced antitumor activity that results from the combination of bortezomib and HDACIs offers promise as a novel treatment for glioma patients. Copyright © 2011 Wiley Periodicals, Inc.

  8. Antibacterial, Antiviral, and Oxygen-Sensing Nanoparticles Prepared from Electrospun Materials

    Czech Academy of Sciences Publication Activity Database

    Henke, P.; Kirakci, Kaplan; Kubát, Pavel; Fraiberk, M.; Forstová, J.; Mosinger, Jiří

    2016-01-01

    Roč. 8, č. 38 (2016), s. 25127-25136 ISSN 1944-8244 R&D Projects: GA ČR(CZ) GA16-15020S; GA MŠk(CZ) LM2015073 Institutional support: RVO:61388980 ; RVO:61388955 Keywords : antibacterial * antiviral * nanoparticles * oxygen-sensing * singlet oxygen Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 7.504, year: 2016

  9. Baryogenesis in the two doublet and inert singlet extension of the Standard Model

    DEFF Research Database (Denmark)

    Alanne, Tommi; Kainulainen, Kimmo; Tuominen, Kimmo

    2016-01-01

    We investigate an extension of the Standard Model containing two Higgs doublets and a singlet scalar field (2HDSM). We show that the model can have a strongly first-order phase transition and give rise to the observed baryon asymmetry of the Universe, consistent with all experimental constraints...... with the critical temperature, Tn Tc, which can significantly alter the usual phase-transition pattern in 2HD models with Tn ≈ Tc. Furthermore, the singlet field can be the dark matter particle. However, in models with a strong first-order transition its abundance is typically but a thousandth of the observed dark...... matter abundance....

  10. On colour non-singlet representations of the quark-gluon system at finite temperature

    International Nuclear Information System (INIS)

    Abbas, A.; Paria, L.

    2000-01-01

    We use a group theoretical technique to project out the partition function for a system of quarks, antiquarks and gluons onto a particular representation of the internal symmetry group SU(3): the colour singlet, colour octet and colour 27-plet, at finite temperature. We do this to calculate the thermodynamic quantities for those representations. We also calculate the change in free energy of the plasma droplet formed from the hot hadronic gas. We find that the size of the droplet in the colour-octet representation is smaller than that in the colour-singlet representations at different temperatures in the vicinity of the critical temperatures of the phase transitions. (orig.)

  11. Coherent dynamics of singlet fission controlled by nonlocal electron-phonon coupling

    Science.gov (United States)

    Yao, Yao

    2016-03-01

    Based on the Frenkel and charge transfer mixing model of singlet fission (SF), we incorporate both the local and nonlocal phonon baths into the Hamiltonian and adopt the algorithm of the time-dependent density matrix renormalization group to simulate the SF process in tetracene and pentacene. The endergonic SF is found to be facilitated by the robust quantum coherence, which concurrently gives rise to a notable quantum beating effect. Being controlled by the nonlocal electron-phonon coupling, the SF process is accelerated and the triplet yield manifests a nonlinear relationship with the singlet density.

  12. Protective effects of topical application of a poorly soluble antioxidant astaxanthin liposomal formulation on ultraviolet-induced skin damage.

    Science.gov (United States)

    Hama, Susumu; Takahashi, Kanako; Inai, Yuko; Shiota, Kanako; Sakamoto, Ryota; Yamada, Asako; Tsuchiya, Hiroyuki; Kanamura, Kiyoshi; Yamashita, Eiji; Kogure, Kentaro

    2012-08-01

    Astaxanthin (Asx) would be expected to prevent ultraviolet (UV)-induced skin damage, as it is regarded as a potent antioxidative carotenoid in biological membranes. However, it is difficult to administer Asx topically to skin because of its poor water solubility. In this study, we attempted to solve this problem by preparing liposomes containing Asx (Asx-lipo), which were dispersible in the water phase, and therefore, suitable for topical application to the skin. Asx-lipo was shown to have potent scavenging ability against chemiluminescence-dependent singlet oxygen production in the water phase. When Asx-lipo was applied to skin before UV exposure, UV-induced skin thickening was prevented. Interestingly, collagen reduction induced by UV exposure was also prevented by preadministration of Asx-lipo. In addition, topical administration of Asx-lipo containing cationic lipid inhibited melanin production in skin exposed to UV. Consequently, we succeeded in preventing UV-induced skin damage using a topical application of a liposomal formulation containing Asx. Copyright © 2012 Wiley Periodicals, Inc.

  13. Research on chemical and discharge oxygen-iodine lasers

    Czech Academy of Sciences Publication Activity Database

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

    2009-01-01

    Roč. 107, č. 5 (2009), s. 816-825 ISSN 0030-400X R&D Projects: GA ČR GA202/07/0323; GA ČR GA202/09/0310; GA MŠk ME 833 Grant - others:US Air Force EOARD(US) FA8655-09-1-3091 Institutional research plan: CEZ:AV0Z10100523 Keywords : oxygen-iodine laser * COIL * DOIL * ElectricOIL * singlet oxygen * atomic iodine Subject RIV: BH - Optics, Masers, Lasers Impact factor: 0.505, year: 2009

  14. Sequence specificity of alkali-labile DNA damage photosensitized by suprofen.

    Science.gov (United States)

    Starrs, S M; Davies, R J

    2000-09-01

    On irradiation at UVB wavelengths, in aerated neutral aqueous solution, the anti-inflammatory drug suprofen (SP) photosensitizes the production of alkali-labile cleavage sites in DNA much more efficiently than direct strand breaks. It is active at submillimolar concentrations despite having no significant binding affinity for DNA. Gel sequencing studies utilizing 32P-end-labeled oligonucleotides have revealed that piperidine-sensitive lesions are formed predominantly at the positions of guanine (G) bases, with the extent of modification being UV dose- and SP concentration-dependent. Quite distinct patterns of G-specific damage are observed in single-stranded and duplex DNA molecules. The uniform attack at all G residues in single-stranded DNA, which is enhanced in D2O, is compatible with a Type-II mechanism. SP is a known generator of singlet oxygen whose participation in the reaction is supported by the effects of quenchers and scavengers. In duplex DNA, piperidine-induced cleavage occurs with high selectivity at the 5'-G of GG and (less prominently) GA doublets. This behavior is characteristic of a Type-I process involving electron transfer from DNA to photoexcited SP molecules. The ability of SP to sensitize the formation of Type-I and Type-II photo-oxidation products from 2'-deoxyguanosine attests to the feasibility of competing mechanisms in DNA.

  15. Harnessing singlet exciton fission to break the Shockley-Queisser limit

    Science.gov (United States)

    Rao, Akshay; Friend, Richard H.

    2017-11-01

    Singlet exciton fission is a carrier multiplication process in organic semiconductors that generates two electron-hole pairs for each photon absorbed. Singlet fission occurs on sub-100 fs timescales with yields of up to 200%, and photovoltaic devices based on singlet fission have achieved external quantum efficiencies above 100%. The major challenge for the field is to use singlet fission to improve the efficiency of conventional inorganic solar cells, such as silicon, and to break the Shockley-Queisser limit on the efficiency of single-junction photovoltaics. Achieving this goal requires a broader and more collaborative effort than the one used at present. Synthetic chemists, spectroscopists, theorists, materials scientists, device physicists and engineers will need to work together. In this Review, we critically assess the current status of the field, highlight the key results and identify the challenges ahead. In doing so, we seek to open the field to new expertise and ideas, which will in turn promote both fundamental science and device applications.

  16. Toward Designed Singlet Fission: Electronic States and Photophysics of 1,3-Diphenylisobenzofuran

    Czech Academy of Sciences Publication Activity Database

    Schwerin, A. F.; Johnson, J. C.; Smith, M. B.; Sreearunothai, P.; Popovič, D.; Černý, Jiří; Havlas, Zdeněk; Paci, I.; Akdag, A.; MacLeod, M. K.; Chen, X.; David, D. E.; Ratner, M. A.; Miller, J. R.; Nozik, A. J.; Michl, Josef

    2010-01-01

    Roč. 114, č. 3 (2010), s. 1457-1473 ISSN 1089-5639 R&D Projects: GA MŠk ME09114 Grant - others:NSF(US) OISE-0532040 Institutional research plan: CEZ:AV0Z40550506 Keywords : photophysics * singlet fission * DFT Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.732, year: 2010

  17. Photocurrent Enhanced by Singlet Fission in a Dye-Sensitized Solar Cell

    Czech Academy of Sciences Publication Activity Database

    Schrauben, J. N.; Zhao, Y.; Mercado, C.; Dron, P. I.; Ryerson, J. L.; Michl, Josef; Zhu, K.; Johnson, J. C.

    2015-01-01

    Roč. 7, č. 4 (2015), s. 2286-2293 ISSN 1944-8244 Institutional support: RVO:61388963 Keywords : photovoltaics * singlet fission * triplet * spectroscopy * charge transfer * photocurrent Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 7.145, year: 2015

  18. 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.

  19. An operator basis for the Standard Model with an added scalar singlet

    Energy Technology Data Exchange (ETDEWEB)

    Gripaios, Ben [Cavendish Laboratory, J.J. Thomson Avenue, Cambridge (United Kingdom); Sutherland, Dave [Cavendish Laboratory, J.J. Thomson Avenue, Cambridge (United Kingdom); Kavli Institute for Theoretical Physics, UCSB Kohn Hall, Santa Barbara CA (United States)

    2016-08-17

    Motivated by the possible di-gamma resonance at 750 GeV, we present a basis of effective operators for the Standard Model plus a scalar singlet at dimensions 5, 6, and 7. We point out that an earlier list at dimensions 5 and 6 contains two redundant operators at dimension 5.

  20. A two-component dark matter model with real singlet scalars ...

    Indian Academy of Sciences (India)

    2016-01-05

    Jan 5, 2016 ... We propose a two-component dark matter (DM) model, each component of which is a real singlet scalar, to explain results from both direct and indirect detection experiments. We put the constraints on the model parameters from theoretical bounds, PLANCK relic density results and direct DM experiments.

  1. Regge-like initial input and evolution of non-singlet structure ...

    Indian Academy of Sciences (India)

    The non-singlet structure functions, evolved in accordance with DGLAP evolution equations up to next-next-to-leading order are studied phenomenologically in comparison with the available experimental and parametrization results taken from NMC, CCFR, NuTeV, CORUS, CDHSW, NNPDF and MSTW Collaborations and ...

  2. The singlet-triplet energy gap in divalent three, five and seven ...

    African Journals Online (AJOL)

    The singlet-triplet energy gap in divalent three, five and seven-membered cyclic C2H2M, C4H4M and C6H6M (M = C, Si, Ge, Sn AND Pb) ... Nuclear independent chemical shifts (NICS) calculations were carried out for determination of aromatic character. The geometrical parameters are calculated and discussed.

  3. Singlet fission/silicon solar cell exceeding 100% EQE (Conference Presentation)

    Science.gov (United States)

    Pazos, Luis M.; Lee, Jumin; Kirch, Anton; Tabachnyk, Maxim; Friend, Richard H.; Ehrler, Bruno

    2016-09-01

    Current matching limits the commercialization of tandem solar cells due to their instability over spectral changes, leading to the need of using solar concentrators and trackers to keep the spectrum stable. We demonstrate that voltage-matched systems show far higher performance over spectral changes; caused by clouds, dust and other variations in atmospheric conditions. Singlet fission is a process in organic semiconductors which has shown very efficient, 200%, down-conversion yield and the generated excitations are long-lived, ideal for solar cells. As a result, the number of publications has grown exponentially in the past 5 years. Yet, so far no one has achieved to combine singlet fission with most low bandgap semiconductors, including crystalline silicon, the dominating solar cell material with a 90% share of the PV Market. Here we show that singlet fission can facilitate the fabrication of voltage-matched systems, opening a simple design route for the effective implementation of down-conversion in commercially available photovoltaic technologies, with no modification of the electronic circuitry of such. The implemention of singlet fission is achieved simply by decoupling the fabrication of the individual subcells. For this demonstration we used an ITO/PEDOT/P3HT/Pentacene/C60/Ag wide-bandgap subcell, and a commercial silicon solar cell as the low-bandgap component. We show that the combination of the two leads to the first tandem silicon solar cell which exceeds 100% external quantum efficiency.

  4. Photocurrent enhanced by singlet fission in a dye-sensitized solar cell.

    Science.gov (United States)

    Schrauben, Joel N; Zhao, Yixin; Mercado, Candy; Dron, Paul I; Ryerson, Joseph L; Michl, Josef; Zhu, Kai; Johnson, Justin C

    2015-02-04

    Investigations of singlet fission have accelerated recently because of its potential utility in solar photoconversion, although only a few reports definitively identify the role of singlet fission in a complete solar cell. Evidence of the influence of singlet fission in a dye-sensitized solar cell using 1,3-diphenylisobenzofuran (DPIBF, 1) as the sensitizer is reported here. Self-assembly of the blue-absorbing 1 with co-adsorbed oxidation products on mesoporous TiO2 yields a cell with a peak internal quantum efficiency of ∼70% and a power conversion efficiency of ∼1.1%. Introducing a ZrO2 spacer layer of thickness varying from 2 to 20 Å modulates the short-circuit photocurrent such that it is initially reduced as thickness increases but 1 with 10-15 Å of added ZrO2. This rise can be explained as being due to a reduced rate of injection of electrons from the S1 state of 1 such that singlet fission, known to occur with a 30 ps time constant in polycrystalline films, has the opportunity to proceed efficiently and produce two T1 states per absorbed photon that can subsequently inject electrons into TiO2. Transient spectroscopy and kinetic simulations confirm this novel mode of dye-sensitized solar cell operation and its potential utility for enhanced solar photoconversion.

  5. Singlet Ground State Magnetism: III Magnetic Excitons in Antiferromagnetic TbP

    DEFF Research Database (Denmark)

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

    1981-01-01

    The dispersion of the lowest magnetic excitations of the singlet ground state system TbP has been studied in the antiferromagnetic phase by inelastic neutron scattering. The magnetic exchange interaction and the magnetic and the rhombohedral molecular fields have been determined....

  6. Optimal free will on one side in reproducing the singlet correlation

    International Nuclear Information System (INIS)

    Banik, Manik; Gazi, MD. Rajjak; Das, Subhadipa; Rai, Ashutosh; Kunkri, Samir

    2012-01-01

    Bell’s theorem teaches us that there are quantum correlations that cannot be simulated by just shared randomness (local hidden variable). There are some recent results which simulate the singlet correlation by using either 1 bit or a binary (no-signaling) correlation which violates Bell’s inequality maximally. But there is one more possible way to simulate quantum correlation by relaxing the condition of independency of measurement on shared randomness. Recently, Hall showed that the statistics of a singlet state can be generated by sacrificing measurement independence where underlying distribution of hidden variables depends on measurement directions of both parties (Hall 2010 Phys. Rev. Lett. 105 250404). He also proved that for any model of singlet correlation, 86% measurement independence is optimal. In this paper, we show that 59% measurement independence is optimal for simulating the singlet correlation when the underlying distribution of hidden variables depends only on the measurements of one party. We also show that a distribution corresponding to this optimal lack of free will already exists in the literature which first appeared in the context of detection efficiency loophole (Gisin and Gisin 1999 Phys. Lett. A 323–7). (paper)

  7. General Approach to the Evolution of Singlet Nanoparticles from a Rapidly Quenched Point Source

    NARCIS (Netherlands)

    Feng, J.; Huang, Luyi; Ludvigsson, Linus; Messing, Maria; Maiser, A.; Biskos, G.; Schmidt-Ott, A.

    2016-01-01

    Among the numerous point vapor sources, microsecond-pulsed spark ablation at atmospheric pressure is a versatile and environmentally friendly method for producing ultrapure inorganic nanoparticles ranging from singlets having sizes smaller than 1 nm to larger agglomerated structures. Due to its fast

  8. Soluble and stable heptazethrenebis(dicarboximide) with a singlet open-shell ground state

    KAUST Repository

    Sun, Zhe

    2011-08-10

    A soluble and stable heptazethrene derivative was synthesized and characterized for the first time. This molecule exhibits a singlet biradical character in the ground state, which is the first case among zethrene homologue series. Exceptional stability of this heptazethrenebis(dicarboximide) raises the likelihood of its practical applications in materials science. © 2011 American Chemical Society.

  9. Singlet Exciton Lifetimes in Conjugated Polymer Films for Organic Solar Cells

    KAUST Repository

    Dimitrov, Stoichko

    2016-01-13

    The lifetime of singlet excitons in conjugated polymer films is a key factor taken into account during organic solar cell device optimization. It determines the singlet exciton diffusion lengths in polymer films and has a direct impact on the photocurrent generation by organic solar cell devices. However, very little is known about the material properties controlling the lifetimes of singlet excitons, with most of our knowledge originating from studies of small organic molecules. Herein, we provide a brief summary of the nature of the excited states in conjugated polymer films and then present an analysis of the singlet exciton lifetimes of 16 semiconducting polymers. The exciton lifetimes of seven of the studied polymers were measured using ultrafast transient absorption spectroscopy and compared to the lifetimes of seven of the most common photoactive polymers found in the literature. A plot of the logarithm of the rate of exciton decay vs. the polymer optical bandgap reveals a medium correlation between lifetime and bandgap, thus suggesting that the Energy Gap Law may be valid for these systems. This therefore suggests that small bandgap polymers can suffer from short exciton lifetimes, which may limit their performance in organic solar cell devices. In addition, the impact of film crystallinity on the exciton lifetime was assessed for a small bandgap diketopyrrolopyrrole co-polymer. It is observed that the increase of polymer film crystallinity leads to reduction in exciton lifetime and optical bandgap again in agreement with the Energy Gap Law.

  10. 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

  11. Fluorescence studies on radiation oxidative damage to membranes ...

    Indian Academy of Sciences (India)

    Unknown

    Keywords. Membrane oxidative damage; cellular radiosensitivity; DPH fluorescence; lipid peroxidation; liposomal membrane; thymocyte membrane permeability. 1. Introduction. Radiation damage to cells and tissues involves generation of reactive oxygen species. (ROS) followed by alterations in lipids, DNA and proteins, ...

  12. Ligands of low electronegativity in the vsepr model: the structures of singlet carbenes

    Science.gov (United States)

    Cuthbertson, Alastair F.; Glidewell, Christopher

    Equilibrium structures and force constants for skeletal bending from linearity have been calculated, in the MNDO approximation, for twenty five singlet carbenes CX 2. When the substituent X bears neither vacant orbitais nor lone pairs, the force constant becomes steadily more negative as the electronegativity of X increases; when X bears vacant orbitais, the C-X π bond order and the force constant both increase with the electronegativity of X. When X bears lone pairs, the force constant parallels the HOMO-LUMO gap at linearity. Previous discussions of the structures of singlet carbenes are shown to be inadequate: the reported results support the interpretation in terms of the second-order Jahn-Teller effect of the observed stereochemical inactivity of lone pairs in the presence of ligands of low electronegativity.

  13. Simulations of Cold Electroweak Baryogenesis: quench from portal coupling to new singlet field

    Science.gov (United States)

    Mou, Zong-Gang; Saffin, Paul M.; Tranberg, Anders

    2018-01-01

    We compute the baryon asymmetry generated from Cold Electroweak Baryogenesis, when a dynamical Beyond-the-Standard-Model scalar singlet field triggers the spinodal transition. Using a simple potential for this additional field, we match the speed of the quench to earlier simulations with a "by-hand" mass flip. We find that for the parameter subspace most similar to a by-hand transition, the final baryon asymmetry shows a similar dependence on quench time and is of the same magnitude. For more general parameter choices the Higgs-singlet dynamics can be very complicated, resulting in an enhancement of the final baryon asymmetry. Our results validate and generalise results of simulations in the literature and open up the Cold Electroweak Baryogenesis scenario to further model building.

  14. Thermal right-handed sneutrino dark matter with a singlet Higgs

    International Nuclear Information System (INIS)

    Cerdeno, David G.

    2009-01-01

    We report on a model in which the right-handed sneutrino is a viable WIMP dark matter candidate. It consists on an extension of the MSSM with a singlet S with coupling SH 1 H 2 in order to solve the μ problem as in the NMSSM, and right-handed neutrinos N with couplings SNN in order to generate dynamically electroweak-scale Majorana masses. Through the direct coupling to the singlet, the sneutrino can not only be thermally produced in the right amount but also have a large enough scattering cross section with nuclei to detect it directly in near future, in contrast with most of other right-handed sneutrino dark matter models.

  15. Nature of the singlet and triplet excitations mediating thermally activated delayed fluorescence

    Science.gov (United States)

    Olivier, Y.; Yurash, B.; Muccioli, L.; D'Avino, G.; Mikhnenko, O.; Sancho-García, J. C.; Adachi, C.; Nguyen, T.-Q.; Beljonne, D.

    2017-12-01

    Despite significant efforts, a complete mechanistic understanding of thermally activated delayed fluorescence (TADF) materials has not yet been fully uncovered. Part of the complexity arises from the apparent dichotomy between the need for close energy resonance and for a significant spin-orbit coupling between alike charge-transfer singlet and triplet excitations. Here we show, in the case of reference carbazole derivatives, that this dichotomy can be resolved in a fully atomistic model accounting for thermal fluctuations of the molecular conformations and microscopic electronic polarization effects in amorphous films. These effects yield electronic excitations with a dynamically mixed charge-transfer and localized character, resulting in thermally averaged singlet-triplet energy differences and interconversion rates in excellent agreement with careful spectroscopic studies.

  16. Transient photocurrent in molecular junctions: singlet switching on and triplet blocking.

    Science.gov (United States)

    Petrov, E G; Leonov, V O; Snitsarev, V

    2013-05-14

    The kinetic approach adapted to describe charge transmission in molecular junctions, is used for the analysis of the photocurrent under conditions of moderate light intensity of the photochromic molecule. In the framework of the HOMO-LUMO model for the single electron molecular states, the analytic expressions describing the temporary behavior of the transient and steady state sequential (hopping) as well as direct (tunnel) current components have been derived. The conditions at which the current components achieve their maximal values are indicated. It is shown that if the rates of charge transmission in the unbiased molecular diode are much lower than the intramolecular singlet-singlet excitation/de-excitation rate, and the threefold degenerated triplet excited state of the molecule behaves like a trap blocking the charge transmission, a possibility of a large peak-like transient switch-on photocurrent arises.

  17. 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.

  18. A novel approach to nonperturbative renormalization of singlet and nonsinglet lattice operators

    Directory of Open Access Journals (Sweden)

    A.J. Chambers

    2015-01-01

    Full Text Available A novel method for nonperturbative renormalization of lattice operators is introduced, which lends itself to the calculation of renormalization factors for nonsinglet as well as singlet operators. The method is based on the Feynman–Hellmann relation, and involves computing two-point correlators in the presence of generalized background fields arising from introducing additional operators into the action. As a first application, and test of the method, we compute the renormalization factors of the axial vector current Aμ and the scalar density S for both nonsinglet and singlet operators for Nf=3 flavors of SLiNC fermions. For nonsinglet operators, where a meaningful comparison is possible, perfect agreement with recent calculations using standard three-point function techniques is found.

  19. Singlet Fission and Excimer Formation in Disordered Solids of Alkyl-Substituted 1,3-Diphenylisobenzofurans.

    Science.gov (United States)

    Dron, Paul I; Michl, Josef; Johnson, Justin C

    2017-11-16

    We describe the preparation and excited state dynamics of three alkyl derivatives of 1,3-diphenylisobenzofuran (1) in both solutions and thin films. The substitutions are intended to disrupt the slip-stacked packing observed in crystals of 1 while maintaining the favorable energies of singlet and triplet for singlet fission (SF). All substitutions result in films that are largely amorphous as judged by the absence of strong X-ray diffraction peaks. The films of 1 carrying a methyl in the para position of one phenyl ring undergo SF relatively efficiently (≥75% triplet yield, Φ T ) but more slowly than thin films of 1. When the methyl is replaced with a t-butyl, kinetic competition in the excited state favors excimer formation rather than SF (Φ T = 55%). When t-Bu groups are placed in both meta positions of the phenyl substituent, SF is slowed further and Φ T = 35%.

  20. Singlet-triplet splittings from the virial theorem and single-particle excitation energies

    Science.gov (United States)

    Becke, Axel D.

    2018-01-01

    The zeroth-order (uncorrelated) singlet-triplet energy difference in single-particle excited configurations is 2Kif, where Kif is the Coulomb self-energy of the product of the transition orbitals. Here we present a non-empirical, virial-theorem argument that the correlated singlet-triplet energy difference should be half of this, namely, Kif. This incredibly simple result gives vertical HOMO-LUMO excitation energies in small-molecule benchmarks as good as the popular TD-B3LYP time-dependent approach to excited states. For linear acenes and nonlinear polycyclic aromatic hydrocarbons, the performance is significantly better than TD-B3LYP. In addition to the virial theorem, the derivation borrows intuitive pair-density concepts from density-functional theory.

  1. Excitonic singlet-triplet ratios in molecular and polymeric organic materials

    Science.gov (United States)

    Baldo, Marc; Agashe, Shashank; Forrest, Stephen

    2002-03-01

    A simple technique is described for the determination of the internal efficiency and excitonic singlet-triplet formation statistics of electroluminescent organic thin films. The internal efficiency is measured by optically exciting a luminescent film within an electroluminescent device under reverse bias. This gives minimum singlet fractions of (0.20+/-0.03) and (0.19+/-0.04) for tris(8-hydroxyquinoline) aluminum (Alq3) and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), respectively. These results are discussed in terms of the current understanding of exciton formation within organic materials. We also present measurements of the out-coupling fraction, or the fraction of photons emitted in the forward direction, as a function of the position of the emitting layer within a microcavity.

  2. Spin singlet formation in MgTi2O4: evidence of a helical dimerization pattern.

    Science.gov (United States)

    Schmidt, M; Ratcliff, W; Radaelli, P G; Refson, K; Harrison, N M; Cheong, S W

    2004-02-06

    The transition-metal spinel MgTi2O4 undergoes a metal-insulator (M-I) transition on cooling below T(M-I)=260 K. A sharp reduction of the magnetic susceptibility below T(M-I) suggests the onset of a magnetic singlet state. Using high-resolution synchrotron and neutron powder diffraction, we have solved the low-temperature crystal structure of MgTi2O4, which is found to contain dimers with short Ti-Ti distances (the locations of the spin singlets) alternating with long bonds to form helices. Band structure calculations based on hybrid exchange density functional theory show that, at low temperatures, MgTi2O4 is an orbitally ordered band insulator.

  3. 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.

  4. Oxygen discharge and post-discharge kinetics experiments and modeling for the electric oxygen-iodine laser system.

    Science.gov (United States)

    Palla, A D; Zimmerman, J W; Woodard, B S; Carroll, D L; Verdeyen, J T; Lim, T C; Solomon, W C

    2007-07-26

    Laser oscillation at 1315 nm on the I(2P1/2)-->I(2P3/2) transition of atomic iodine has been obtained by a near resonant energy transfer from O2(a1Delta) produced using a low-pressure oxygen/helium/nitric oxide discharge. In the electric discharge oxygen-iodine laser (ElectricOIL) the discharge production of atomic oxygen, ozone, and other excited species adds levels of complexity to the singlet oxygen generator (SOG) kinetics which are not encountered in a classic purely chemical O2(a1Delta) generation system. The advanced model BLAZE-IV has been introduced to study the energy-transfer laser system dynamics and kinetics. Levels of singlet oxygen, oxygen atoms, and ozone are measured experimentally and compared with calculations. The new BLAZE-IV model is in reasonable agreement with O3, O atom, and gas temperature measurements but is under-predicting the increase in O2(a1Delta) concentration resulting from the presence of NO in the discharge and under-predicting the O2(b1Sigma) concentrations. A key conclusion is that the removal of oxygen atoms by NOX species leads to a significant increase in O2(a1Delta) concentrations downstream of the discharge in part via a recycling process; however, there are still some important processes related to the NOX discharge kinetics that are missing from the present modeling. Further, the removal of oxygen atoms dramatically inhibits the production of ozone in the downstream kinetics.

  5. Reactive oxygen species and transcript analysis upon excess light treatment in wild-type Arabidopsis thaliana vs a photosensitive mutant lacking zeaxanthin and lutein

    Directory of Open Access Journals (Sweden)

    Roncaglia Enrica

    2011-04-01

    Full Text Available Abstract Background Reactive oxygen species (ROS are unavoidable by-products of oxygenic photosynthesis, causing progressive oxidative damage and ultimately cell death. Despite their destructive activity they are also signalling molecules, priming the acclimatory response to stress stimuli. Results To investigate this role further, we exposed wild type Arabidopsis thaliana plants and the double mutant npq1lut2 to excess light. The mutant does not produce the xanthophylls lutein and zeaxanthin, whose key roles include ROS scavenging and prevention of ROS synthesis. Biochemical analysis revealed that singlet oxygen (1O2 accumulated to higher levels in the mutant while other ROS were unaffected, allowing to define the transcriptomic signature of the acclimatory response mediated by 1O2 which is enhanced by the lack of these xanthophylls species. The group of genes differentially regulated in npq1lut2 is enriched in sequences encoding chloroplast proteins involved in cell protection against the damaging effect of ROS. Among the early fine-tuned components, are proteins involved in tetrapyrrole biosynthesis, chlorophyll catabolism, protein import, folding and turnover, synthesis and membrane insertion of photosynthetic subunits. Up to now, the flu mutant was the only biological system adopted to define the regulation of gene expression by 1O2. In this work, we propose the use of mutants accumulating 1O2 by mechanisms different from those activated in flu to better identify ROS signalling. Conclusions We propose that the lack of zeaxanthin and lutein leads to 1O2 accumulation and this represents a signalling pathway in the early stages of stress acclimation, beside the response to ADP/ATP ratio and to the redox state of both plastoquinone pool. Chloroplasts respond to 1O2 accumulation by undergoing a significant change in composition and function towards a fast acclimatory response. The physiological implications of this signalling specificity are

  6. Dibenzoheptazethrene isomers with different biradical characters: An exercise of clar's aromatic sextet rule in singlet biradicaloids

    KAUST Repository

    Sun, Zhe

    2013-12-04

    Clar\\'s aromatic sextet rule has been widely used for the prediction of the reactivity and stability of polycyclic aromatic hydrocarbons with a closed-shell electronic configuration. Recent advances in open-shell biradicaloids have shown that the number of aromatic sextet rings plays an important role in determination of their ground states. In order to test the validity of this rule in singlet biradicaloids, the two soluble and stable dibenzoheptazethrene isomers DBHZ1 and DBHZ2 were prepared by different synthetic approaches and isolated in crystalline form. These two molecules have different numbers of aromatic sextet rings in their respective biradical resonance forms and thus are expected to exhibit varied singlet biradical character. This assumption was verified by different experimental methods, including nuclear magnetic resonance (NMR), electron spin resonance (ESR), superconducting quantum interference device (SQUID), steady-state and transient absorption spectroscopy (TA), and X-ray crystallographic analysis, assisted by unrestricted symmetry-broken density functional theory (DFT) calculations. DBHZ2, with more aromatic sextet rings in the biradical form, was demonstrated to possess greater biradical character than DBHZ1; as a result, DBHZ2 exhibited an intense one-photon absorption (OPA) in the near-infrared region (λabs max = 804 nm) and a large two-photon absorption (TPA) cross-section (σ(2)max = 2800 GM at 1600 nm). This investigation together with previous studies indicates that Clar\\'s aromatic sextet rule can be further extended to the singlet biradicaloids to predict their ground states and singlet biradical characters. © 2013 American Chemical Society.

  7. Singlet extensions of the standard model at LHC Run 2: benchmarks and comparison with the NMSSM

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Raul [Centro de Física Teórica e Computacional, Faculdade de Ciências,Universidade de Lisboa, Campo Grande, Edifício C8 1749-016 Lisboa (Portugal); Departamento de Física da Universidade de Aveiro,Campus de Santiago, 3810-183 Aveiro (Portugal); Mühlleitner, Margarete [Institute for Theoretical Physics, Karlsruhe Institute of Technology,76128 Karlsruhe (Germany); Sampaio, Marco O.P. [Departamento de Física da Universidade de Aveiro,Campus de Santiago, 3810-183 Aveiro (Portugal); CIDMA - Center for Research Development in Mathematics and Applications,Campus de Santiago, 3810-183 Aveiro (Portugal); Santos, Rui [Centro de Física Teórica e Computacional, Faculdade de Ciências,Universidade de Lisboa, Campo Grande, Edifício C8 1749-016 Lisboa (Portugal); ISEL - Instituto Superior de Engenharia de Lisboa,Instituto Politécnico de Lisboa, 1959-007 Lisboa (Portugal)

    2016-06-07

    The Complex singlet extension of the Standard Model (CxSM) is the simplest extension that provides scenarios for Higgs pair production with different masses. The model has two interesting phases: the dark matter phase, with a Standard Model-like Higgs boson, a new scalar and a dark matter candidate; and the broken phase, with all three neutral scalars mixing. In the latter phase Higgs decays into a pair of two different Higgs bosons are possible. In this study we analyse Higgs-to-Higgs decays in the framework of singlet extensions of the Standard Model (SM), with focus on the CxSM. After demonstrating that scenarios with large rates for such chain decays are possible we perform a comparison between the NMSSM and the CxSM. We find that, based on Higgs-to-Higgs decays, the only possibility to distinguish the two models at the LHC run 2 is through final states with two different scalars. This conclusion builds a strong case for searches for final states with two different scalars at the LHC run 2. Finally, we propose a set of benchmark points for the real and complex singlet extensions to be tested at the LHC run 2. They have been chosen such that the discovery prospects of the involved scalars are maximised and they fulfil the dark matter constraints. Furthermore, for some of the points the theory is stable up to high energy scales. For the computation of the decay widths and branching ratios we developed the Fortran code sHDECAY, which is based on the implementation of the real and complex singlet extensions of the SM in HDECAY.

  8. High Triplet Yield from Singlet Fission in a Thin Film of 1,3-Diphenylisobenzofuran

    Czech Academy of Sciences Publication Activity Database

    Johnson, J. C.; Nozik, A. J.; Michl, Josef

    2010-01-01

    Roč. 132, č. 46 (2010), s. 16302-16303 ISSN 0002-7863 Grant - others:Department of Energy(US) XAT-5-33636-01; Department of Energy(US) DE- FG36 -08GO18017 Institutional research plan: CEZ:AV0Z40550506 Keywords : singlet fission * thin solid films * heterocycles Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.019, year: 2010

  9. Covalent Dimers of 1,3-Diphenylisobenzofuran for Singlet Fission: Synthesis and Electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Akdag, Akin; Wahab, Abdul; Beran, Pavel; Rulíšek, Lubomír; Dron, P. I.; Ludvík, Jiří; Michl, Josef

    2015-01-01

    Roč. 80, č. 1 (2015), s. 80-89 ISSN 0022-3263 R&D Projects: GA ČR GA13-21704S; GA ČR(CZ) GA14-31419S Institutional support: RVO:61388963 ; RVO:61388955 Keywords : singlet fission * reduction potentials * electrochemistry * theoretical calculations Subject RIV: CC - Organic Chemistry; CG - Electrochemistry (UFCH-W) Impact factor: 4.785, year: 2015

  10. Observations of the singlets of higher modes based on the OSE

    Science.gov (United States)

    Zeng, Shiyu; Shen, Wen-Bin

    2016-04-01

    In this study, we select 18 SG (superconducting gravimeter) records from 15 GGP stations (http://www.eas.slu.edu/GGP/ggphome.html) and 99 radial, 69 transverse components of IRIS broadband seismograms (http://ds.iris.edu/ds/nodes/dmc/) during 2004 Sumatra Earthquake to detect the splitting of higher Earth's free oscillations modes (0S4, 0S7~0S10, 2S4, 1S5, 2S5, 1S6) and 13 inner-core sensitive modes (25S2, 27S2, 6S3, 9S3, 13S3, 15S3, 11S4, 18S4, 8S5, 11S5, 23S5, 16S6, 21S6) by using OSE (optimal sequence estimation) method. Results indicate that OSE can completely isolate singlets of high-degree modes in time-domain, and significantly reduce the possibility of mode mixing and end effect, so that OSE could improve some signals' SNR (signal-to-noise ratio). We also compare the results of SG records with seismic data sets, and it shows that the number of SG records is limited to observe all of the singlets of higher modes. Hence we mainly select seismograms of IRIS to observe the mutiplets of higher modes. This study demonstrates that OSE is effective in isolating singlets of Earth's free oscillations modes. We estimate frequencies of the singlets using AR method (Chao & Gilbert, 1980) and following Häfner & Widmer-Schnidrig (2013) we obtain the error bars through the bootstrap method (Efron & Tibshirani, 1986). Finally we compared the observations with the predictions of PREM model (Dziewonski & Anderson, 1981) and 1066A model (Dahlen & Sailor, 1979). Our experimental results may provide constraints to the construction of 3D Earth model. This study is supported by National 973 Project China (grant No. 2013CB733305), NSFC (grant Nos. 41174011, 41429401, 41210006, 41128003, 41021061).

  11. 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.

  12. Coherent dynamics of singlet fission controlled by nonlocal electron-phonon coupling

    OpenAIRE

    Yao, Yao

    2015-01-01

    Based on the Frenkel-charge transfer (CT) mixing model of singlet fission (SF), we incorporate both the local and nonlocal phonon baths in the Hamiltonian and adopt the algorithm of time-dependent density matrix renormalization group to simulate the fission process in tetracene. The endergonic SF is found to be facilitated by the robust quantum coherence, which concurrently gives rise to a notable quantum beating effect. Controlled by the nonlocal electron-phonon coupling, the density of trip...

  13. 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.

  14. Predicting singlet-triplet energy splittings with projected Hartree-Fock methods.

    Science.gov (United States)

    Rivero, Pablo; Jiménez-Hoyos, Carlos A; Scuseria, Gustavo E

    2013-08-22

    Hartree-Fock (HF) and density functional theory (DFT) methods are known for having problems in predicting singlet-triplet energy splittings when the system displays significant diradical character. Multireference methods are traditionally advocated to deal with the spin-contamination problem inherent in broken-symmetry mean-field methods. In the present work, spin-contamination is rigorously eliminated by means of a symmetry projection approach, carried out in a variation-after-projection fashion, recently implemented in our research group. We here explore the performance of a variety of projected Hartree-Fock (PHF) approaches (SUHF, KSUHF, SGHF, and KSGHF) in predicting singlet-triplet energy gaps in a broad set of diradical systems: small diatomic molecules, carbenes and silenes, and a few larger molecules (trimethylenemethane and benzyne isomers). For most of these systems, accurate experimental data is available in the literature. Additionally, we assess the quality of the geometrical parameters obtained in SUHF-based optimizations for some of the systems considered. Our results indicate that PHF methods yield high-quality multireference wave functions, providing a good description of the ground state potential surface as well as an accurate singlet-triplet splitting gap, all within a modest mean-field computational cost.

  15. Probability of color singlet chain states in e+e- annihilation

    International Nuclear Information System (INIS)

    Wang, Qun; Gustafson, Gosta; Jin, Yi; Xie, Qu-bing

    2001-01-01

    We use the method of the color effective Hamiltonian to study the structure of color singlet chain states in N c =3 and in the large N c limit. In order to obtain their total fraction when N c is finite, we illustrate how to orthogonalize these nonorthogonal states. We give numerical results for the fraction of orthogonalized states in e + e - ->q bar qgg. With the help of a diagram technique, we derive their fraction up to O(1/N c 2 ) for the general multigluon process. For large N c the singlet chain states correspond to well-defined color topologies. Therefore we may expect that the fraction of non-color-singlet-chain states is an estimate of the fraction of events where color reconnection is possible. In the case of soft gluon bremsstrahlung, we give an explicit form for the color effective Hamiltonian which leads to the dipole cascade formulation for parton showering in leading order in N c . The next-to-leading order corrections are also given for e + e - ->qbar qg 1 g 2 and e + e - ->qbar qg 1 g 2 g 3

  16. Decamethylytterbocene complexes of bipyridines and diazabutadines: multiconfigurational ground states and open-shell singlet formation

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Eric D [Los Alamos National Laboratory; Booth, C H [LBNL; Walter, M D [LBNL; Kazhdan, D [LBNL; Hu, Y - J [LBNL; Lukens, Wayne [LBNL; Maron, Laurent [INSA TOULOUSE; Eisentein, Odile [UNIV MONTPELLIER 2; Anderson, Richard [LBNL

    2009-01-01

    Partial ytterbium f-orbital occupancy (i.e. intermediate valence) and open-shell singlet Draft 12/formation are established for a variety of bipyridine and diazabutadiene adducts to decamethylytterbocene, (C{sub 5}Me{sub 5}){sub 2}Yb or Cp*{sub 2}Yb. Data used to support this claim includes ytterbium valence measurements using Yb Lm-edge x-ray absorption near-edge structure (XANES) spectroscopy, magnetic susceptibility and Complete Active Space Self-Consistent Field (CASSCF) multi configurational calculations, as well as structural measurements compared to density-functional theory (DFT) calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground state wave function that has both an open-shell singlet f{sup 13} and a closed-shell singlet f{sup 14} component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the presence of intermediate valence and its lack of any significant temperature dependence. These results have implications for understanding chemical bonding not only in organolanthanide complexes, but also for organometallic chemistry in general, as well as understanding magnetic interactions in nanopartic1es and devices.

  17. Global potential energy surface of ground state singlet spin O4

    Science.gov (United States)

    Mankodi, Tapan K.; Bhandarkar, Upendra V.; Puranik, Bhalchandra P.

    2018-02-01

    A new global potential energy for the singlet spin state O4 system is reported using CASPT2/aug-cc-pVTZ ab initio calculations. The geometries for the six-dimensional surface are constructed using a novel point generation scheme that employs randomly generated configurations based on the beta distribution. The advantage of this scheme is apparent in the reduction of the number of required geometries for a reasonably accurate potential energy surface (PES) and the consequent decrease in the overall computational effort. The reported surface matches well with the recently published singlet surface by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. In addition to the O4 PES, the ground state N4 PES is also constructed using the point generation scheme and compared with the existing PES [Y. Paukku et al., J. Chem. Phys. 139, 044309 (2013)]. The singlet surface is constructed with the aim of studying high energy O2-O2 collisions and predicting collision induced dissociation cross section to be used in simulating non-equilibrium aerothermodynamic flows.

  18. Phototoxicity Evaluation of Pharmaceutical Substances with a Reactive Oxygen Species Assay Using Ultraviolet A

    Science.gov (United States)

    Lee, Yong Sun; Yi, Jung-Sun; Lim, Hye Rim; Kim, Tae Sung; Ahn, Il Young; Ko, Kyungyuk; Kim, JooHwan; Park, Hye-Kyung; Sohn, Soo Jung; Lee, Jong Kwon

    2017-01-01

    With ultraviolet and visible light exposure, some pharmaceutical substances applied systemically or topically may cause phototoxic skin irritation. The major factor in phototoxicity is the generation of reactive oxygen species (ROS) such as singlet oxygen and superoxide anion that cause oxidative damage to DNA, lipids and proteins. Thus, measuring the generation of ROS can predict the phototoxic potential of a given substance indirectly. For this reason, a standard ROS assay (ROS assay) was developed and validated and provides an alternative method for phototoxicity evaluation. However, negative substances are over-predicted by the assay. Except for ultraviolet A (UVA), other UV ranges are not a major factor in causing phototoxicity and may lead to incorrect labeling of some non-phototoxic substances as being phototoxic in the ROS assay when using a solar simulator. A UVA stimulator is also widely used to evaluate phototoxicity in various test substances. Consequently, we identified the applicability of a UVA simulator to the ROS assay for photoreactivity. In this study, we tested 60 pharmaceutical substances including 50 phototoxins and 10 non-phototoxins to predict their phototoxic potential via the ROS assay with a UVA simulator. Following the ROS protocol, all test substances were dissolved in dimethyl sulfoxide or sodium phosphate buffer. The final concentration of the test solutions in the reaction mixture was 20 to 200 μM. The exposure was with 2.0~2.2 mW/cm2 irradiance and optimization for a relevant dose of UVA was performed. The generation of ROS was compared before and after UVA exposure and was measured by a microplate spectrophotometer. Sensitivity and specificity values were 85.7% and 100.0% respectively, and the accuracy was 88.1%. From this analysis, the ROS assay with a UVA simulator is suitable for testing the photoreactivity and estimating the phototoxic potential of various test pharmaceutical substances. PMID:28133512

  19. Radiation damage

    CERN Document Server

    Heijne, Erik H M; CERN. Geneva

    1998-01-01

    a) Radiation damage in organic materials. This series of lectures will give an overview of radiation effects on materials and components frequently used in accelerator engineering and experiments. Basic degradation phenomena will be presented for organic materials with comprehensive damage threshold doses for commonly used rubbers, thermoplastics, thermosets and composite materials. Some indications will be given for glass, scintillators and optical fibres. b) Radiation effects in semiconductor materials and devices. The major part of the time will be devoted to treat radiation effects in semiconductor sensors and the associated electronics, in particular displacement damage, interface and single event phenomena. Evaluation methods and practical aspects will be shown. Strategies will be developed for the survival of the materials under the expected environmental conditions of the LHC machine and detectors. I will describe profound revolution in our understanding of black holes and their relation to quantum me...

  20. Zethrenes, Extended p -Quinodimethanes, and Periacenes with a Singlet Biradical Ground State

    KAUST Repository

    Sun, Zhe

    2014-08-19

    ConspectusResearchers have studied polycyclic aromatic hydrocarbons (PAHs) for more than 100 years, and most PAHs in the neutral state reported so far have a closed-shell electronic configuration in the ground state. However, recent studies have revealed that specific types of polycyclic hydrocarbons (PHs) could have a singlet biradical ground state and exhibit unique electronic, optical, and magnetic activities. With the appropriate stabilization, these new compounds could prove useful as molecular materials for organic electronics, nonlinear optics, organic spintronics, organic photovoltaics, and energy storage devices. However, before researchers can use these materials to design new devices, they need better methods to synthesize these molecules and a better understanding of the fundamental relationship between the structure and biradical character of these compounds and their physical properties. Their biradical character makes these compounds difficult to synthesize. These compounds are also challenging to physically characterize and require the use of various experimental techniques and theoretic methods to comprehensively describe their unique properties.In this Account, we will discuss the chemistry and physics of three types of PHs with a significant singlet biradical character, primarily developed in our group. These structures are zethrenes, Z-shaped quinoidal hydrocarbons; hydrocarbons that include a proaromatic extended p-quinodimethane unit; and periacenes, acenes fused in a peri-Arrangement. We used a variety of synthetic methods to prepare these compounds and stabilized them using both thermodynamic and kinetic approaches. We probed their ground-state structures by electronic absorption, NMR, ESR, SQUID, Raman spectroscopy, and X-ray crystallography and also performed density functional theory calculations. We investigated the physical properties of these PHs using various experimental methods such as one-photon absorption, two-photon absorption

  1. Prevention of oxygen toxicity in divers

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-02-01

    This report summarises the findings of a project investigating the conversion of xanthine dehydrogenase to xanthine oxidase in cultured cells exposed to hypoxia, and examines the effects of reoxygenating the hypoxic cells. The role of xanthine oxidase in the production of oxygen free radicals leading to tissue damage due to oxygen toxicity after reperfusion of hypoxic and ischaemic tissues is discussed. (UK)

  2. Tripping up Trp: Modification of protein tryptophan residues by reactive oxygen species, modes of detection, and biological consequences.

    Science.gov (United States)

    Ehrenshaft, Marilyn; Deterding, Leesa J; Mason, Ronald P

    2015-12-01

    Proteins comprise a majority of the dry weight of a cell, rendering them a major target for oxidative modification. Oxidation of proteins can result in significant alterations in protein molecular mass such as breakage of the polypeptide backbone and/or polymerization of monomers into dimers, multimers, and sometimes insoluble aggregates. Protein oxidation can also result in structural changes to amino acid residue side chains, conversions that have only a modest effect on protein size but can have widespread consequences for protein function. There are a wide range of rate constants for amino acid reactivity, with cysteine, methionine, tyrosine, phenylalanine, and tryptophan having the highest rate constants with commonly encountered biological oxidants. Free tryptophan and tryptophan protein residues react at a diffusion-limited rate with hydroxyl radical and also have high rate constants for reactions with singlet oxygen and ozone. Although oxidation of proteins in general and tryptophan residues specifically can have effects detrimental to the health of cells and organisms, some modifications are neutral, whereas others contribute to the function of the protein in question or may act as a signal that damaged proteins need to be replaced. This review provides a brief overview of the chemical mechanisms by which tryptophan residues become oxidized, presents both the strengths and the weaknesses of some of the techniques used to detect these oxidative interactions, and discusses selected examples of the biological consequences of tryptophan oxidation in proteins from animals, plants, and microbes. Published by Elsevier Inc.

  3. Tort Damages

    NARCIS (Netherlands)

    L.T. Visscher (Louis)

    2008-01-01

    textabstractAbstract: In this Chapter, I provide an overview of Law and Economics literature regarding tort damages. Where necessary, attention is also spent to rules of tort liability. Both types of rules provide behavioral incentives to both injurers and victims, with respect to their level of

  4. Wipes coated with a singlet-oxygen-producing photosensitizer are effective against human influenza virus but not against norovirus

    NARCIS (Netherlands)

    Verhaelen, Katharina; Bouwknegt, Martijn; Rutjes, Saskia; de Roda Husman, Ana Maria; Duizer, Erwin

    2014-01-01

    Transmission of enteric and respiratory viruses, including human norovirus (hNoV) and human influenza virus, may involve surfaces. In food preparation and health care settings, surfaces are cleaned with wipes; however, wiping may not efficiently reduce contamination or may even spread viruses,

  5. Identification of singlet oxygen photosensitizes in lambs drinking water in an alveld risk area in West Norway

    DEFF Research Database (Denmark)

    Tønnesen, Hanne Hjorth; Mysterud, Ivar; Karlsen, Jan

    2013-01-01

    Alveld is a hepatogenous photosensitivity disorder in lambs. Although alveld has been known in Norway for more than 100years, there are still questions related to the cause of the disease. Phytoporphyrin has long been incriminated as the photosensitizer in hepatogenous photosensitivity diseases....... Meteorological data indicate a warm and wet May with a high radiation exposure leading up to a colder and wet June with an even higher solar irradiance. The seasonal variation in the amount of photosensitizers in lamb's drinking water combined meteorological data can be important to predict the outbreak...

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

    Czech Academy of Sciences Publication Activity Database

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

    2016-01-01

    Roč. 55, č. 2 (2016), s. 803-809 ISSN 0020-1669 R&D Projects: GA ČR GA13-05114S Institutional support: RVO:61388980 ; RVO:61388955 ; RVO:68378271 Keywords : photodynamic therapy * nanoparticles * cancer-treatment Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (FZU-D); CF - Physical ; Theoretical Chemistry (UFCH-W) Impact factor: 4.857, year: 2016

  7. The role of oxygen in photochemical transformations of the anthraquinone solutions

    International Nuclear Information System (INIS)

    Akylbaev, Zh.S.; Karitskaya, S.G.; Kobzev, G.I.

    2001-01-01

    The analysis of possible spin conditions of reaction key product reagents proceeding in anthraquinone solution has been conducted. It is shown that photoproduct molecules of anthraquinone with excited electrons appear in the solution as a result of interaction of triplet anthraquinone molecules with alcohol molecules. The considerable influence of singlet oxygen on quenching the photoproduct luminescence and its ability to reduce anthraquinone solution into the triplet condition are shown. (author)

  8. Ex-vivo and in vitro protective effects of kolaviron against oxygen-derived radical-induced DNA damage and oxidative stress in human lymphocytes and rat liver cells

    DEFF Research Database (Denmark)

    Farombi, E.O.; Moller, P.; Dragsted, L.O.

    2004-01-01

    at concentrations between 30-90 mumol/L and decreased H2O2-induced DNA strand breaks and oxidized bases. Neither alpha-tocopherol nor curcumin decreased H2O2-induced DNA damage in this assay. In lymphocytes incubated with Fe3+ /GSH, Fe3+ was reduced to Fe2+ by GSH initiating a free radical generating reaction which...

  9. Oxygen safety

    Science.gov (United States)

    ... sure you have working smoke detectors and a working fire extinguisher in your home. If you move around the house with your oxygen, you may need more than one fire extinguisher in different locations. Smoking can be very dangerous. No one should smoke ...

  10. Photosensitized Oxygenations of Hexamethylbenzene in Phase Contact Enhanced Microreactor

    International Nuclear Information System (INIS)

    Park, Chan Yi; Park, Jeong Hyeon; Lim Hyo Jin; Hwang, Geumsook; Park, Chan Pil

    2014-01-01

    Activated singlet oxygen ( 1 O 2 ) has successfully been utilized in production of various compounds including fragrances, pharmaceuticals, and fine chemicals. However, the traditional reaction required a prolonged reaction time due to the difficulty of introducing adequate light and oxygen into the solution. Low contact probability between four species of oxygen, photosensitizer, light, and reagent is an inherent drawback of the traditional photoreaction. Molecular diffusion distance is the most important factor in the heterogeneous reactions including gas-liquid, gassolid, liquid-solid, and immiscible liquid-liquid. Therefore, rates of reaction are closely depended on the distance. Microreactor has provided a distinct advantage in the short molecular diffusion distance due to the high surface-to-volume ratio driven by narrow fluidic channels

  11. Photosensitized Oxygenations of Hexamethylbenzene in Phase Contact Enhanced Microreactor

    Energy Technology Data Exchange (ETDEWEB)

    Park, Chan Yi; Park, Jeong Hyeon; Lim Hyo Jin; Hwang, Geumsook; Park, Chan Pil [Chungnam National Univ., Daejeon (Korea, Republic of)

    2014-04-15

    Activated singlet oxygen ({sup 1}O{sub 2}) has successfully been utilized in production of various compounds including fragrances, pharmaceuticals, and fine chemicals. However, the traditional reaction required a prolonged reaction time due to the difficulty of introducing adequate light and oxygen into the solution. Low contact probability between four species of oxygen, photosensitizer, light, and reagent is an inherent drawback of the traditional photoreaction. Molecular diffusion distance is the most important factor in the heterogeneous reactions including gas-liquid, gassolid, liquid-solid, and immiscible liquid-liquid. Therefore, rates of reaction are closely depended on the distance. Microreactor has provided a distinct advantage in the short molecular diffusion distance due to the high surface-to-volume ratio driven by narrow fluidic channels.

  12. Atomic Oxygen Cleaning of Unpainted Plaster Sculptures

    Science.gov (United States)

    Banks, Bruce A.; Miller, Sharon K.

    2017-01-01

    Atomic oxygen erosion of polymers has been found to be a threat to spacecraft in low Earth orbit. As a result ground facilities have been developed to identify coatings to protect polymers such as used for solar array blankets. As a result of extensive laboratory testing, it was discovered that soot and other organic contamination on paintings could be readily removed by atomic oxygen interactions with minimal damage to the artwork. No method, other than dusting, has been found to be effective in the cleaning of unpainted plaster sculptures This presentation discusses the atomic oxygen interaction processes and how effective they are for cleaning soot damaged unpainted plaster sculptures.

  13. One-loop radiative correction to the triple Higgs coupling in the Higgs singlet model

    Directory of Open Access Journals (Sweden)

    Shi-Ping He

    2017-01-01

    Full Text Available Though the 125 GeV Higgs boson is consistent with the standard model (SM prediction until now, the triple Higgs coupling can deviate from the SM value in the physics beyond the SM (BSM. In this paper, the radiative correction to the triple Higgs coupling is calculated in the minimal extension of the SM by adding a real gauge singlet scalar. In this model there are two scalars h and H and both of them are mixing states of the doublet and singlet. Provided that the mixing angle is set to be zero, namely the SM limit, h is the pure left-over of the doublet and its behavior is the same as that of the SM at the tree level. However the loop corrections can alter h-related couplings. In this SM limit case, the effect of the singlet H may show up in the h-related couplings, especially the triple h coupling. Our numerical results show that the deviation is sizable. For λΦS=1 (see text for the parameter definition, the deviation δhhh(1 can be 40%. For λΦS=1.5, the δhhh(1 can reach 140%. The sizable radiative correction is mainly caused by three reasons: the magnitude of the coupling λΦS, light mass of the additional scalar and the threshold enhancement. The radiative corrections for the hVV, hff couplings are from the counter-terms, which are the universal correction in this model and always at O(1%. The hZZ coupling, which can be precisely measured, may be a complementarity to the triple h coupling to search for the BSM. In the optimal case, the triple h coupling is very sensitive to the BSM physics, and this model can be tested at future high luminosity hadron colliders and electron–positron colliders.

  14. Direct Detection of the Open-Shell Singlet Phenyloxenium Ion: An Atom-Centered Diradical Reacts as an Electrophile.

    Science.gov (United States)

    Du, Lili; Qiu, Yunfan; Lan, Xin; Zhu, Ruixue; Phillips, David Lee; Li, Ming-De; Dutton, Andrew S; Winter, Arthur H

    2017-10-25

    A new photoprecursor to the phenyloxenium ion, 4-methoxyphenoxypyridinium tetrafluoroborate, was investigated using trapping studies, product analysis, computational investigations, and laser flash photolysis experiments ranging from the femtosecond to the millisecond time scale. These experiments allowed us to trace the complete arc of the photophysics and photochemistry of this photoprecursor beginning with the initially populated excited states to its sequential formation of transient intermediates and ultimate formation of stable photoproducts. We find that the excited state of the photoprecursor undergoes heterolysis to generate the phenyloxenium ion in ∼2 ps but surprisingly generates the ion in its open-shell singlet diradical configuration ( 1 A 2 ), permitting an unexpected look at the reactivity of an atom-centered open-shell singlet diradical. The open-shell phenyloxenium ion ( 1 A 2 ) has a much shorter lifetime (τ ∼ 0.2 ns) in acetonitrile than the previously observed closed-shell singlet ( 1 A 1 ) phenyloxenium ion (τ ∼ 5 ns). Remarkably, despite possessing no empty valence orbitals, this open-shell singlet oxenium ion behaves as an even more powerful electrophile than the closed-shell singlet oxenium ion, undergoing solvent trapping by weakly nucleophilic solvents such as water and acetonitrile or externally added nucleophiles (e.g., azide) rather than engaging in typical diradical chemistry, such as H atom abstraction, which we have previously observed for a triplet oxenium ion. In acetonitrile, the open-shell singlet oxenium ion is trapped to generate ortho and para Ritter intermediates, one of which (para) is directly observed as a longer-lived species (τ ∼ 0.1 ms) in time-resolved resonance Raman experiments. The Ritter intermediates are ultimately trapped by either the 4-methoxypyridine leaving group (in the case of para addition) or trapped internally via an essentially barrierless rearrangement (in the case of ortho addition) to

  15. 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

  16. Long-range corrected density functional theory study on static second hyperpolarizabilities of singlet diradical systems.

    Science.gov (United States)

    Kishi, Ryohei; Bonness, Sean; Yoneda, Kyohei; Takahashi, Hideaki; Nakano, Masayoshi; Botek, Edith; Champagne, Benoît; Kubo, Takashi; Kamada, Kenji; Ohta, Koji; Tsuneda, Takao

    2010-03-07

    Within the spin-unrestricted density functional theory (DFT) the long-range correction (LC) scheme combined with the Becke-Lee-Yang-Parr exchange-correlation functional, referred to as LC-UBLYP method, has been applied to the calculation of the second hyperpolarizability (gamma) of open-shell singlet diradical systems of increasing complexity and has demonstrated good performance: (i) for the simplest H(2) dissociation model, the gamma values calculated by the LC-UBLYP method significantly overshoot the full configuration interaction result but reproduce qualitatively the evolution of gamma as a function of the diradical character, (ii) for small singlet diradical 1,3-dipole systems, the diradical character dependence of gamma determined by the UCCSD and UCCSD(T) reference methods is reproduced semiquantitatively by the LC-UBLYP method except in the small diradical character region, where the spin-unrestricted solutions coincide with spin-restricted solutions, (iii) the LC-UBLYP method also closely reproduces the UCCSD(T) results on the diradical character dependence of gamma of the p-quinodimethane model system, particularly in the intermediate and large diradical character regions, whereas it shows an abrupt change for a diradical character (y) close to 0.2 originating from the triplet instability, (iv) the reliability of LC-UBLYP to reproduce reference coupled cluster results on open-shell singlet systems with intermediate and large diradical characters has also been substantiated in the case of gamma of 1,4-bis-(imidazol-2-ylidene)-cyclohexa-2,5-diene (BI2Y), then (v), for real systems built from a pair of phenalenyl radicals separated by a conjugated linker, the LC-UBLYP results have been found to closely match the UBHandHLYP values-which, for small systems are in good agreement with those obtained using correlated molecular orbital methods-whereas the UB3LYP results can be much different. These results are not only important from the viewpoint of an efficient

  17. Hybrid spin and valley quantum computing with singlet-triplet qubits.

    Science.gov (United States)

    Rohling, Niklas; Russ, Maximilian; Burkard, Guido

    2014-10-24

    The valley degree of freedom in the electronic band structure of silicon, graphene, and other materials is often considered to be an obstacle for quantum computing (QC) based on electron spins in quantum dots. Here we show that control over the valley state opens new possibilities for quantum information processing. Combining qubits encoded in the singlet-triplet subspace of spin and valley states allows for universal QC using a universal two-qubit gate directly provided by the exchange interaction. We show how spin and valley qubits can be separated in order to allow for single-qubit rotations.

  18. Storage of magnetization as singlet order by optimal control designed pulses

    DEFF Research Database (Denmark)

    Laustsen, Christoffer; Bowen, Sean; Vinding, Mads Sloth

    2014-01-01

    . With this aim, optimal control theory was applied to create pulses that for near‐equivalent spins accomplish transfers in and out of the singlet state with maximum efficiency while ensuring robustness toward variations in the nuclear spin system Hamiltonian (chemical shift, J‐couplings, B1 and B magnetic field...... inhomogeneity). The pulses are designed to accomplish efficient transfer with low B1 amplitude, essential for applications on preclinical and clinical MR scanners. It is demonstrated that significantly improved efficiency and robustness can be obtained within the limitations of typical MR scanner performance...

  19. Non-anticommutative N=2 super-Yang-Mills theory with singlet deformation

    CERN Document Server

    Ferrara, Sergio; Ferrara, Sergio; Sokatchev, Emery; 10.1016/j.physletb.2003.10.093

    2004-01-01

    We consider a non-anticommutative N=2 superspace with an SU(2) singlet and Lorentz scalar deformation parameter, $\\{\\theta^{\\alpha i}, \\theta^{\\beta j}\\}_\\star = -2iP \\epsilon^{\\alpha\\beta}\\epsilon^{ij}$. We exploit this unique feature of the N=2 case to construct a deformation of the rank-one super-Yang-Mills theory which preserves the full N=2 supersymmetry together with the SU(2) R symmetry and Lorentz invariance. The resulting action describes a kind of "heterotic special geometry" with antiholomorphic prepotential $\\bar(\\bar\\phi) = \\bar\\phi^2 (1+P\\bar\\phi)^{-2}$.

  20. Standard model extended by a heavy singlet: Linear vs. nonlinear EFT

    Energy Technology Data Exchange (ETDEWEB)

    Buchalla, G., E-mail: gerhard.buchalla@lmu.de; Catà, O.; Celis, A.; Krause, C.

    2017-04-15

    We consider the Standard Model extended by a heavy scalar singlet in different regions of parameter space and construct the appropriate low-energy effective field theories up to first nontrivial order. This top-down exercise in effective field theory is meant primarily to illustrate with a simple example the systematics of the linear and nonlinear electroweak effective Lagrangians and to clarify the relation between them. We discuss power-counting aspects and the transition between both effective theories on the basis of the model, confirming in all cases the rules and procedures derived in previous works from a bottom-up approach.

  1. Superconducting 2D system with lifted spin degeneracy: mixed singlet-triplet state.

    Science.gov (United States)

    Gor'kov, L P; Rashba, E I

    2001-07-16

    Motivated by recent experimental findings, we have developed a theory of the superconducting state for 2D metals without inversion symmetry modeling the geometry of a surface superconducting layer in a field-effect transistor or near the boundary doped by adsorbed ions. In such systems the twofold spin degeneracy is lifted by spin-orbit interaction, and singlet and triplet pairings are mixed in the wave function of the Cooper pairs. As a result, spin magnetic susceptibility becomes anisotropic and Knight shift retains finite and rather high value at T = 0.

  2. Superconducting 2D System with Lifted Spin Degeneracy: Mixed Singlet-Triplet State

    Energy Technology Data Exchange (ETDEWEB)

    Gor' kov, Lev P.; Rashba, Emmanuel I.

    2001-07-16

    Motivated by recent experimental findings, we have developed a theory of the superconducting state for 2D metals without inversion symmetry modeling the geometry of a surface superconducting layer in a field-effect transistor or near the boundary doped by adsorbed ions. In such systems the twofold spin degeneracy is lifted by spin-orbit interaction, and singlet and triplet pairings are mixed in the wave function of the Cooper pairs. As a result, spin magnetic susceptibility becomes anisotropic and Knight shift retains finite and rather high value at T=0 .

  3. The two-mass contribution to the three-loop pure singlet operator matrix element

    Science.gov (United States)

    Ablinger, J.; Blümlein, J.; De Freitas, A.; Schneider, C.; Schönwald, K.

    2018-02-01

    We present the two-mass QCD contributions to the pure singlet operator matrix element at three loop order in x-space. These terms are relevant for calculating the structure function F2 (x ,Q2) at O (αs3) as well as for the matching relations in the variable flavor number scheme and the heavy quark distribution functions at the same order. The result for the operator matrix element is given in terms of generalized iterated integrals that include square root letters in the alphabet, depending also on the mass ratio through the main argument. Numerical results are presented.

  4. Excitonic singlet-triplet ratio in a semiconducting organic thin film

    Science.gov (United States)

    Baldo, M. A.; O'brien, D. F.; Thompson, M. E.; Forrest, S. R.

    1999-11-01

    A technique is presented to determine the spin statistics of excitons formed by electrical injection in a semiconducting organic thin film. With the aid of selective addition of luminescent dyes, we generate either fluorescence or phosphorescence from the archetype organic host material aluminum tris (8-hydroxyquinoline) (Alq3). Spin statistics are calculated from the ratio of fluorescence to phosphorescence in the films under electrical excitation. After accounting for varying photoluminescent efficiencies, we find a singlet fraction of excitons in Alq3 of (22+/-3)%.

  5. The two-mass contribution to the three-loop pure singlet operator matrix element

    Energy Technology Data Exchange (ETDEWEB)

    Ablinger, J.; Schneider, C. [Johannes Kepler Univ., Linz (Austria). Research Inst. for Symbolic Computation (RISC); Bluemlein, J.; Freitas, A. de; Schoenwald, K. [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany)

    2017-11-15

    We present the two-mass QCD contributions to the pure singlet operator matrix element at three loop order in x-space. These terms are relevant for calculating the structure function F{sub 2}(x,Q{sup 2}) at O(α{sup 3}{sub s}) as well as for the matching relations in the variable flavor number scheme and the heavy quark distribution functions at the same order. The result for the operator matrix element is given in terms of generalized iterated integrals that include square root letters in the alphabet, depending also on the mass ratio through the main argument. Numerical results are presented.

  6. Theoretical rationalization of the singlet-triplet gap in OLEDs materials: impact of charge-transfer character.

    Science.gov (United States)

    Moral, M; Muccioli, L; Son, W-J; Olivier, Y; Sancho-García, J C

    2015-01-13

    New materials for OLED applications with low singlet-triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet-triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet-triplet transition. Finally, we quantitatively correlate the singlet-triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.

  7. Renal transplantation induces mitochondrial uncoupling, increased kidney oxygen consumption, and decreased kidney oxygen tension

    NARCIS (Netherlands)

    Papazova, Diana A.; Friederich-Persson, Malou; Joles, Jaap A.; Verhaar, Marianne C.

    2015-01-01

    Hypoxia is an acknowledged pathway to renal injury and ischemia-reperfusion (I/R) and is known to reduce renal oxygen tension (PO2). We hypothesized that renal I/R increases oxidative damage and induces mitochondrial uncoupling, resulting in increased oxygen consumption and hence kidney

  8. 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

  9. Forbidden singlet exciton transitions induced by localization in polymer light-emitting diodes in a strong electric field.

    Science.gov (United States)

    Sun, Zheng; Xu, Yuan-Ping; Li, Sheng; George, Thomas F

    2011-02-10

    Through combining the electron transition process and dipole moment evolution as well as electron-phonon coupling, molecular dynamics calculations show that the radiative decay of singlet excitons in a conjugated polymer, such as a polymer light-emitting diode (PLED), is largely determined by the evolution of the dipole moment. Without an electric field, the decay life of a singlet exciton is about 1 ns. Once an electric field is applied and exceeds a critical value, with electron-phonon coupling, the original lattice structure evolves into two new localized lattice distortions, consistent with the experimental results. Owing to the new lattice structure and self-trapping, the dipole moment rapidly decreases to zero within 5 fs, eliminating the radiative decay of the singlet exciton.

  10. Absence of Intramolecular Singlet Fission in Pentacene-Perylenediimide Heterodimers: The Role of Charge Transfer State.

    Science.gov (United States)

    Wang, Long; Wu, Yishi; Chen, Jianwei; Wang, Lanfen; Liu, Yanping; Yu, Zhenyi; Yao, Jiannian; Fu, Hongbing

    2017-11-16

    A new class of donor-acceptor heterodimers based on two singlet fission (SF)-active chromophores, i.e., pentacene (Pc) and perylenediimide (PDI), was developed to investigate the role of charge transfer (CT) state on the excitonic dynamics. The CT state is efficiently generated upon photoexcitation. However, the resulting CT state decays to different energy states depending on the energy levels of the CT state. It undergoes extremely rapid deactivation to the ground state in polar CH 2 Cl 2 , whereas it undergoes transformation to a Pc triplet in nonpolar toluene. The efficient triplet generation in toluene is not due to SF but CT-mediated intersystem crossing. In light of the energy landscape, it is suggested that the deep energy level of the CT state relative to that of the triplet pair state makes the CT state actually serve as a trap state that cannot undergoes an intramolecular singlet fission process. These results provide guidance for the design of SF materials and highlight the requisite for more widely applicable design principles.

  11. Enhanced Higgs associated production with a top quark pair in the NMSSM with light singlets

    Energy Technology Data Exchange (ETDEWEB)

    Badziak, Marcin [Institute of Theoretical Physics, Faculty of Physics, University of Warsaw,ul. Pasteura 5, PL-02-093 Warsaw (Poland); Berkeley Center for Theoretical Physics, Department of Physics andTheoretical Physics Group, Lawrence Berkeley National Laboratory, University of California,Berkeley, CA 94720 (United States); Wagner, Carlos E.M. [Enrico Fermi Institute, University of Chicago,Chicago, IL 60637 (United States); High Energy Physics Division, Argonne National Laboratory,Argonne, IL 60439 (United States); Kavli Institute for Cosmological Physics, University of Chicago,Chicago, IL 60637 (United States)

    2017-02-09

    Precision measurements of the 125 GeV Higgs resonance recently discovered at the LHC have determined that its properties are similar to the ones of the Standard Model (SM) Higgs boson. However, the current uncertainties in the determination of the Higgs boson couplings leave room for significant deviations from the SM expectations. In fact, if one assumes no correlation between the top-quark and gluon couplings to the Higgs, the current global fit to the Higgs data lead to central values of the Higgs couplings to the bottom-quark and the top-quark that are about 2 σ away from the SM predictions. In a previous work, we showed that such a scenario could be realized in the Next to Minimal Supersymmetric extension of the SM (NMSSM), for heavy singlets and light MSSM-like Higgs bosons and scalar top quarks, but for couplings that ruined the perturbative consistency of the theory up to the GUT scale. In this work we show that a perturbative consistent scenario, for somewhat heavier stops, may be obtained in the presence of light singlets. An interesting bonus of this scenario is the possibility of explaining an excess of events observed in CP-even Higgs searches at LEP2.

  12. 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).

  13. Role of N2 molecules in pulse discharge production of I atoms for a pulsed chemical oxygen-iodine laser

    International Nuclear Information System (INIS)

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

    2011-01-01

    A pulsed electric discharge is the most effective means to turn chemical oxygen-iodine laser (COIL) operation into the pulse mode by fast production of iodine atoms. Experimental studies and numerical simulations are performed on a pulsed COIL initiated by an electric discharge in a mixture CF 3 I : N 2 : O 2 ( 3 X) : O 2 (a 1 Δ g ) flowing out of a chemical singlet oxygen generator. A transverse pulsed discharge is realized at various iodide pressures. The model comprises a system of kinetic equations for neutral and charged species, the electric circuit equation, the gas thermal balance equation and the photon balance equation. Reaction rate coefficients for processes involving electrons are repeatedly re-calculated by the electron Boltzmann equation solver when the plasma parameters are changed. The processes accounted for in the Boltzmann equation include direct and stepwise excitation and ionization of atoms and molecules, dissociation of molecules, electron attachment processes, electron-ion recombination, electron-electron collisions and second-kind collisions. The last processes are particularly important because of a high singlet oxygen concentration in gas flow from the singlet oxygen chemical generator. A conclusion is drawn about satisfactory agreement between the theory and the experiment.

  14. Lycopene Offers Protection against Oxidative Damage in Frozen-Thawn Bovine Semen

    Directory of Open Access Journals (Sweden)

    Eva Tvrdá

    2016-05-01

    Full Text Available Excessive amounts of reactive oxygen species (ROS associated with spermatozoa freezing and thawing cycles have the ability to cause oxidative stress, which may result in sperm membrane lipid peroxidation (LPO, DNA damage and apoptosis, leading to decreased sperm motility and fertilization ability. Lycopene, the most powerful singlet oxygen quencher of all carotenoids, may be a possible option for a more effective semen cryopreservation because of its antioxidant properties. By reacting with and neutralizing ROS, lycopene could reduce the incidence of oxidative stress and therefore, lessen the damage otherwise inflicted on frozen-thawn human or animal spermatozoa. This study focused to evaluate possible protective effects of lycopene on post-thawn bovine sperm and selected oxidative stress parameters. Ten bovine ejaculates were used in the study. Each ejaculate was splitted into two equal aliquots and diluted with a commercial semen extender containing lycopene (1.5 mM/L or no supplement (control, cooled to 4°C, frozen and kept in liquid nitrogen. Frozen straws were thawn in a water bath for subsequent experiments. Computer assisted semen analysis was used to evaluate spermatozoa motility, ROS generation was quantified using luminol-based luminometry and LPO was assessed via the TBARS assay and UV/VIS spectrophotometry. Lycopene supplementation to the semen extender significantly (P<0.001 increased the post-thawn spermatozoa motility (50.80±1.43% in comparison with the control (32.40±1.20%. Lycopene administration provided a significantly (P<0.001 higher protection against ROS overgeneration caused by semen freezing and thawing (17.80±2.82 RLU/sec/106 sperm when compared to the lycopene-free control (36.19±3.41 RLU/sec/106 sperm. It was determined that the presence of lycopene in the semen extender resulted in a significantly (P<0.001 lower lipid peroxidation of the spermatozoa membranes (16.43±0.56 µM/L in comparison to the control group

  15. Effect of extracellular generation of the reactive oxygen species, singlet oxygen (1O2), on the electrophysiological properties of cultured cortical neurons

    DEFF Research Database (Denmark)

    Breitenbach, Thomas; Sinks, Louise, E.; Vionogradov, Sergej A.

    Several models to mimic oxidative stress of cells have been reported. However, these models are often limited to known ROS (e.g. H2O2) or exposure times, which may exceed the pathophysiological stimulation. We have previously investigated neuronal functioning following controlled production of 1O2...... (ABM) were made from cultured rat cortical neurons to provide insight into the events following extracellular generation of 1O2. Membrane resistance (Rm), capacitance (Cm), holding current (Ihold), and firing properties were monitored throughout. The V/I relationship was investigated with 1 s duration...... current steps of 0.1 nA (-0.4 - 1 nA). The PS, dissolved in ABM (10 µM), was administered by local application directly to the neuron monitored. The intensity of the applied light at 455 nm was adjusted by neutral density filters. Phosphorescence at 700 nm proved the presence of the PS, which was absent...

  16. Effect of oxygen and iodine on the optical and magnetic properties of fullerite C60

    Science.gov (United States)

    Bagrov, I. V.; Belousova, I. M.; Ermakov, A. V.; Kiselev, V. M.; Kislyakov, I. M.; Sosnov, E. N.

    2009-04-01

    The effect of oxygen and iodine on the optical and magnetic properties of fullerite C60 is studied by luminescence and EPR spectroscopy within widely varied experimental conditions (temperature of the medium, oxygen or buffer gas pressure, concentration of iodine vapor). It is demonstrated that the efficiency of the singlet oxygen formation when a fullerene sample is irradiated by a neodymium laser at a wavelength of 532 nm and the amplitude of the EPR signal emitted from the unirradiated sample are strongly affected by the concentrations of both oxygen and iodine vapor sorbed by the fullerene sample, as well as by its surface temperature. The spin-spin and spin-lattice relaxation times of paramagnetic centers in fullerite samples studied in the presence of molecular oxygen are determined by the method of microwave radiation absorption saturation.

  17. Direct Detection of a Chemical Equilibrium between a Localized Singlet Diradical and Its σ-Bonded Species by Time-Resolved UV/Vis and IR Spectroscopy.

    Science.gov (United States)

    Yoshidomi, Shohei; Mishima, Megumi; Seyama, Shin; Abe, Manabu; Fujiwara, Yoshihisa; Ishibashi, Taka-Aki

    2017-03-06

    Localized singlet diradicals are key intermediates in bond homolyses. The singlet diradicals are energetically much less stable than the σ-bonded species. In general, only one-way reactions from diradicals to σ-bonded species are observed. In this study, a thermal equilibrium between a singlet 1,2-diazacyclopentane-3,5-diyl diradical and the corresponding σ-bonded species was directly observed. The singlet diradical was more stable than the σ-bonded species. The solvent effect clarified key features, such as the zwitterionic character of the singlet diradical. The effect of the nitrogen atoms is discussed in detail. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Attenuation of Scattered Thermal Energy Atomic Oxygen

    Science.gov (United States)

    Banks, Bruce A.; Seroka, Katelyn T.; McPhate, Jason B.; Miller, Sharon K.

    2011-01-01

    The attenuation of scattered thermal energy atomic oxygen is relevant to the potential damage that can occur within a spacecraft which sweeps through atomic oxygen in low Earth orbit (LEO). Although there can be significant oxidation and resulting degradation of polymers and some metals on the external surfaces of spacecraft, there are often openings on a spacecraft such as telescope apertures, vents, and microwave cavities that can allow atomic oxygen to enter and scatter internally to the spacecraft. Atomic oxygen that enters a spacecraft can thermally accommodate and scatter to ultimately react or recombine on surfaces. The atomic oxygen that does enter a spacecraft can be scavenged by use of high erosion yield polymers to reduce its reaction on critical surfaces and materials. Polyoxymethylene and polyethylene can be used as effective atomic oxygen scavenging polymers.

  19. Focal point analysis of the singlet-triplet energy gap of octacene and larger acenes.

    Science.gov (United States)

    Hajgató, Balázs; Huzak, Matija; Deleuze, Michael S

    2011-08-25

    A benchmark theoretical study of the electronic ground state and of the vertical and adiabatic singlet-triplet (ST) excitation energies of n-acenes (C(4n+2)H(2n+4)) ranging from octacene (n = 8) to undecacene (n = 11) is presented. The T1 diagnostics of coupled cluster theory and further energy-based criteria demonstrate that all investigated systems exhibit predominantly a (1)A(g) singlet closed-shell electronic ground state. Singlet-triplet (S(0)-T(1)) energy gaps can therefore be very accurately determined by applying the principle of a focal point analysis (FPA) onto the results of a series of single-point and symmetry-restricted calculations employing correlation consistent cc-pVXZ basis sets (X = D, T, Q, 5) and single-reference methods [HF, MP2, MP3, MP4SDQ, CCSD, and CCSD(T)] of improving quality. According to our best estimates, which amount to a dual extrapolation of energy differences to the level of coupled cluster theory including single, double, and perturbative estimates of connected triple excitations [CCSD(T)] in the limit of an asymptotically complete basis set (cc-pV∞Z), the S(0)-T(1) vertical (adiabatic) excitation energies of these compounds amount to 13.40 (8.21), 10.72 (6.05), 8.05 (3.67), and 7.10 (2.58) kcal/mol, respectively. In line with the absence of Peierls distortions (bond length alternations), extrapolations of results obtained at this level for benzene (n = 1) and all studied n-acenes so far (n = 2-11) indicate a vanishing S(0)-T(1) energy gap, in the limit of an infinitely large polyacene, within an uncertainty of 1.5 kcal/mol (0.06 eV). Lacking experimental values for the S(0)-T(1) energy gaps of n-acenes larger than hexacene, comparison is made with recent optical and electrochemical determinations of the HOMO-LUMO band gap. Further issues such as scalar relativistic, core correlation, and diagonal Born-Oppenheimer corrections (DBOCs) are tentatively examined. © 2011 American Chemical Society

  20. 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

  1. Structural damage

    International Nuclear Information System (INIS)

    Gray, R.E.; Bruhn, R.W.

    1992-01-01

    Virtually all structures show some signs of distress due to deterioration of the building components, to changed loads, or to changed support conditions. Changed support conditions result from ground movements. In mining regions many cases of structural distress are attributed to mining without considering alternative causes. This is particularly true of coal mining since it occurs under extensive areas. Coal mining is estimated to have already undermined more than eight million acres and may eventually undermine 40 million acres in the United States. Other nonmetal and metal underground mines impact much smaller areas. Although it is sometimes difficult, even with careful study, to identify the actual cause of damage, persons responsible for underground coal mining should at least be aware of possible causes of building stress other than mine subsidence. This paper presents information on distress to structures and briefly reviews a number of causes of ground movements other than subsidence: Mass movements, dissolution, erosion, frost action, shrinking and swelling, yield into excavations and compressibility

  2. Damaged Skylab

    Science.gov (United States)

    1973-01-01

    The Saturn V vehicle, carrying the unmarned orbital workshop for the Skylab-1 mission, lifted off successfully and all systems performed normally. Sixty-three seconds into the flight, engineers in the operation support and control center saw an unexpected telemetry indication that signalled that damages occurred on one solar array and the micrometeoroid shield during the launch. The micrometeoroid shield, a thin protective cylinder surrounding the workshop protecting it from tiny space particles and the sun's scorching heat, ripped loose from its position around the workshop. This caused the loss of one solar wing and jammed the other. Still unoccupied, the Skylab was stricken with the loss of the heat shield and sunlight beat mercilessly on the lab's sensitive skin. Internal temperatures soared, rendering the station uninhabitable, threatening foods, medicines, films, and experiments. This image, taken during a fly-around inspection by the Skylab-2 crew, shows a crippled Skylab in orbit. The crew found their home in space to be in serious shape; the heat shield gone, one solar wing gone, and the other jammed. The Marshall Space Flight Center (MSFC) developed, tested, rehearsed, and approved three repair options. These options included a parasol sunshade and a twin-pole sunshade to restore the temperature inside the workshop, and a set of metal cutting tools to free the jammed solar panel.

  3. Singlet and triplet state transitions of carotenoids in the antenna complexes of higher-plant photosystem I

    NARCIS (Netherlands)

    Croce, Roberta; Mozzo, Milena; Morosinotto, Tomas; Romeo, Alessandro; Hienerwadel, Rainer; Bassi, Roberta

    2007-01-01

    In this work, the spectroscopic characteristics of carotenoids associated with the antenna complexes of Photosystem I have been studied. Pigment composition, absorption spectra, and laser-induced triplet-minus-singlet (T-S) spectra were determined for native LHCI from the wild type (WT) and lut2

  4. Thermal transport in topological-insulator-based superconducting hybrid structures with mixed singlet and triplet pairing states.

    Science.gov (United States)

    Li, Hai; Zhao, Yuan Yuan

    2017-11-22

    In the framework of the Bogoliubov-de Gennes equation, we investigate the thermal transport properties in topological-insulator-based superconducting hybrid structures with mixed spin-singlet and spin-triplet pairing states, and emphasize the different manifestations of the spin-singlet and spin-triplet pairing states in the thermal transport signatures. It is revealed that the temperature-dependent differential thermal conductance strongly depends on the components of the pairing state, and the negative differential thermal conductance only occurs in the spin-singlet pairing state dominated regime. It is also found that the thermal conductance is profoundly sensitive to the components of the pairing state. In the spin-singlet pairing state controlled regime, the thermal conductance obviously oscillates with the phase difference and junction length. With increasing the proportion of the spin-triplet pairing state, the oscillating characteristic of the thermal conductance fades out distinctly. These results suggest an alternative route for distinguishing the components of pairing states in topological-insulator-based superconducting hybrid structures.

  5. Tunneling Conductance in Ferromagnetic Metal/Normal Metal/Spin-Singlet -Wave Ferromagnetic Superconductor Junctions

    Directory of Open Access Journals (Sweden)

    Hamidreza Emamipour

    2013-01-01

    Full Text Available In the framework of scattering theory, we study the tunneling conductance in a system including two junctions, ferromagnetic metal/normal metal/ferromagnetic superconductor, where ferromagnetic superconductor is in spin-singlet -wave pairing state. The non-magnetic normal metal is placed in the intermediate layer with the thickness ( which varies from 1 nm to 10000 nm. The interesting result which we have found is the existence of oscillations in conductance curves. The period of oscillations is independent of FS and FN exchange field while it depends on . The obtained results can serve as a useful tool to determine the kind of pairing symmetry in ferromagnetic superconductors.

  6. Liquid direct correlation function, singlet densities and the theory of freezing

    International Nuclear Information System (INIS)

    March, N.H.; Tosi, M.P.

    1981-04-01

    We have examined the solutions for the singlet density rho(r) in the hierarchical equation connecting rho(r) with the liquid direct correlation function c(r). In addition to the homogeneous solution rho(r)=rhosub(liquid), we exhibit a periodic solution which can co-exist with the liquid solution. If the defining equation for this is linearized, we recover the bifurcation condition of Lovett and Buff. We stress the difference between the two treatments as that between first and second-order transitions. It turns out that the treatment presented here leads to the same periodic density as that derived, using the hypernetted chain approximation, by Ramakrishnan and Yussouff in their theory of freezing. Invoking that approximation is shown thereby to be inessential. (author)

  7. Thermal transport properties of graphene-based ferromagnetic/singlet superconductor/ferromagnetic junctions

    Science.gov (United States)

    Salehi, Morteza; Alidoust, Mohammad; Rahnavard, Yousef; Rashedi, Gholamreza

    2010-06-01

    We present an investigation of heat transport in gapless graphene-based ferromagnetic/singlet superconductor/ferromagnetic junctions. We find that unlike the uniform increase in the thermal conductance versus temperature, the thermal conductance exhibits intensive oscillatory behavior versus width of sandwiched s-wave superconducting region between the two ferromagnetic layers. This oscillatory form rises from interference of the massless Dirac fermions in graphene. Also we find that thermal conductance versus exchange field h displays a minimal value at h /Ef≃1 within the low temperature regime where this finding demonstrates that propagating modes of the Dirac fermions in this value reach to their minimum numbers and verify the previous results for electronic conductance. We find that for thin widths of superconducting region, the thermal conductance versus temperature shows linear increment, i.e., Γ ∝T. At last we propose an experimental setup to detect our predicted effects.

  8. Planck scale boundary conditions in the standard model with singlet scalar dark matter

    Energy Technology Data Exchange (ETDEWEB)

    Haba, Naoyuki [Graduate School of Science and Engineering, Shimane University, Matsue, Shimane 690-8504 (Japan); Kaneta, Kunio [Kavli IPMU (WPI), The University of Tokyo, Kashiwa, Chiba 277-8568 (Japan); Takahashi, Ryo [Graduate School of Science and Engineering, Shimane University, Matsue, Shimane 690-8504 (Japan)

    2014-04-04

    We investigate Planck scale boundary conditions on the Higgs sector of the standard model with a gauge singlet scalar dark matter. We will find that vanishing self-coupling and Veltman condition at the Planck scale are realized with the 126 GeV Higgs mass and top pole mass, 172 GeV≲M{sub t}≲173.5 GeV, where a correct abundance of scalar dark matter is obtained with mass of 300 GeV≲m{sub S}≲1 TeV. It means that the Higgs potential is flat at the Planck scale, and this situation can not be realized in the standard model with the top pole mass.

  9. 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.

  10. Properties of pseudoscalar flavour-singlet mesons from 2+1+1 twisted mass lattice QCD

    Energy Technology Data Exchange (ETDEWEB)

    Cichy, Krzysztof [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Poznan Univ. (Poland). Faculty of Physics; Drach, Vincent; Garcia Ramos, Elena; Jansen, Karl [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Michael, Chris [Liverpool Univ. (United Kingdom). Dept. of Mathematical Sciences; Ottnad, Konstantin; Urbach, Carsten; Zimmermann, Falk [Bonn Univ. (Germany). Inst. fuer Strahlen- und Kernphysik

    2012-11-15

    We study properties of pseudoscalar flavour-singlet mesons from Wilson twisted mass lattice QCD with N{sub f}=2+1+1 dynamical quark flavors. Results for masses are presented at three values of the lattice spacing and light quark masses corresponding to values of the pion mass from 230 MeV to 500 MeV. We briefly discuss scaling effects and the light and strange quark mass dependence of M{sub {eta}}. In addition we present an exploratory study using Osterwalder-Seiler type strange and charm valence quarks. This approach avoids some of the complications of the twisted mass heavy doublet. We present first results for matching valence and unitary actions and a comparison of statistical uncertainties.

  11. Next-to-next-to-leading order evolution of non-singlet fragmentation functions

    International Nuclear Information System (INIS)

    Mitov, A.; Moch, S.; Vogt, A.

    2006-04-01

    We have investigated the next-to-next-to-leading order (NNLO) corrections to inclusive hadron production in e + e - annihilation and the related parton fragmentation distributions, the 'time-like' counterparts of the 'space-like' deep-inelastic structure functions and parton densities. We have re-derived the corresponding second-order coefficient functions in massless perturbative QCD, which so far had been calculated only by one group. Moreover we present, for the first time, the third-order splitting functions governing the NNLO evolution of flavour non-singlet fragmentation distributions. These results have been obtained by two independent methods relating time-like quantities to calculations performed in deep-inelastic scattering. We briefly illustrate the numerical size of the NNLO corrections, and make a prediction for the difference of the yet unknown time-like and space-like splitting functions at the fourth order in the strong coupling constant. (Orig.)

  12. Covalent dimers of 1,3-diphenylisobenzofuran for singlet fission: synthesis and electrochemistry.

    Science.gov (United States)

    Akdag, Akin; Wahab, Abdul; Beran, Pavel; Rulíšek, Lubomír; Dron, Paul I; Ludvík, Jiří; Michl, Josef

    2015-01-02

    The synthesis of covalent dimers in which two 1,3-diphenylisobenzofuran units are connected through one phenyl substituent on each is reported. In three of the dimers, the subunits are linked directly, and in three others, they are linked via an alkane chain. A seventh new compound in which two 1,3-diphenylisobenzofuran units share a phenyl substituent is also described. These materials are needed for investigations of the singlet fission process, which promises to increase the efficiency of solar cells. The electrochemical oxidation and reduction of the monomer, two previously known dimers, and the seven new compounds have been examined, and reversible redox potentials have been compared with results obtained from density functional theory. Although the overall agreement is satisfactory, some discrepancies are noted and discussed.

  13. Universal doublet-singlet Higgs couplings and phenomenology at the CERN Large Hadron Collider

    CERN Document Server

    Bhattacharyya, Gautam; Nandi, S

    2008-01-01

    We consider a minimal extension of the Standard Model where a real, gauge singlet scalar field is added to the standard spectrum. Introducing the Ansatz of universality of scalar couplings, we are led to a scenario which has a set of very distinctive and testable predictions: (i) the mixing between the SM Higgs and the new state is near maximal, (ii) the ratio of the two Higgs mass eigenstates is fixed ($\\sim \\sqrt{3}$), (iii) the decay modes of each of the two eigenstates are Standard Model like. We also study how electroweak precision tests constrain this scenario. We predict the lighter Higgs to lie in the range of 114 and 145 GeV, and hence the heavier one between 198 and 250 GeV. The predictions of the model can be tested at the upcoming LHC.

  14. Effect of CP violation in the singlet-doublet dark matter model

    Directory of Open Access Journals (Sweden)

    Tomohiro Abe

    2017-08-01

    Full Text Available We revisit the singlet-doublet dark matter model with a special emphasis on the effect of CP violation on the dark matter phenomenology. The CP violation in the dark sector induces a pseudoscalar interaction of a fermionic dark matter candidate with the SM Higgs boson. The pseudoscalar interaction helps the dark matter candidate evade the strong constraints from the dark matter direct detection experiments. We show that the model can explain the measured value of the dark matter density even if dark matter direct detection experiments do not observe any signal. We also show that the electron electric dipole moment is an important complement to the direct detection for testing this model. Its value is smaller than the current upper bound but within the reach of future experiments.

  15. LHC benchmark scenarios for the real Higgs singlet extension of the standard model

    International Nuclear Information System (INIS)

    Robens, Tania; Stefaniak, Tim

    2016-01-01

    We present benchmark scenarios for searches for an additional Higgs state in the real Higgs singlet extension of the Standard Model in Run 2 of the LHC. The scenarios are selected such that they fulfill all relevant current theoretical and experimental constraints, but can potentially be discovered at the current LHC run. We take into account the results presented in earlier work and update the experimental constraints from relevant LHC Higgs searches and signal rate measurements. The benchmark scenarios are given separately for the low-mass and high-mass region, i.e. the mass range where the additional Higgs state is lighter or heavier than the discovered Higgs state at around 125 GeV. They have also been presented in the framework of the LHC Higgs Cross Section Working Group. (orig.)

  16. 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....

  17. Induced quadrupolar singlet ground state of praseodymium in a modulated pyrochlore

    Science.gov (United States)

    van Duijn, J.; Kim, K. H.; Hur, N.; Ruiz-Bustos, R.; Adroja, D. T.; Bridges, F.; Daoud-Aladine, A.; Fernandez-Alonso, F.; Wen, J. J.; Kearney, V.; Huang, Q. Z.; Cheong, S.-W.; Perring, T. G.; Broholm, C.

    2017-09-01

    The complex structure and magnetism of Pr2 -xBixRu2O7 was investigated by neutron scattering and extended x-ray absorption fine structure. Pr has an approximate doublet ground state and the first excited state is a singlet. While the B -site (Ru) is well ordered throughout, this is not the case for the A -site (Pr/Bi). A broadened distribution for the Pr-O2 bond length at low temperature indicates the Pr environment varies from site to site even for x =0 . The environment about the Bi site is highly disordered ostensibly due to the 6 s lone pairs on Bi3 +. Correspondingly, we find that the non-Kramers doublet ground-state degeneracy, otherwise anticipated for Pr in the pyrochlore structure, is lifted so as to produce a quadrupolar singlet ground state with a spatially varying energy gap. For x =0 , below TN, the Ru sublattice orders antiferromagnetically, with propagation vector k =(0 ,0 ,0 ) as for Y2Ru2O7 . No ordering associated with the Pr sublattice is observed down to 100 mK. The low-energy magnetic response of Pr2 -xBixRu2O7 features a broad spectrum of magnetic excitations associated with inhomogeneous splitting of the Pr quasidoublet ground state. For x =0 (x =0.97 ), the spectrum is temperature dependent (independent). It appears disorder associated with Bi alloying enhances the inhomogeneous Pr crystal-field level splitting so that intersite interactions become irrelevant for x =0.97 . The structural complexity for the A -site may be reflected in the hysteretic uniform magnetization of B -site ruthenium in the Néel phase.

  18. Conformal complex singlet extension of the Standard Model: scenario for dark matter and a second Higgs boson

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhi-Wei; Steele, T.G. [Department of Physics and Engineering Physics, University of Saskatchewan,116 Science Place, Saskatoon, SK, S7N 5E2 (Canada); Hanif, T. [Department of Theoretical Physics, University of Dhaka,Dhaka-1000 (Bangladesh); Mann, R.B. [Department of Physics, University of Waterloo,Waterloo, ON, N2L 3G1 (Canada)

    2016-08-09

    We consider a conformal complex singlet extension of the Standard Model with a Higgs portal interaction. The global U(1) symmetry of the complex singlet can be either broken or unbroken and we study each scenario. In the unbroken case, the global U(1) symmetry protects the complex singlet from decaying, leading to an ideal cold dark matter candidate with approximately 100 GeV mass along with a significant proportion of thermal relic dark matter abundance. In the broken case, we have developed a renormalization-scale optimization technique to significantly narrow the parameter space and in some situations, provide unique predictions for all the model’s couplings and masses. We have found there exists a second Higgs boson with a mass of approximately 550 GeV that mixes with the known 125 GeV Higgs with a large mixing angle sin θ≈0.47 consistent with current experimental limits. The imaginary part of the complex singlet in the broken case could provide axion dark matter for a wide range of models. Upon including interactions of the complex scalar with an additional vector-like fermion, we explore the possibility of a diphoton excess in both the unbroken and the broken cases. In the unbroken case, the model can provide a natural explanation for diphoton excess if extra terms are introduced providing extra contributions to the singlet mass. In the broken case, we find a set of coupling solutions that yield a second Higgs boson of mass 720 GeV and an 830 GeV extra vector-like fermion F, which is able to address the 750 GeV LHC diphoton excess. We also provide criteria to determine the symmetry breaking pattern in both the Higgs and hidden sectors.

  19. Determination of reactive oxygen species from ZnO micro-nano structures with shape-dependent photocatalytic activity

    International Nuclear Information System (INIS)

    He, Weiwei; Zhao, Hongxiao; Jia, Huimin; Yin, Jun-Jie; Zheng, Zhi

    2014-01-01

    Graphical abstract: ZnO micro/nano structures with shape dependent photocatalytic activity were prepared by hydrothermal reaction. The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were identified precisely by electron spin resonance spectroscopy. The type of reactive oxygen species was determined by band gap structure of ZnO. - Highlights: • ZnO micro/nano structures with different morphologies were prepared by solvothermal reaction. • Multi-pod like ZnO structures exhibited superior photocatalytic activity. • The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were characterized precisely by electron spin resonance spectroscopy. • The type of reactive oxygen species was determined by band gap structure of ZnO. - Abstract: ZnO micro/nano structures with different morphologies have been prepared by the changing solvents used during their synthesis by solvothermal reaction. Three typical shapes of ZnO structures including hexagonal, bell bottom like and multi-pod formed and were characterized by scanning electron microscopy and X-ray diffraction. Multi pod like ZnO structures exhibited the highest photocatalytic activity toward degradation of methyl orange. Using electron spin resonance spectroscopy coupled with spin trapping techniques, we demonstrate an effective way to identify precisely the generation of hydroxyl radicals, superoxide and singlet oxygen from the irradiated ZnO multi pod structures. The type of reactive oxygen species formed was predictable from the band gap structure of ZnO. These results indicate that the shape of micro-nano structures significantly affects the photocatalytic activity of ZnO, and demonstrate the value of electron spin resonance spectroscopy for characterizing the type of reactive oxygen species formed during photoexcitation of semiconductors

  20. 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.