WorldWideScience

Sample records for singlet oxygen yields

  1. X-ray induced singlet oxygen generation by nanoparticle-photosensitizer conjugates for photodynamic therapy: determination of singlet oxygen quantum yield

    OpenAIRE

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

    2016-01-01

    Singlet oxygen is a primary cytotoxic agent in photodynamic therapy. We show that CeF3 nanoparticles, pure as well as conjugated through electrostatic interaction with the photosensitizer verteporfin, are able to generate singlet oxygen as a result of UV light and 8?keV X-ray irradiation. The X-ray stimulated singlet oxygen quantum yield was determined to be 0.79???0.05 for the conjugate with 31 verteporfin molecules per CeF3 nanoparticle, the highest conjugation level used. From this result ...

  2. 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

  3. 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)

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

    DEFF Research Database (Denmark)

    Nielsen, Christian Benedikt

    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...... for making efficient two-photon singlet oxygen sensitizers were then constructed from these results. Charge-transfer in the excited state of the prepared molecules was shown to play a pivotal role in the generationof singlet oxygen. This was established through studies of substituent effects on both...... 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...

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

    Science.gov (United States)

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

    2014-12-01

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

  6. 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...

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

    Energy Technology Data Exchange (ETDEWEB)

    Barik, Atanu; Indira Priyadarsini, K; Mohan, Hari; Bajaj, P N; Sapre, A V; Mittal, J P; Mukherjee, T [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India)

    2006-10-15

    Singlet molecular oxygen ({sup 1}O{sub 2}) is an excited state of molecular oxygen, having antiparallel spin in the same {pi} 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)

  8. 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)

  9. 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...... for singlet oxygen, was examined. Despite published claims to the contrary, the data presented herein indicate that SOSG can, in fact, be incorporated into a living mammalian cell. However, for a number of reasons, caution must be exercised when using SOSG. First, it is shown that the immediate product...... 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...

  10. Bromorhodamines - new singlet oxygen photosensitizers for oxidative water and wastewater treatment

    Energy Technology Data Exchange (ETDEWEB)

    Slivka, L.; Alekseeva, V.; Kuznetsova, N.; Marinina, L.; Savvina, L.; Kaliya, O.; Lukyanets, E.; Vorozhtsov, G. [Organic Intermediates and Dyes Inst., Moscow (Russian Federation); Krasnovsky, A.; Butorina, D. [Inst. of Biochemistry RAS, Moscow (Russian Federation)

    2003-07-01

    The cationic mono-, di- and tetrabromoderivatives of rhodamine 123 have been synthesized and studied as sensitizers for singlet oxygen formation in application for oxidative water treatment. Singlet oxygen quantum yields for compounds under investigation have been determined by using its near IR luminescence at 1270 nm. Bromorhodamines123 have been shown to sensitize the formation of singlet oxygen in aqueous solution with high quantum yields. Efficient oxidation of tryptophan in aqueous solutions sensitized by dibromorhodamine 123 has been demonstrated. This dye was tested as sensitizer for photodynamic treatment of water contaminated with coliform bacteria. It was shown to participate in the photosensitization of coliform bacteria, resulting in their efficient killing. (orig.)

  11. 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

  12. 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.

  13. 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.

  14. 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%.

  15. 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.

  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

    2015-01-01

    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

  17. Singlet oxygen produced by quasi-continuous photo-excitation of hypericin in dimethyl-sulfoxide

    Energy Technology Data Exchange (ETDEWEB)

    Varchola, J.; Želonková, K. [Department of Biophysics, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); Chorvat Jr, D. [International Laser Centre, Ilkovicova 3, 841 05 Bratislava (Slovakia); Jancura, D. [Department of Biophysics, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); Center for Interdisciplinary Biosciences, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); Miskovsky, P. [Department of Biophysics, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); International Laser Centre, Ilkovicova 3, 841 05 Bratislava (Slovakia); Center for Interdisciplinary Biosciences, Faculty of Science, P. J. Šafárik University, Jesenná 5, 041 54 Košice (Slovakia); and others

    2016-09-15

    Singlet oxygen (O{sub 2}({sup 1}Δ{sub g})) production by photo-excited hypericin (Hyp) dissolved in dimethyl-sulfoxide (DMSO) was studied by means of time-resolved phosphorescence measurements. In order to minimize photo-bleaching, the samples were excited in quasi-continuous mode using long-pulse (35 μs) laser excitation. The measured lifetime of singlet oxygen is τ{sub Δ}=5.5±0.3 μs. This result helps to resolve the discrepancy existing in the literature concerning singlet oxygen lifetime in DMSO. The obtained quantum yield of singlet oxygen photosensitized by Hyp in air-saturated DMSO is Φ{sub Δ}=0.4±0.03. The rate constant for Hyp triplet state depopulation in reaction with ground state molecular oxygen is measured to be k{sub q}=1.6±0.3×10{sup 9} M{sup −1} s{sup −1}.

  18. Highly efficient oxidation of amines to imines by singlet oxygen and its application in Ugi-type reactions.

    Science.gov (United States)

    Jiang, Gaoxi; Chen, Jian; Huang, Jie-Sheng; Che, Chi-Ming

    2009-10-15

    A variety of secondary benzylic amines were oxidized to imines in 90% to >99% yields by singlet oxygen generated from oxygen and a porphyrin photosensitizer. On the basis of these reactions, a protocol was developed for oxidative Ugi-type reactions with singlet oxygen as the oxidant. This protocol has been used to synthesize C1- and N-functionalized benzylic amines in up to 96% yields.

  19. 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.

  20. Scope and limitations of the TEMPO/EPR method for singlet oxygen detection: the misleading role of electron transfer.

    Science.gov (United States)

    Nardi, Giacomo; Manet, Ilse; Monti, Sandra; Miranda, Miguel A; Lhiaubet-Vallet, Virginie

    2014-12-01

    For many biological and biomedical studies, it is essential to detect the production of (1)O2 and quantify its production yield. Among the available methods, detection of the characteristic 1270-nm phosphorescence of singlet oxygen by time-resolved near-infrared (TRNIR) emission constitutes the most direct and unambiguous approach. An alternative indirect method is electron paramagnetic resonance (EPR) in combination with a singlet oxygen probe. This is based on the detection of the TEMPO free radical formed after oxidation of TEMP (2,2,6,6-tetramethylpiperidine) by singlet oxygen. Although the TEMPO/EPR method has been widely employed, it can produce misleading data. This is demonstrated by the present study, in which the quantum yields of singlet oxygen formation obtained by TRNIR emission and by the TEMPO/EPR method are compared for a set of well-known photosensitizers. The results reveal that the TEMPO/EPR method leads to significant overestimation of singlet oxygen yield when the singlet or triplet excited state of the photosensitizer is efficiently quenched by TEMP, acting as electron donor. In such case, generation of the TEMP(+) radical cation, followed by deprotonation and reaction with molecular oxygen, gives rise to an EPR-detectable TEMPO signal that is not associated with singlet oxygen production. This knowledge is essential for an appropriate and error-free application of the TEMPO/EPR method in chemical, biological, and medical studies. Copyright © 2014 Elsevier Inc. All rights reserved.

  1. Singlet oxygen production and quenching mechanisms in travelling microwave discharges

    International Nuclear Information System (INIS)

    Savin, Yu V; Goryachev, L V; Adamenkov, Yu A; Rakhimova, T V; Mankelevich, Yu A; Popov, N A; Adamenkov, A A; Egorov, V V; Ilyin, S P; Kolobyanin, Yu V; Kudryashov, E A; Rogozhnikov, G S; Vyskubenko, B A

    2004-01-01

    Experimental and theoretical studies of singlet oxygen excitation in travelling microwave (TMW) discharges are presented. Singlet oxygen O 2 (a 1 Δ g ) concentrations and atomic oxygen mole fraction have been measured for different pressures, input powers and distances from the MW resonator. It was shown that a steady-state TMW discharge with a coaxial cavity resonator could provide a maximal O 2 (a 1 Δ g ) yield of 22% for 2 Torr of pure oxygen and 27-30% for He : O 2 = 1 : 1 mixture. The two-dimensional (r, z) model developed for calculations of plasma-chemical kinetics, heat and mass transfer was used for simulation of processes in the TMW discharge under study. Effects of gas pressure, gas flow rate and input power are studied and compared with experimental measurements of O 2 (a 1 Δ g ) concentrations and atomic oxygen mole fractions

  2. 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

  3. 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"1Δ), oxygen atom removal and ozone formation. It is shown that the process O_3(υ ⩾ 2) + O_2(a"1Δ) → 2O_2 + O is the main O_2(a"1Δ) 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"1Δ) 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.

  4. In-vivo singlet oxygen threshold doses for PDT.

    Science.gov (United States)

    Zhu, Timothy C; Kim, Michele M; Liang, Xing; Finlay, Jarod C; Busch, Theresa M

    2015-02-01

    Dosimetry of singlet oxygen ( 1 O 2 ) is of particular interest because it is the major cytotoxic agent causing biological effects for type-II photosensitizers during photodynamic therapy (PDT). An in-vivo model to determine the singlet oxygen threshold dose, [ 1 O 2 ] rx,sh , for PDT was developed. An in-vivo radiation-induced fibrosarcoma (RIF) tumor mouse model was used to correlate the radius of necrosis to the calculation based on explicit PDT dosimetry of light fluence distribution, tissue optical properties, and photosensitizer concentrations. Inputs to the model include five photosensitizer-specific photochemical parameters along with [ 1 O 2 ] rx,sh . Photosensitizer-specific model parameters were determined for benzoporphyrin derivative monoacid ring A (BPD) and compared with two other type-II photosensitizers, Photofrin ® and m-tetrahydroxyphenylchlorin (mTHPC) from the literature. The mean values (standard deviation) of the in-vivo [ 1 O 2 ] rx,sh are approximately 0.56 (0.26) and 0.72 (0.21) mM (or 3.6×10 7 and 4.6×10 7 singlet oxygen per cell to reduce the cell survival to 1/e) for Photofrin ® and BPD, respectively, assuming that the fraction of generated singlet oxygen that interacts with the cell is 1. While the values for the photochemical parameters (ξ, σ, g , β) used for BPD were preliminary and may need further refinement, there is reasonable confidence for the values of the singlet oxygen threshold doses. In comparison, the [ 1 O 2 ] rx,sh value derived from in-vivo mouse study was reported to be 0.4 mM for mTHPC-PDT. However, the singlet oxygen required per cell is reported to be 9×10 8 per cell per 1/ e fractional kill in an in-vitro mTHPC-PDT study on a rat prostate cancer cell line (MLL cells) and is reported to be 7.9 mM for a multicell in-vitro EMT6/Ro spheroid model for mTHPC-PDT. A theoretical analysis is provided to relate the number of in-vitro singlet oxygen required per cell to reach cell killing of 1/ e to in-vivo singlet

  5. 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...... including across the cell membrane into the extracellular environment. On one hand, these results demonstrate that the behavior of singlet oxygen in an intact cell can be significantly different from that inferred from model bulk studies. More generally, these results provide a new perspective...

  6. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Azyazov, V.N., E-mail: azyazov@fian.smr.ru [Samara State Aerospace University, 443086 (Russian Federation); Lebedev Physical Institute of RAS, Samara 443011 (Russian Federation); Torbin, A.P.; Pershin, A.A. [Samara State Aerospace University, 443086 (Russian Federation); Lebedev Physical Institute of RAS, Samara 443011 (Russian Federation); Mikheyev, P.A., E-mail: mikheyev@fian.smr.ru [Samara State Aerospace University, 443086 (Russian Federation); Lebedev Physical Institute of RAS, Samara 443011 (Russian Federation); Heaven, M.C., E-mail: mheaven@emory.edu [Emory University, Atlanta, GA 30322 (United States)

    2015-12-16

    Highlights: • Vibrational excitation of O{sub 3} increases the rate constant for O{sub 3} + O{sub 2}(a) → 2O{sub 2}(X) + O. • Vibrationally excited O{sub 3} is produced by the O + O{sub 2}(X) + M → O{sub 3} + M reaction. • Ozone concentrations are impacted by the reactions of vibrationally excited O{sub 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{sub 3}(υ) formed in O + O{sub 2} recombination is thought to be a significant agent in the deactivation of singlet oxygen O{sub 2}(a{sup 1}Δ), oxygen atom removal and ozone formation. It is shown that the process O{sub 3}(υ ⩾ 2) + O{sub 2}(a{sup 1}Δ) → 2O{sub 2} + O is the main O{sub 2}(a{sup 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{sub 2}(a{sup 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.

  8. 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.

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

    DEFF Research Database (Denmark)

    Gollmer, Anita

    2012-01-01

    of the general methodology to generate and detect singlet oxygen is currently of great importance in order to better understand the roles played by singlet oxygen in photo-induced cell death. From a mechanistic perspective, experiments performed at the level of a single cell provide unique insight......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......, and that is the perspective of this study. Although the direct optical detection of singlet oxygen by its near IR phosphorescence is the ideal way to monitor this species, it suffers from the problem of weak signal intensity. Fluorescent probes can be a more sensitive way to detect singlet oxygen. The photochemical behavior...

  10. 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.

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

    DEFF Research Database (Denmark)

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

    2011-01-01

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

  12. Metal bacteriochlorins which act as dual singlet oxygen and superoxide generators.

    Science.gov (United States)

    Fukuzumi, Shunichi; Ohkubo, Kei; Zheng, Xiang; Chen, Yihui; Pandey, Ravindra K; Zhan, Riqiang; Kadish, Karl M

    2008-03-06

    A series of stable free-base, Zn(II) and Pd(II) bacteriochlorins containing a fused six- or five-member diketo- or imide ring have been synthesized as good candidates for photodynamic therapy sensitizers, and their electrochemical, photophysical, and photochemical properties were examined. Photoexcitation of the palladium bacteriochlorin affords the triplet excited state without fluorescence emission, resulting in formation of singlet oxygen with a high quantum yield due to the heavy atom effect of palladium. Electrochemical studies revealed that the zinc bacteriochlorin has the smallest HOMO-LUMO gap of the investigated compounds, and this value is significantly lower than the triplet excited-state energy of the compound in benzonitrile. Such a small HOMO-LUMO gap of the zinc bacteriochlorin enables intermolecular photoinduced electron transfer from the triplet excited state to the ground state to produce both the radical cation and the radical anion. The radical anion thus produced can transfer an electron to molecular oxygen to produce superoxide anion which was detected by electron spin resonance. The same photosensitizer can also act as an efficient singlet oxygen generator. Thus, the same zinc bacteriochlorin can function as a sensitizer with a dual role in that it produces both singlet oxygen and superoxide anion in an aprotic solvent (benzonitrile).

  13. Cytotoxicity But No Mutagenicity In Bacteria With Externally Generated Singlet Oxygen

    Science.gov (United States)

    Midden, W. Robert; Dahl, Thomas A.; Hartman, Philip E.

    1988-02-01

    Singlet oxygen is believed to be an important intermediate responsible for the cytotoxicity of HpD phototherapy. It has been recognized as a possible intermediate in photosensitization for more than 20 years. However, it has been difficult to obtain conclusive evidence of its biological characteristics in the past because most of the methods available for its generation that are compatible with biological systems also generate other reactive intermediates whose effects are difficult to distinguish from singlet oxygen. We have used a recently devised separated-surface-sensi-tizer (S-S-S) system for singlet oxygen generation' to measure the cytotoxicity and mutagenicity of singlet oxygen in bacteria. The S-S-S system employs rose bengal as a sensitizer immobilized on one surface of a glass plate. The glass plate is placed sensitizer-side down a small distance (plate is illuminated from above to generate singlet oxygen at the surface of the sensitizer. The singlet oxygen thus generated can diffuse the short dis-tance to the surface of the membrane to react with the bacteria. Because of the short lifetime of singlet oxygen in air, increasing the distance between the sensitizer and the membrane causes a decline in the amount of singlet oxygen reaching the membrane according to a function derived from the Einstein-Smoluchowski equation for net displacement by diffusion. Plotting the log of the effect measured (e.g., cytotoxicity) vs. the square of the distance gives a straight line. The slope of this line can be used to calculate the gas phase half life of the intermediate responsible for the observed effects. We have found that bacteria are rapidly killed in the illuminated S-S-S system and that the gas phase half life of the agent responsible for cell killing is the same as that of singlet oxygen. This observation and other simple chemical tests have conclusively estab-lished that singlet oxygen is responsible for the cytotoxicity observed with bacteria. Dosimetry

  14. Molecular and Cell Mechanisms of Singlet Oxygen Effect on Biosystems

    OpenAIRE

    Martusevich А.А.; Peretyagin S.P.; Martusevich А.К.

    2012-01-01

    There has been considered a poorly studied form of activated oxygensinglet oxygen. Its physicochemical properties (electron configuration of a molecule, reactive capacity, features) are analyzed, and enzymic and nonenzymic ways of singlet oxygen generation in body are specified. There are shown in detail biological effects of the compound as a regulator of cell activity including that determining the mechanism of apoptosis initiation. The relation of singlet oxygen and photodynamic effect ...

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

    International Nuclear Information System (INIS)

    Wright, A.; Policarpio, V.

    2003-01-01

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

  16. Singlet-oxygen 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 ...

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

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan

    2003-01-01

    by the transfer of energy to ground state (triplet) molecular oxygen by either protein-bound, or other, chromophores. Singlet oxygen can also be generated by a range of other enzymatic and non-enzymatic reactions including processes mediated by heme proteins, lipoxygenases, and activated leukocytes, as well...... the absorption of UV radiation by the protein, or bound chromophore groups, thereby generating excited states (singlet or triplets) or radicals via photo-ionisation. The second major process involves indirect oxidation of the protein via the formation and subsequent reactions of singlet oxygen generated...... 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...

  18. The effect of gold nanoparticles on exchange processes in collision complexes of triplet and singlet oxygen molecules with excited eosin molecules

    Science.gov (United States)

    Bryukhanov, V. V.; Minaev, B. M.; Tsibul'nikova, A. V.; Slezhkin, V. A.

    2015-07-01

    We have studied exchange processes in contact complexes of triplet eosin molecules with oxygen molecules in the triplet (3Σ{/g -}) and singlet (1Δ g ) states in thin polyvinylbutyral films in the presence of gold nanoparticles. Upon resonant excitation of surface plasmons in gold nanoparticles into the absorption band of eosin molecules-singlet oxygen sensitizers-we have obtained an increase in the intensity of the delayed fluorescence and an increase in the lifetime of the dye with simultaneous quenching of the luminescence of singlet oxygen. The kinetics of the delayed fluorescence of the dye as a result of singlet-triplet annihilation of triplet eosin molecules with singlet oxygen molecules has been investigated. To compare theoretical and experimental data, we have numerically simulated energy transfer processes. Rate constants of energy transfer and of singlet-triplet annihilation, as well as quenching constants of triplet states of the dye by molecular oxygen, have been calculated. Luminescence quantum yield 1Δ g of polyvinylbutyral has been estimated. We have analyzed quantum-chemically electronic mechanisms of singlet-triplet annihilation of oxygen and eosin.

  19. 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...

  20. 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.

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

    KAUST Repository

    Filatov, Mikhail A.; Karuthedath, Safakath; Polestshuk, Pavel M.; Callaghan, Susan; Flanagan, Keith J.; Wiesner, Thomas; Laquai, Fré dé ric; Senge, Mathias O.

    2018-01-01

    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.

  2. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    Mthethwa, Thandekile; Nyokong, Tebello, E-mail: t.nyokong@ru.ac.za

    2015-01-15

    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.

  4. 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

  5. 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.

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

    Science.gov (United States)

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

    2012-01-01

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

  7. 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 at the Laundromat

    Science.gov (United States)

    Keeports, David

    1995-09-01

    Singlet molecular oxygen is an interesting molecule both visually and theoretically, since its red chemiluminescence can be analyzed by the application of simple molecular orbital theory. It can be produced from the reaction of hydrogen peroxide from either chlorine gas or hypochlorite ion from household bleach. Here we demostrate how to produce it using simple laundry cleansers.

  9. Singlet oxygen generator for a solar powered chemically pumped iodine laser

    Science.gov (United States)

    Busch, G. E.

    1984-01-01

    The potential of solid phase endoperoxides as a means to produce single-delta oxygen in the gas phase in concentrations useful to chemical oxygen-iodine lasers was investigated. The 1,4 - endoperoxide of ethyl 3- (4-methyl - 1-naphthyl) propanoate was deposited over an indium-oxide layer on a glass plate. Single-delta oxygen was released from the endoperoxide upon heating the organic film by means of an electrical discharge through the conductive indium oxide coating. The evolution of singlet-delta oxygen was determined by measuring the dimol emission signal at 634 nm. Comparison of the measured signal with an analytic model leads to two main conclusions: virtually all the oxygen being evolved is in the singlet-delta state and in the gas phase, and there is no significant quenching other than energy pooling on the time scale of the experiment (approximately 10 msec). The use of solid phase endoperoxide as a singlet-delta oxygen generator for an oxygen-iodine laser appears promising.

  10. Mechanism of singlet oxygen deactivation in an electric discharge oxygen – iodine laser

    Energy Technology Data Exchange (ETDEWEB)

    Azyazov, V N; Mikheyev, P A; Torbin, A P [Samara Branch of the P.N. Lebedev Physical Institute, Russian Academy of Sciences, Samara (Russian Federation); Pershin, A A [S.P. Korolev Samara State Aerospace University, Samara (Russian Federation); Heaven, M C [Emory University, Atlanta, GA, 30322 (United States)

    2014-12-31

    We have determined the influence of the reaction of molecular singlet oxygen with a vibrationally excited ozone molecule O{sub 2}(a {sup 1}Δ) + O{sub 3}(ν) → 2O{sub 2} + O on the removal rate of O{sub 2}(a {sup 1}Δ) in an electric-discharge-driven oxygen – iodine laser. This reaction has been shown to be a major channel of O{sub 2}(a {sup 1}Δ) loss at the output of an electric-discharge singlet oxygen generator. In addition, it can also contribute significantly to the loss of O{sub 2}(a {sup 1}Δ) in the discharge region of the generator. (lasers)

  11. Regulation of singlet oxygen-induced apoptosis by cytosolic NADP+-dependent isocitrate dehydrogenase.

    Science.gov (United States)

    Kim, Sun Yee; Lee, Su Min; Tak, Jean Kyoung; Choi, Kyeong Sook; Kwon, Taeg Kyu; Park, Jeen-Woo

    2007-08-01

    Singlet oxygen is a highly reactive form of molecular oxygen that may harm living systems by oxidizing critical cellular macromolecules and it also promotes deleterious processes such as cell death. Recently, we demonstrated that the control of redox balance and the cellular defense against oxidative damage are the primary functions of cytosolic NADP(+)-dependent isocitrate dehydrogenase (IDPc) through supplying NADPH for antioxidant systems. In this report, we demonstrate that modulation of IDPc activity in HL-60 cells regulates singlet oxygen-induced apoptosis. When we examined the protective role of IDPc against singlet oxygen-induced apoptosis with HL-60 cells transfected with the cDNA for mouse IDPc in sense and antisense orientations, a clear inverse relationship was observed between the amount of IDPc expressed in target cells and their susceptibility to apoptosis. The results suggest that IDPc plays an important protective role in apoptosis of HL-60 cells induced by singlet oxygen.

  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. Advanced Singlet Oxygen Generator for a COIL

    National Research Council Canada - National Science Library

    Kodymova, Jarmila; Zagidullin, M; Nikolaev, V; Svistun, M; Khvatov, N; Hruby, J; Spalek, O; Jirasek, V; Censsky, M

    2005-01-01

    This report results from a contract tasking Academy of Sciences as follows: The Grantee will develop new and radically different ideas for a high performance, advanced singlet oxygen generator for driving a supersonic COIL...

  14. 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.

  15. Microscopic time-resolved imaging of singlet oxygen by delayed fluorescence in living cells.

    Science.gov (United States)

    Scholz, Marek; Dědic, Roman; Hála, Jan

    2017-11-08

    Singlet oxygen is a highly reactive species which is involved in a number of processes, including photodynamic therapy of cancer. Its very weak near-infrared emission makes imaging of singlet oxygen in biological systems a long-term challenge. We address this challenge by introducing Singlet Oxygen Feedback Delayed Fluorescence (SOFDF) as a novel modality for semi-direct microscopic time-resolved wide-field imaging of singlet oxygen in biological systems. SOFDF has been investigated in individual fibroblast cells incubated with a well-known photosensitizer aluminium phthalocyanine tetrasulfonate. The SOFDF emission from the cells is several orders of magnitude stronger and much more readily detectable than the very weak near-infrared phosphorescence of singlet oxygen. Moreover, the analysis of SOFDF kinetics enables us to estimate the lifetimes of the involved excited states. Real-time SOFDF images with micrometer spatial resolution and submicrosecond temporal-resolution have been recorded. Interestingly, a steep decrease in the SOFDF intensity after the photodynamically induced release of a photosensitizer from lysosomes has been demonstrated. This effect could be potentially employed as a valuable diagnostic tool for monitoring and dosimetry in photodynamic therapy.

  16. 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, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−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. PMID:22802966

  17. 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

    Substituent-dependent features and properties of the sensitizer play an important role in the photosensitized production of singlet oxygen, O2(a1Δg). In this work, we systematically examine the effect of molecular changes in the sensitizer on the efficiency of singlet oxygen production using......, as the sensitizer, oligophenylene-vinylene derivatives designed to optimally absorb light in a nonlinear two-photon process. We demonstrate that one cannot always rely on rule-of-thumb guidelines when attempting to construct efficient two-photon singlet oxygen sensitizers. Rather, as a consequence of behavior...... 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...

  18. Phenomenological model of photoluminescence degradation and photoinduced defect formation in silicon nanocrystal ensembles under singlet oxygen generation

    Energy Technology Data Exchange (ETDEWEB)

    Gongalsky, Maxim B., E-mail: mgongalsky@gmail.com; Timoshenko, Victor Yu. [Faculty of Physics, Moscow State M.V. Lomonosov University, 119991 Moscow (Russian Federation)

    2014-12-28

    We propose a phenomenological model to explain photoluminescence degradation of silicon nanocrystals under singlet oxygen generation in gaseous and liquid systems. The model considers coupled rate equations, which take into account the exciton radiative recombination in silicon nanocrystals, photosensitization of singlet oxygen generation, defect formation on the surface of silicon nanocrystals as well as quenching processes for both excitons and singlet oxygen molecules. The model describes well the experimentally observed power law dependences of the photoluminescence intensity, singlet oxygen concentration, and lifetime versus photoexcitation time. The defect concentration in silicon nanocrystals increases by power law with a fractional exponent, which depends on the singlet oxygen concentration and ambient conditions. The obtained results are discussed in a view of optimization of the photosensitized singlet oxygen generation for biomedical applications.

  19. Highly sensitive time resolved singlet oxygen luminescence detection using LEDs as the excitation source

    International Nuclear Information System (INIS)

    Hackbarth, S; Schlothauer, J; Preuss, A; Röder, B

    2013-01-01

    For the first time singlet oxygen luminescence kinetics in living cells were detected at high precision using LED light for excitation. As LED technology evolves, the light intensity emitted by standard LEDs allows photosensitized singlet oxygen luminescence detection in solution and cell suspensions. We present measurements superior to those of most actual laser powered setups regarding precision of singlet oxygen kinetics in solutions and cell suspensions. Data presented here show that LED based setups allow the determination of the photosensitizer triplet and singlet oxygen decay times in vitro with an accuracy of 0.1 μs. This enables monitoring of the photosensitizer efficiency and interaction with the cellular components using illumination doses small enough not to cause cell death. (letter)

  20. Continuous-flow oxidative cyanation of primary and secondary amines using singlet oxygen.

    Science.gov (United States)

    Ushakov, Dmitry B; Gilmore, Kerry; Kopetzki, Daniel; McQuade, D Tyler; Seeberger, Peter H

    2014-01-07

    Primary and secondary amines can be rapidly and quantitatively oxidized to the corresponding imines by singlet oxygen. This reactive form of oxygen was produced using a variable-temperature continuous-flow LED-photoreactor with a catalytic amount of tetraphenylporphyrin as the sensitizer. α-Aminonitriles were obtained in good to excellent yields when trimethylsilyl cyanide served as an in situ imine trap. At 25°C, primary amines were found to undergo oxidative coupling prior to cyanide addition and yielded secondary α-aminonitriles. Primary α-aminonitriles were synthesized from the corresponding primary amines for the first time, by an oxidative Strecker reaction at -50 °C. This atom-economic and protecting-group-free pathway provides a route to racemic amino acids, which was exemplified by the synthesis of tert-leucine hydrochloride from neopentylamine. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Bactericidal action of photogenerated singlet oxygen from photosensitizers used in plaque disclosing agents.

    Directory of Open Access Journals (Sweden)

    Kirika Ishiyama

    Full Text Available BACKGROUND: Photodynamic therapy (PDT has been suggested as an efficient clinical approach for the treatment of dental plaque in the field of dental care. In PDT, once the photosensitizer is irradiated with light of a specific wavelength, it transfers the excitation energy to molecular oxygen, which gives rise to singlet oxygen. METHODOLOGY/PRINCIPAL FINDINGS: Since plaque disclosing agents usually contain photosensitizers such as rose bengal, erythrosine, and phloxine, they could be used for PTD upon photoactivation. The aim of the present study is to compare the ability of these three photosensitizers to produce singlet oxygen in relation to their bactericidal activity. The generation rates of singlet oxygen determined by applying an electron spin resonance technique were in the order phloxine > erythrosine ≒ rose bengal. On the other hand, rose bengal showed the highest bactericidal activity against Streptococcus mutans, a major causative pathogen of caries, followed by erythrosine and phloxine, both of which showed activity similar to each other. One of the reasons for the discrepancy between the singlet oxygen generating ability and bactericidal activity was the incorporation efficiency of the photosensitizers into the bacterial cells. The incorporation rate of rose bengal was the highest among the three photosensitizers examined in the present study, likely leading to the highest bactericidal activity. Meanwhile, the addition of L-histidine, a singlet oxygen quencher, cancelled the bactericidal activity of any of the three photoactivated photosensitizers, proving that singlet oxygen was responsible for the bactericidal action. CONCLUSIONS: It is strongly suggested that rose bengal is a suitable photosensitizer for the plaque disclosing agents as compared to the other two photosensitizers, phloxine and erythrosine, when used for PDT.

  2. 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

  3. Wavelength dependence of the efficiency of singlet oxygen generation upon photoexcitation of photosensitizers

    Directory of Open Access Journals (Sweden)

    Starukhin A.

    2017-01-01

    Full Text Available The dependence of the efficiency of singlet oxygen (1Δg generation upon excitation of photosensitizer at different wavelength was observed for several derivatives of palladium porphyrin in carbon tetrachloride. The efficiency of singlet oxygen generation upon excitation in a blue region of the spectrum (Soret band exceeds by several times the efficiency at excitation in the red spectral region (Q band. The effect of enhancement of singlet oxygen generation upon CW photoexcitation to Soret band of photosensitizer may be explained by influence of high laying triplet states of a donor molecule on the triplet-triplet energy transfer.

  4. 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

  5. Cellular defense against singlet oxygen-induced oxidative damage by cytosolic NADP+-dependent isocitrate dehydrogenase.

    Science.gov (United States)

    Kim, Sun Yee; Park, Jeen-Woo

    2003-03-01

    Singlet oxygen (1O2) is a highly reactive form of molecular oxygen that may harm living systems by oxidizing critical cellular macromolecules. Recently, we have shown that NADP+-dependent isocitrate dehydrogenase is involved in the supply of NADPH needed for GSH production against cellular oxidative damage. In this study, we investigated the role of cytosolic form of NADP+-dependent isocitrate dehydrogenase (IDPc) against singlet oxygen-induced cytotoxicity by comparing the relative degree of cellular responses in three different NIH3T3 cells with stable transfection with the cDNA for mouse IDPc in sense and antisense orientations, where IDPc activities were 2.3-fold higher and 39% lower, respectively, than that in the parental cells carrying the vector alone. Upon exposure to singlet oxygen generated from photoactivated dye, the cells with low levels of IDPc became more sensitive to cell killing. Lipid peroxidation, protein oxidation, oxidative DNA damage and intracellular peroxide generation were higher in the cell-line expressing the lower level of IDPc. However, the cells with the highly over-expressed IDPc exhibited enhanced resistance against singlet oxygen, compared to the control cells. The data indicate that IDPc plays an important role in cellular defense against singlet oxygen-induced oxidative injury.

  6. 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

  7. Real-Time Monitoring of Singlet Oxygen and Oxygen Partial Pressure During the Deep Photodynamic Therapy In Vitro.

    Science.gov (United States)

    Li, Weitao; Huang, Dong; Zhang, Yan; Liu, Yangyang; Gu, Yueqing; Qian, Zhiyu

    2016-09-01

    Photodynamic therapy (PDT) is an effective noninvasive method for the tumor treatment. The major challenge in current PDT research is how to quantitatively evaluate therapy effects. To our best knowledge, this is the first time to combine multi-parameter detection methods in PDT. More specifically, we have developed a set of system, including the high-sensitivity measurement of singlet oxygen, oxygen partial pressure and fluorescence image. In this paper, the detection ability of the system was validated by the different concentrations of carbon quantum dots. Moreover, the correlation between singlet oxygen and oxygen partial pressure with laser irradiation was observed. Then, the system could detect the signal up to 0.5 cm tissue depth with 660 nm irradiation and 1 cm tissue depth with 980 nm irradiation by using up-conversion nanoparticles during PDT in vitro. Furthermore, we obtained the relationship among concentration of singlet oxygen, oxygen partial pressure and tumor cell viability under certain conditions. The results indicate that the multi-parameter detection system is a promising asset to evaluate the deep tumor therapy during PDT. Moreover, the system might be potentially used for the further study in biology and molecular imaging.

  8. Singlet oxygenation in microemulsion catalysed by vanadium chloroperoxidase

    NARCIS (Netherlands)

    Renirie, R.; Pierlot, C.; Wever, R.; Aubry, J.-M.

    2009-01-01

    Non-ionic microemulsions compatible with the enzyme vanadium chloroperoxidase were designed to perform singlet oxygenation of apolar substrates. The media were based on mono- and polydisperse ethoxylated fatty alcohols (CiEj). octane and aqueous buffer. "Fish" diagrams were determined to identify

  9. Development of Singlet Oxygen Luminescence Kinetics during the Photodynamic Inactivation of Green Algae

    Directory of Open Access Journals (Sweden)

    Tobias Bornhütter

    2016-04-01

    Full Text Available Recent studies show the feasibility of photodynamic inactivation of green algae as a vital step towards an effective photodynamic suppression of biofilms by using functionalized surfaces. The investigation of the intrinsic mechanisms of photodynamic inactivation in green algae represents the next step in order to determine optimization parameters. The observation of singlet oxygen luminescence kinetics proved to be a very effective approach towards understanding mechanisms on a cellular level. In this study, the first two-dimensional measurement of singlet oxygen kinetics in phototrophic microorganisms on surfaces during photodynamic inactivation is presented. We established a system of reproducible algae samples on surfaces, incubated with two different cationic, antimicrobial potent photosensitizers. Fluorescence microscopy images indicate that one photosensitizer localizes inside the green algae while the other accumulates along the outer algae cell wall. A newly developed setup allows for the measurement of singlet oxygen luminescence on the green algae sample surfaces over several days. The kinetics of the singlet oxygen luminescence of both photosensitizers show different developments and a distinct change over time, corresponding with the differences in their localization as well as their photosensitization potential. While the complexity of the signal reveals a challenge for the future, this study incontrovertibly marks a crucial, inevitable step in the investigation of photodynamic inactivation of biofilms: it shows the feasibility of using the singlet oxygen luminescence kinetics to investigate photodynamic effects on surfaces and thus opens a field for numerous investigations.

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

    Science.gov (United States)

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

    2017-09-01

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

  12. 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...... cells in a 1 cm cuvette. Data were recorded using hydrophilic and, independently, hydrophobic sensitizers. The microscope-based single cell results are consistent with a model in which the behavior of singlet oxygen reflects the environment in which it is produced; nevertheless, the data also indicate...... that a significant fraction of a given singlet oxygen population readily crosses barriers between phase-separated intracellular domains. The singlet oxygen phosphorescence signals reflect the effects of singlet-oxygen-mediated damage on cell components which, at the limit, mean that data were collected from dead...

  13. A comparative study of the processes of generation of singlet oxygen upon irradiation of aqueous preparations on the basis of chlorin e6 and coproporphyrin III

    Science.gov (United States)

    Bagrov, I. V.; Belousova, I. M.; Gorelov, S. I.; Dobrun, M. V.; Kiselev, V. M.; Kislyakov, I. M.; Kris'ko, A. V.; Kris'ko, T. K.

    2017-02-01

    The photosensitizing ability of an agent based on chlorin e6 (Photoditazin), which is used for photodynamic diagnosis and therapy, is compared with that of a new preparation on the basis of coproporphyrin III in the environment of a phosphate buffer and a simulated biological environment (albumin solution). The efficiency of singlet-oxygen production was estimated by EPR spectroscopy and spectroscopy in the UV and visible ranges with the use of "chemical traps" of singlet oxygen. By irradiating drugs with LED emission centered at λmax = 520 nm, we determined the quantum yield of singlet-oxygen production in a buffer solution; the obtained values are 0.60 and 0.37 for chlorine and coproporphyrin, respectively. The steady-state concentration of singlet oxygen upon irradiation of solutions of the studied photosensitizers with concentrations of 12-43 μM and the density of radiation power within the 6-96 W/cm2 region was found to be in the region of 1010-1011 molecules/cm3. It is shown that the introduction into the solution of egg albumin (0.1%) reduces the sensitizing properties of the two drugs by two to three times, while the efficiencies of the preparations with respect to singlet-oxygen production become almost identical (0.19 and 0.17).

  14. Singlet Oxygen and Free Radical Reactions of Retinoids and Carotenoids—A Review

    Science.gov (United States)

    Truscott, T. George

    2018-01-01

    We report on studies of reactions of singlet oxygen with carotenoids and retinoids and a range of free radical studies on carotenoids and retinoids with emphasis on recent work, dietary carotenoids and the role of oxygen in biological processes. Many previous reviews are cited and updated together with new data not previously reviewed. The review does not deal with computational studies but the emphasis is on laboratory-based results. We contrast the ease of study of both singlet oxygen and polyene radical cations compared to neutral radicals. Of particular interest is the switch from anti- to pro-oxidant behavior of a carotenoid with change of oxygen concentration: results for lycopene in a cellular model system show total protection of the human cells studied at zero oxygen concentration, but zero protection at 100% oxygen concentration. PMID:29301252

  15. 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.

  16. 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

  17. 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...

  18. 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 octaarginin...... indicate that efficient photodynamic endosomal escape is strongly dependent on the quantum yield for photochemical singlet oxygen formation, photostability as well as the lipophilicity of the chromophore....

  19. Cytometric quantification of singlet oxygen in the human malaria parasite Plasmodium falciparum

    NARCIS (Netherlands)

    Butzloff, Sabine; Groves, Matthew R; Wrenger, Carsten; Müller, Ingrid B

    The malaria parasite Plasmodium falciparum proliferates within human erythrocytes and is thereby exposed to a variety of reactive oxygen species (ROS) such as hydrogen peroxide, hydroxyl radical, superoxide anion, and highly reactive singlet oxygen ((1)O(2)). While most ROS are already well studied

  20. Characterization of photoactivated singlet oxygen damage in single-molecule optical trap experiments.

    Science.gov (United States)

    Landry, Markita P; McCall, Patrick M; Qi, Zhi; Chemla, Yann R

    2009-10-21

    Optical traps or "tweezers" use high-power, near-infrared laser beams to manipulate and apply forces to biological systems, ranging from individual molecules to cells. Although previous studies have established that optical tweezers induce photodamage in live cells, the effects of trap irradiation have yet to be examined in vitro, at the single-molecule level. In this study, we investigate trap-induced damage in a simple system consisting of DNA molecules tethered between optically trapped polystyrene microspheres. We show that exposure to the trapping light affects the lifetime of the tethers, the efficiency with which they can be formed, and their structure. Moreover, we establish that these irreversible effects are caused by oxidative damage from singlet oxygen. This reactive state of molecular oxygen is generated locally by the optical traps in the presence of a sensitizer, which we identify as the trapped polystyrene microspheres. Trap-induced oxidative damage can be reduced greatly by working under anaerobic conditions, using additives that quench singlet oxygen, or trapping microspheres lacking the sensitizers necessary for singlet state photoexcitation. Our findings are relevant to a broad range of trap-based single-molecule experiments-the most common biological application of optical tweezers-and may guide the development of more robust experimental protocols.

  1. A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds

    Directory of Open Access Journals (Sweden)

    Anabela Sousa Oliveira

    2009-01-01

    Full Text Available This paper deals with a series of new unsymmetrically substituted mesoporphyrins: 5-(2-hydroxyphenyl-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHO, 5-(3-hydroxyphenyl-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHM, 5-(4-hydroxyphenyl-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHP, 5-(2-hydroxyphenyl-10,15,20-tris-butyl-21,23-H-porphyrin (TBPOHO, and their parent nonsubstituted compounds, respectively, 5,10,15,20-tetrakis-phenyl-21,23-H-porphyrin (TPP and 5,10,15,20-tetrakis-butyl-21,23-H-porphyrin (TBP. Several photophysical studies were carried out to access the influence of the unsymmetrical substitution at the porphyrinic macrocycle on porthyrin's photophysical properties, especially porthyrin's efficiency as singlet oxygen sensitizers. The quantum yields of singlet oxygen generation were determined in benzene (ΦΔ(TPP = 0.66 ± 0.05; ΦΔ(TPPOHO = 0.69 ± 0.04; ΦΔ(TPPOHM = 0.62 ± 0.04; ΦΔ(TPPOHP = 0.73 ± 0.03; ΦΔ(TBP = 0.76 ± 0.03; ΦΔ(TBPOHO = 0.73 ± 0.02 using the 5,10,15,20-tetraphenyl-21,23-H-porphine (ΦΔ(TPP = 0.66 and Phenazine (ΦΔ(Phz = 0.83 as reference compounds. Their fluorescence quantum yields were found to be (Φf(TPPOHO = 0.10 ± 0.04; Φf(TPPOHM = 0.09 ± 0.03; Φf(TPPOHP = 0.13 ± 0.02; Φf(TBP = 0.08 ± 0.03 and Φf(TBPOHO = 0.08 ± 0.02 using 5,10,15,20-tetraphenyl-21,23-H-porphine as reference Φf(TPP = 0.13. Singlet state lifetimes were also determined in the same solvent. All the porphyrins presented very similar fluorescence lifetimes (mean values of τS (with O2, air equilibrated = 9.6 ± 0.3 nanoseconds and (without O2, argon purged = 10.1 ± 0.6 nanoseconds, resp.. The phosphorescence emission was found to be negligible for this series of unsymmetrically substituted mesoporphyrins, but an E-type, thermally activated, delayed fluorescence process was proved to occur at room temperature.

  2. 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.

  3. Luminescence spectroscopic observation of singlet oxygen formation in extra virgin olive oil as affected by irradiation light wavelengths, 1,4-diazabicyclo[2.2.2]octane, irradiation time, and oxygen bubbling.

    Science.gov (United States)

    Jung, Mun Y; Choi, Dong S; Park, Ki H; Lee, Bosoon; Min, David B

    2011-01-01

    A spectrofluorometer equipped with a highly sensitive near-IR InGaAs detector was used for the direct visualization of singlet oxygen emission at 1268 nm in olive oil during light irradiation with various different wavelengths. The virgin olive oil in methylene chloride (20% w/v, oxygen saturated) was irradiated at the 301, 417, 454, 483, and 668 nm, then the emission at 1268 nm, singlet oxygen dimole decaying was observed. The result showed the highest production of (1)O(2) with light irradiation at 417 nm, and followed by at 668 nm in virgin olive oil, indicating that pheophytin a and chlorophyll a were the most responsible components for the production of singlet oxygen. The UV light irradiations at the wavelength of 200, 250, and 300 nm did not induce any detectable luminescence emission at 1268 nm, but 350 nm produced weak emission at 1269 nm. The quantity of (1)O(2) produced with excitation at 350 nm was about 1/6 of that of irradiation at 417 nm. Addition of an efficient (1)O(2) quencher, 1,4-diazabicyclo[2.2.2]octane, in virgin olive oil in methylene chloride greatly decreased the luminescence emission at 1268 nm, confirming the singlet oxygen production in olive oil. Singlet oxygen production was more efficient in oxygen-purged virgin olive oil than in oxygen non-purged olive oil. This represents first report on the direct observation of singlet oxygen formation in olive oil as well as in real-food system after visible light illumination. Practical Application: The present results show the positive evidence of the singlet oxygen involvement in rapid oxidative deterioration of virgin olive oil under visible light. This paper also shows the effects of different wavelength of light irradiation on the formation of singlet oxygen in olive oil. The present results would provide important information for the understanding of the mechanism involved in rapid oxidative quality deterioration of virgin olive oil under light illumination and for searching the

  4. 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

  5. Singlet oxygen oxygenation of enol ethers; the synthesis of optically active 1,2-dioxetanes. II

    NARCIS (Netherlands)

    Meijer, E.W.; Wynberg, H.

    1979-01-01

    (+)-(Methoxymethylene)fenchane I (R = H, R1 = OMe) on singlet O oxidn. gave dioxetanes II and III, which on thermal decompn. underwent chemiluminescence in which (+)-fenchone was the only chemiluminescent species at lmax 420 nm. Photosensitized oxygenation of I (R = OMe, R1 = H) also gave 2 isomeric

  6. 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 particular, are major targets for 1O2 as a result of their abundance and high rate constants for reaction. In this study it is shown that long-lived peroxides are formed on free Tyr, Tyr residues in peptides and proteins, and model compounds on exposure to 1O2 generated by both photochemical and chemical....... These studies demonstrate that long-lived Tyr-derived peroxides are formed on proteins exposed to 1O2 and that these may promote damage to other targets via further radical generation....

  7. Detection of Singlet Oxygen Formation inside Photoactive Biohybrid Composite Material

    Directory of Open Access Journals (Sweden)

    Kata Hajdu

    2017-12-01

    Full Text Available Photosynthetic reaction center proteins (RCs are the most efficient light energy converter systems in nature. The first steps of the primary charge separation in photosynthesis take place in these proteins. Due to their unique properties, combining RCs with nano-structures promising applications can be predicted in optoelectronic systems. In the present work RCs purified from Rhodobacter sphaeroides purple bacteria were immobilized on multiwalled carbon nanotubes (CNTs. Carboxyl—and amine-functionalised CNTs were used, so different binding procedures, physical sorption and chemical sorption as well, could be applied as immobilization techniques. Light-induced singlet oxygen production was measured in the prepared photoactive biocomposites in water-based suspension by histidine mediated chemical trapping. Carbon nanotubes were applied under different conditions in order to understand their role in the equilibration of singlet oxygen concentration in the suspension. CNTs acted as effective quenchers of 1O2 either by physical (resonance energy transfer or by chemical (oxidation reaction and their efficiency showed dependence on the diffusion distance of 1O2.

  8. 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

  9. 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

  10. 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.

  11. 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

  12. Singlet oxygen feedback delayed fluorescence of protoporphyrin IX in organic solutions.

    Science.gov (United States)

    Vinklárek, Ivo S; Scholz, Marek; Dědic, Roman; Hála, Jan

    2017-04-12

    Delayed fluorescence (DF) of protoporphyrin IX (PpIX) has been recently proposed as a tool for monitoring of mitochondrial oxygen tension in vivo as well as for observation of the effectiveness of photodynamic therapy (PDT) [E. G. Mik, Anesth. Analg., 2013, 117, 834-346; F. Piffaretti et al., J. Biomed. Opt., 2012, 17, 115007]. However, the efficiency of the mechanism of thermal activation (E-type DF), which was considered in the papers, is limited due to a large energy gap between the first excited singlet and the first triplet state of PpIX at room or body temperatures. Moreover, the energy gap is roughly equal to other porphyrinoid photosensitizers that generate DF mostly through the Singlet Oxygen Feedback-Induced mechanism (SOFDF) under certain conditions [M. Scholz and R. Dědic, Singlet Oxygen: Applications in Biosciences and Nanosciences, 2016, vol. 2, pp. 63-81]. The mechanisms of delayed fluorescence of PpIX dissolved either in dimethylformamide (DMF) or in the mixture of DMF with ethylene glycol (EG) were investigated at atmospheric partial pressure of oxygen by means of a simultaneous time-resolved detection of 1 O 2 phosphorescence and PpIX DF which makes a direct comparison of the kinetics and lifetimes of both the luminescence channels possible. Samples of PpIX (100 μM) exhibit concave DF kinetics, which is a typical footprint of the SOFDF mechanism. The dramatic decrease in the DF intensity after adding a selective 1 O 2 quencher sodium azide (NaN 3 , 10 mM) proves that >90% of DF is indeed generated through SOFDF. Moreover, the analysis of the DF kinetics in the presence of NaN 3 implies that the second significant mechanism of DF generation is the triplet-triplet annihilation (P-type DF). The bimolecular mechanism of DF was further confirmed by the decrease of the DF intensity in the more viscous mixture DMF/EG and by the increase of the ratio of DF to the prompt fluorescence (PF) intensity with the increasing excitation intensity. These results

  13. 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

  14. 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®.

  15. 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

  16. Photo-oxidation of histidine peptides yields high concentrations of unstable peroxides

    International Nuclear Information System (INIS)

    Policarpio, V.V.; Hawkins, C.L.; Davies, M.J.

    2003-01-01

    Oxidation of proteins by UV, and visible light in the presence of sensitizers, results in side chain modification as well as aggregation and fragmentation. In particular, singlet oxygen has been reported to oxidize Met, Trp, Tyr, Cys and His side chains in a selective manner. In this study the oxidation of histidine and its derivatives, and His-containing peptides is examined using a range of sensitizers, to determine whether peroxides are major intermediates, and the mechanism of formation of these species. Visible light-sensitised oxidation of Gly-His-Gly in the presence of oxygen and rose bengal gives unstable substrate-derived peroxides with the peroxide yield increasing with increasing photolysis time. Similar behaviour was detected with other photosensitizers, though the peroxide yields varied with the sensitizer at identical concentrations with rose bengal > aluminium phthalocyanine > hematoporphyrin IX > zinc phthalocyanine > tetrakisporphine. The peroxide yield was decreased in the presence of azide and enhanced when deuterium oxide was employed as the solvent, consistent with peroxide formation being singlet oxygen mediated. Experiments using anoxic conditions gave low yields of peroxides confirming the oxygen-dependence of these reactions. HPLC analysis showed rapid loss of the parent peptide, with subsequent formation of both stable and unstable products; these are currently being characterized by MS and NMR. Similar behavior has been observed with other His derivatives. The yield of singlet oxygen formed in these reactions has been estimated using a bleaching assay (N, N-dimethyl-4-nitrosoaniline). Quantification of singlet oxygen formation and Gly-His-Gly derived peroxide during rose bengal-mediated photooxidation indicated a conversion efficiency of the initial singlet oxygen into substrate-derived peroxides of ca. 75% indicating that peroxide formation is a highly efficient and major reaction pathway

  17. Physics and engineering of singlet delta oxygen production in low-temperature plasma

    International Nuclear Information System (INIS)

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

    2007-01-01

    An overview is presented of experimental and theoretical research in the field of physics and engineering of singlet delta oxygen (SDO) production in low-temperature plasma of various electric discharges. Attention is paid mainly to the SDO production with SDO yield adequate for the development of an electric discharge oxygen-iodine laser (DOIL). The review comprises a historical sketch describing the main experimental results on SDO physics in low-temperature plasma obtained since the first detection of SDO in electric discharge in the 1950s and the first attempt to launch a DOIL in the 1970s up to the mid-1980s when several research groups started their activity aimed at DOIL development, stimulated by success in the development of a chemical oxygen-iodine laser (COIL). A detailed analysis of theoretical and experimental research on SDO production in electric discharge from the mid-1980s to the present, when the first DOIL has been launched, is given. Different kinetic models of oxygen low-temperature plasma are compared with the model developed by the authors. The latter comprises electron kinetics based on the accompanying solution of the electron Boltzmann equation, plasma chemistry including reactions of excited molecules and numerous ion-molecular reactions, thermal energy balance and electric circuit equation. The experimental part of the overview is focused on the experimental methods of SDO detection including experiments on the measurements of the Einstein coefficient for SDO transition a 1 Δ g - X 3 Σ g - and experimental procedures of SDO production in self-sustained and non-self-sustained discharges and analysis of different plasma-chemical processes occurring in oxygen low-temperature plasma which brings limitation to the maximum SDO yield and to the lifetime of the SDO in an electric discharge and its afterglow. Quite recently obtained results on gain and output characteristics of DOIL and some projects aimed at the development of high-power DOIL

  18. BODIPY-Au(I): A Photosensitizer for Singlet Oxygen Generation and Photodynamic Therapy.

    Science.gov (United States)

    Üçüncü, Muhammed; Karakuş, Erman; Kurulgan Demirci, Eylem; Sayar, Melike; Dartar, Suay; Emrullahoğlu, Mustafa

    2017-05-19

    Upon complexation with Au(I), a photoinactive BODIPY derivative was transformed into a highly photoactive triplet sensitizer. Along with high efficiency in singlet oxygen generation (Φ Δ = 0.84), the new BODIPY-Au(I) skeleton showed excellent photocytotoxic activity against cancer cell lines (EC 50 = 2.5 nM).

  19. Effects of light irradiation upon photodynamic therapy based on 5-aminolevulinic acid–gold nanoparticle conjugates in K562 cells via singlet oxygen generation

    Directory of Open Access Journals (Sweden)

    Xu H

    2012-09-01

    Full Text Available Hao Xu, Chen Liu, Jiansheng Mei, Cuiping Yao, Sijia Wang, Jing Wang, Zheng Li, Zhenxi ZhangKey Laboratory of Biomedical Information Engineering of Education Ministry, Institute of Biomedical Analytical Technology and Instrumentation, School of Life Science and Technology, Xi’an Jiaotong University, Xi’an, Shannxi, People’s Republic of ChinaPurpose: As a precursor of the potent photosensitizer protoporphyrin IX (PpIX, 5-aminolevulinic acid (5-ALA, was conjugated onto cationic gold nanoparticles (GNPs to improve the efficacy of photodynamic therapy (PDT.Methods: Cationic GNPs reduced by branched polyethyleneimine and 5-ALA were conjugated onto the cationic GNPs by creating an electrostatic interaction at physiological pH. The efficacy of ALA-GNP conjugates in PDT was investigated under irradiation with a mercury lamp (central wavelength of 395 nm and three types of light-emitting diode arrays (central wavelengths of 399, 502, and 621 nm, respectively. The impacts of GNPs on PDT were then analyzed by measuring the intracellular PpIX levels in K562 cells and the singlet oxygen yield of PpIX under irradiation.Results: The 2 mM ALA-GNP conjugates showed greater cytotoxicity against K562 cells than ALA alone. Light-emitting diode (505 nm irradiation of the conjugates caused a level of K562 cell destruction similar to that with irradiation by a mercury lamp, although it had no adverse effects on drug-free control cells. These results may be attributed to the singlet oxygen yield of PpIX, which can be enhanced by GNPs.Conclusion: Under irradiation with a suitable light source, ALA-GNP conjugates can effectively destroy K562 cells. The technique offers a new strategy of PDT.Keywords: nonradiative energy transfer, photodamage, protoporphyrin IX, selective destruction, singlet oxygen sensor green reagent, surface plasmon resonance

  20. 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.

  1. 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...

  2. Theoretical study of singlet oxygen molecule generation via an exciplex with valence-excited thiophene.

    Science.gov (United States)

    Sumita, Masato; Morihashi, Kenji

    2015-02-05

    Singlet-oxygen [O2((1)Δg)] generation by valence-excited thiophene (TPH) has been investigated using multireference Møller-Plesset second-order perturbation (MRMP2) theory of geometries optimized at the complete active space self-consistent field (CASSCF) theory level. Our results indicate that triplet TPH(1(3)B2) is produced via photoinduced singlet TPH(2(1)A1) because 2(1)A1 TPH shows a large spin-orbit coupling constant with the first triplet excited state (1(3)B2). The relaxed TPH in the 1(3)B2 state can form an exciplex with O2((3)Σg(-)) because this exciplex is energetically more stable than the relaxed TPH. The formation of the TPH(1(3)B2) exciplex with O2((3)Σg(-)) whose total spin multiplicity is triplet (T1 state) increases the likelihood of transition from the T1 state to the singlet ground or first excited singlet state. After the transition, O2((1)Δg) is emitted easily although the favorable product is that from a 2 + 4 cycloaddition reaction.

  3. Pharmaceutical micelles featured with singlet oxygen-responsive cargo release and mitochondrial targeting for enhanced photodynamic therapy

    Science.gov (United States)

    Zhang, Xin; Yan, Qi; Naer Mulatihan, Di; Zhu, Jundong; Fan, Aiping; Wang, Zheng; Zhao, Yanjun

    2018-06-01

    The efficacy of nanoparticulate photodynamic therapy is often compromised by the short life time and limited diffusion radius of singlet oxygen as well as uncontrolled intracellular distribution of photosensitizer. It was hypothesized that rapid photosensitizer release upon nanoparticle internalization and its preferred accumulation in mitochondria would address the above problems. Hence, the aim of this study was to engineer a multifunctional micellar nanosystem featured with singlet oxygen-responsive cargo release and mitochondria-targeting. An imidazole-bearing amphiphilic copolymer was employed as the micelle building block to encapsulate triphenylphosphonium-pyropheophorbide a (TPP-PPa) conjugate or PPa. Upon laser irradiation, the singlet oxygen produced by TPP-PPa/PPa oxidized the imidazole moiety to produce hydrophilic urea, leading to micelle disassembly and rapid cargo release. The co-localization analysis showed that the TPP moiety significantly enhanced the photosensitizer uptake by mitochondria, improved mitochondria depolarization upon irradiation, and hence boosted the cytotoxicity in 4T1 cells. The targeting strategy also dramatically reduced the intracellular ATP concentration as a consequence of mitochondria injury. The mitochondria damage was accompanied with the activation of the apoptosis signals (caspase 3 and caspase 9), whose level was directly correlated to the apoptosis extent. The current work provides a facile and robust means to enhance the efficacy of photodynamic therapy.

  4. Reactive species formed on proteins exposed to singlet oxygen

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan

    2004-01-01

    Singlet oxygen ((1)O(2)) is believed to be generated in biological systems by a range of endogenous processes (e.g. enzymatic and chemical reactions) and exogenous stimuli (e.g. UV or visible light in the presence of a sensitiser). Kinetic data is consistent with proteins being a major target...... 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...

  5. 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.

  6. Effects of the oxygenation level on formation of different reactive oxygen species during photodynamic therapy.

    Science.gov (United States)

    Price, Michael; Heilbrun, Lance; Kessel, David

    2013-01-01

    We examined the effect of the oxygenation level on efficacy of two photosensitizing agents, both of which target lysosomes for photodamage, but via different photochemical pathways. Upon irradiation, the chlorin termed NPe6 forms singlet oxygen in high yield while the bacteriopheophorbide WST11 forms only oxygen radicals (in an aqueous environment). Photokilling efficacy by WST11 in cell culture was impaired when the atmospheric oxygen concentration was reduced from 20% to 1%, while photokilling by NPe6 was unaffected. Studies in a cell-free system revealed that the rates of photobleaching of these agents, as a function of the oxygenation level, were correlated with results described above. Moreover, the rate of formation of oxygen radicals by either agent was more sensitive to the level of oxygenation than was singlet oxygen formation by NPe6. These data indicate that the photochemical process that leads to oxygen radical formation is more dependent on the oxygenation level than is the pathway leading to formation of singlet oxygen. © 2013 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2013 The American Society of Photobiology.

  7. 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.; Karuthedath, Safakath; Polestshuk, Pavel M.; Savoie, Huguette; Flanagan, Keith J.; Sy, Cindy; Sitte, Elisabeth; Telitchko, Maxime; Laquai, Fré dé ric; Boyle, Ross W.; Senge, Mathias O.

    2017-01-01

    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.

  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. Spatial and temporal distribution of singlet oxygen in Lake Superior.

    Science.gov (United States)

    Peterson, Britt M; McNally, Ann M; Cory, Rose M; Thoemke, John D; Cotner, James B; McNeill, Kristopher

    2012-07-03

    A multiyear field study was undertaken on Lake Superior to investigate singlet oxygen ((1)O(2)) photoproduction. Specifically, trends within the lake were examined, along with an assessment of whether correlations existed between chromophoric dissolved organic matter (CDOM) characteristics and (1)O(2) production rates and quantum yields. Quantum yield values were determined and used to estimate noontime surface (1)O(2) steady-state concentrations ([(1)O(2)](ss)). Samples were subdivided into three categories based on their absorbance properties (a300): riverine, river-impacted, or open lake sites. Using calculated surface [(1)O(2)](ss), photochemical half-lives under continuous summer sunlight were calculated for cimetidine, a pharmaceutical whose reaction with (1)O(2) has been established, to be on the order of hours, days, and a week for the riverine, river-impacted, and open lake waters, respectively. Of the CDOM properties investigated, it was found that dissolved organic carbon (DOC) and a300 were the best parameters for predicting production rates of [(1)O(2)](ss). For example, given the correlations found, one could predict [(1)O(2)](ss) within a factor of 4 using a300 alone. Changes in the quantum efficiency of (1)O(2) production upon dilution of river water samples with lake water samples demonstrated that the CDOM found in the open lake is not simply diluted riverine organic matter. The open lake pool was characterized by low absorption coefficient, low fluorescence, and low DOC, but more highly efficient (1)O(2) production and predominates the Lake Superior system spatially. This study establishes that parameters that reflect the quantity of CDOM (e.g., a300 and DOC) correlate with (1)O(2) production rates, while parameters that characterize the absorbance spectrum (e.g., spectral slope coefficient and E2:E3) correlate with (1)O(2) production quantum yields.

  10. Efficient and selective singlet oxygen sensitized NIR luminescence of a neodymium(III) complex and its application in biological imaging

    Energy Technology Data Exchange (ETDEWEB)

    Lo, Wai-Sum [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Li, Hongguang [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Law, Ga-Lai, E-mail: ga-lai.law@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak, E-mail: bcwtwong@polyu.edu.hk [Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

    2016-01-15

    A responsive neodymium NIR emission ({sup 4}F{sub 3/2}→{sup 4}I{sub 11/2,} {sub 9/2}) was recorded upon binding with singlet oxygen (K{sub B}=1.79×10{sup 6} M{sup −1}) via the anthracene moiety. The motif ytterbium analog served as a negative control with no significant NIR enhancement/quenching with the addition of the same amount of singlet oxygen. Our complex was also found to react with {sup 1}O{sub 2} generated by a known photosensitizer TMPyP inside HeLa cells without inducing cell death and display no significant cytotoxicity. - Highlights: • A turn-on NIR-emissive {sup 1}O{sub 2} probe has been synthesized for potential biological applications. • It has a binding constant of 1.9×10{sup 6} M{sup −1} and the emission intensity has a 5-fold increase upon binding. • The probe was also found to quench singlet oxygen in vitro generated by known photosensitizer TMPyP.

  11. 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...... photosensitizer molecule conjugated to a selected DNA origami staple strand on an origami structure. We demonstrate a distance-dependent oxidation of organic moieties incorporated in specific positions on DNA origami by singlet oxygen produced from a single photosensitizer located at the center of each origami....

  12. 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.

  13. 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.

  14. 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.

  15. 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.

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

    Science.gov (United States)

    Graindorge, Dany; Martineau, Sylvain; Machon, Christelle; Arnoux, Philippe; Guitton, Jérôme; Francesconi, Stefania; Frochot, Céline; Sage, Evelyne; Girard, Pierre-Marie

    2015-01-01

    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. PMID:26485711

  17. Effects of the Oxygenation level on Formation of Different Reactive Oxygen Species During Photodynamic Therapy

    OpenAIRE

    Price, Michael; Heilbrun, Lance; Kessel, David

    2013-01-01

    We examined the effect of the oxygenation level on efficacy of two photosensitizing agents, both of which target lysosomes for photodamage but via different photochemical pathways. Upon irradiation, the chlorin termed NPe6 forms singlet oxygen in high yield while the bacteriopheophorbide WST11 forms only oxygen radicals (in an aqueous environment). Photokilling efficacy by WST11 in cell culture was impaired when the atmospheric oxygen concentration was reduced from 20% to 1%, while photokilli...

  18. 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

  19. Singlet oxygen-induced oxidation of alkylthiocarboxylic acids

    International Nuclear Information System (INIS)

    Celuch, M.; Pogocki, D.; Enache, M.

    2006-01-01

    Singlet oxygen ( 1 O 2 ) could be generated in biological systems by endogenous and exogenous processes (e.g. enzymatic and chemical reactions, UV or visible light in the presence of a sensitizer). Numerous data show that proteins are the major targets of 1 O 2 -induced damage in the living cells. In particular, reaction of 1 O 2 with thioether sulphur of methionine (Met) leads to the formation of persulphoxide >S (+) O-O (-) which is in equilibrium with superoxide radical-anion (O 2 ·- ) and respective sulphur-centered-radical-cation >S ·+ . In presented work, investigation the mechanisms of deprotonation and decarboxylation of the S ·+ - the irreversible processes, which competes with the formation of sulphoxide. Using thioethers dissevering by the number and positions of carboxylate groups it has been shown that efficiency of both decarboxylation and deprotonation could be influenced by various factors such as neighbouring group participation and environmental effects. The observed influence of carboxylate groups in β-position relative to the sulphur on the efficiency of decarboxylation suggests furthermore that they may also catalyze decarboxylation of α-positioned carboxylate in a manner similar to hydroxide anion

  20. 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...

  1. 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.

  2. 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.

  3. 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...

  4. 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...

  5. Intramolecular singlet-singlet energy transfer in antenna-substituted azoalkanes.

    Science.gov (United States)

    Pischel, Uwe; Huang, Fang; Nau, Werner M

    2004-03-01

    Two novel azoalkane bichromophores and related model compounds have been synthesised and photophysically characterised. Dimethylphenylsiloxy (DPSO) or dimethylnaphthylsiloxy (DNSO) serve as aromatic donor groups (antenna) and the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) as the acceptor. The UV spectral window of DBO (250-300 nm) allows selective excitation of the donor. Intramolecular singlet-singlet energy transfer to DBO is highly efficient and proceeds with quantum yields of 0.76 with DPSO and 0.99 with DNSO. The photophysical and spectral properties of the bichromophoric systems suggest that energy transfer occurs through diffusional approach of the donor and acceptor within a van der Waals contact at which the exchange mechanism is presumed to dominate. Furthermore, akin to the behaviour of electron-transfer systems in the Marcus inverted region, a rate of energy transfer 2.5 times slower was observed for the system with the more favourable energetics, i.e. singlet-singlet energy transfer from DPSO proceeded slower than from DNSO, although the process is more exergonic for DPSO (-142 kJ mol(-1) for DPSO versus-67 kJ mol(-1) for DNSO).

  6. Layered Double Hydroxides with Intercalated Porphyrins as Photofunctional Materials: Subtle Structural Changes Modify Singlet Oxygen Production

    Czech Academy of Sciences Publication Activity Database

    Lang, Kamil; Bezdička, Petr; Bourdelande, J.L.; Hernando, J.; Jirka, Ivan; Káfuňková, Eva; Kubát, Pavel; Mosinger, Jiří; Wagnerová, Dana Marie

    2007-01-01

    Roč. 19, č. 15 (2007), s. 3822-3829 ISSN 0897-4756 R&D Projects: GA ČR(CZ) GA203/06/1244; GA ČR GA203/07/1424; GA AV ČR KAN100500651 Grant - others:MESS(ES) CTQ2006-01040 Institutional research plan: CEZ:AV0Z40320502; CEZ:AV0Z40400503 Keywords : singlet oxygen Subject RIV: CA - Inorganic Chemistry Impact factor: 4.883, year: 2007

  7. A pulse radiolysis based singlet oxygen luminescence facility

    International Nuclear Information System (INIS)

    Gorman, A.A.; Hamblett, I.; Land, E.J.

    1989-01-01

    In this paper the authors report the first successful time-resolved detection of singlet oxygen, O 2 ( 1 Δ g ), luminescence using the pulse radiolysis technique. The use of this technique (a) to produce high concentrations of solute (S) triplet states in aerated benzene (B) via a combination of channels 1-4 and (b) to subsequently form O 2 ( 1 Δ g ) via channel 5 has already been described. The method complements direct pulsed laser excitation of S in that formation of 3 S*, and therefore of O 2 ( 1 Δ g ), is still efficient in those instances where intersystem crossing (channel 4) is unimportant. In the latter situation a laser-based experiment would require an additional light-absorbing sensitizer which could subsequently transfer triplet energy to high concentrations of S. Such experiments, certainly of a quantitative nature, are usually doomed to failure because of competitive light absorption problems. No such problems exist with pulse radiolysis, and the high available triplet energy of 3 B* (84 kcal mol -1 ) ensures that virtually any solute of interest, in the O 2 ( 1 Δ g ) context, will be efficiently promoted to its triplet state

  8. High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

    Science.gov (United States)

    Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

    2016-04-18

    One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. 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.

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

    International Nuclear Information System (INIS)

    Vargová, Veronika; Giménez, Rodrigo E.; Černocká, Hana; Trujillo, Diana Chito; Tulli, Fiorella; Zanini, Verónica I. Paz; Paleček, Emil; Borsarelli, Claudio D.; Ostatná, Veronika

    2016-01-01

    Oxidative damage of proteins results in changes of their structures and functions. In this work, the singlet oxygen ( 1 O 2 )-mediated oxidation of bovine serum albumin (BSA) and urease by blue-light photosensitization of the tris(2,2′-bipyridine)ruthenium(II) cation [Ru(bpy) 3 ] 2+ was studied by square wave voltammetry at glassy carbon electrode and by constant current chronopotentiometry at mercury electrode. Small changes in voltammetric oxidation Tyr and Trp peaks did not indicate significant changes in the BSA structure after photo-oxidation at carbon electrode. On the other hand chronopotentiometric peak H of BSA at HMDE increased during blue-light photosensitization, indicating that photo-oxidized BSA was more susceptible to the electric field-induced denaturation than non-oxidized native BSA. Similar results were obtained for urease, where enzymatic activity was also evaluated. The present results show the capability of label- and reagent-free electrochemical methods to detect oxidative changes in proteins. We believe that these methods will become important tools for detection of various protein damages.

  11. 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

  12. Deep inelastic singlet structure functions and scaling violation

    Energy Technology Data Exchange (ETDEWEB)

    Wen-zhu, Li; Bing-xun, Hu

    1984-02-01

    The flavour singlet structure functions of deep inelastic scattering processes can yield more decisive tests of QCD than the non-singlet. We give analytical expression for flavour singlet structure functions through analysing the lepton-nucleon deep inelastic scattering processes by means of QCD and using Jacobi polynomials. This expression contains 4 to 5 parameters and shows the changes of the singlet structure functions with x and Q/sup 2/ very well. In QCD leading order, the conclusion is in reasonable agreement with experimental data.

  13. 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.

  14. 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.

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

    Directory of Open Access Journals (Sweden)

    Athinoula L. Petrou

    2018-02-01

    Full Text Available 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.

  16. Investigation of the generation of singlet oxygen in ensembles of photoexcited silicon nanocrystals by electron paramagnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Konstantinova, E. A.; Demin, V. A.; Timoshenko, V. Yu.

    2008-01-01

    The generation of singlet oxygen is investigated and its concentration upon photoexcitation of silicon nanocrystals in porous silicon layers is determined using electron paramagnetic resonance spectroscopy. The relaxation times of spin centers, i.e., silicon dangling bonds, in vacuum and in an oxygen atmosphere in the dark and under illumination of the samples are measured for the first time. It is revealed that the spin-lattice relaxation in porous silicon is retarded as compared to that in a single-crystal substrate. From analyzing experimental data, a microscopic model is proposed for interaction of oxygen molecules in the triplet state and spin centers at the surface of silicon nanocrystals. The results obtained have demonstrated that porous silicon holds promise for the use as a photosensitizer of molecular oxygen in biomedical applications

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

    Science.gov (United States)

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

    2018-01-01

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

  18. Benchmarking singlet and triplet excitation energies of molecular semiconductors for singlet fission: Tuning the amount of HF exchange and adjusting local correlation to obtain accurate functionals for singlet-triplet gaps

    Science.gov (United States)

    Brückner, Charlotte; Engels, Bernd

    2017-01-01

    Vertical and adiabatic singlet and triplet excitation energies of molecular p-type semiconductors calculated with various DFT functionals and wave-function based approaches are benchmarked against MS-CASPT2/cc-pVTZ reference values. A special focus lies on the singlet-triplet gaps that are very important in the process of singlet fission. Singlet fission has the potential to boost device efficiencies of organic solar cells, but the scope of existing singlet-fission compounds is still limited. A computational prescreening of candidate molecules could enlarge it; yet it requires efficient methods accurately predicting singlet and triplet excitation energies. Different DFT formulations (Tamm-Dancoff approximation, linear response time-dependent DFT, Δ-SCF) and spin scaling schemes along with several ab initio methods (CC2, ADC(2)/MP2, CIS(D), CIS) are evaluated. While wave-function based methods yield rather reliable singlet-triplet gaps, many DFT functionals are shown to systematically underestimate triplet excitation energies. To gain insight, the impact of exact exchange and correlation is in detail addressed.

  19. Light-triggered liposomal cargo delivery platform incorporating photosensitizers and gold nanoparticles for enhanced singlet oxygen generation and increased cytotoxicity

    Science.gov (United States)

    Kautzka, Zofia; Clement, Sandhya; Goldys, Ewa M.; Deng, Wei

    2018-02-01

    We developed light-triggered liposomes incorporating gold nanoparticles and Rose Bengal (RB), a well-known photosensitizer used for photodynamic therapy. Singlet oxygen generated by these liposomes with 532 nm light illumination was characterized by adjusting the molar ratio of lipids and gold nanoparticles while keeping the amount of RB constant. Gold nanoparticles were found to enhance the singlet oxygen generation rate, with a maximum enhancement factor of 1.75 obtained for the molar ratio of HSPC: PE-NH2: gold of 57:5:17 compared with liposomes loaded with RB alone. The experimental results could be explained by the local electric field enhancement caused by gold nanoparticles. We further assessed cellular cytotoxicity of these liposomes by encapsulating an antitumor drug, doxorubicin (Dox); such Dox loaded liposomes were applied to human colorectal cancer cells, HCT116, and exposed to light. Gold-loaded liposomes containing RB and Dox where Dox release was triggered by light were found to exhibit higher cytotoxicity, compared to the liposomes loaded with RB and Dox alone. Our results indicate that gold-loaded liposomes incorporating photosensitizers may have improved therapeutic efficacy in photodynamic therapy and chemotherapy.

  20. 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

  1. 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...

  2. SU-E-T-191: First Principle Calculation of Quantum Yield in Photodynamic Therapy

    Energy Technology Data Exchange (ETDEWEB)

    Abolfath, R; Guo, F; Chen, Z; Nath, R [Yale New Haven Hospital, New Haven, CT (United States)

    2014-06-01

    Purpose: We present a first-principle method to calculate the spin transfer efficiency in oxygen induced by any photon fields especially in MeV energy range. The optical pumping is mediated through photosensitizers, e.g., porphyrin and/or ensemble of quantum dots. Methods: Under normal conditions, oxygen molecules are in the relatively non-reactive triplet state. In the presence of certain photosensitizer compounds such as porphyrins, electromagnetic radiation of specific wavelengths can excite oxygen to highly reactive singlet state. With selective uptake of photosensitizers by certain malignant cells, photon irradiation of phosensitized tumors can lead to selective killing of cancer cells. This is the basis of photodynamic therapy (PDT). Despite several attempts, PDT has not been clinically successful except in limited superficial cancers. Many parameters such as photon energy, conjugation with quantum dots etc. can be potentially combined with PDT in order to extend the role of PDT in cancer management. The key quantity for this optimization is the spin transfer efficiency in oxygen by any photon field. The first principle calculation model presented here, is an attempt to fill this need. We employ stochastic density matrix description of the quantum jumps and the rate equation methods in quantum optics based on Markov/Poisson processes and calculate time evolution of the population of the optically pumped singlet oxygen. Results: The results demonstrate the feasibility of our model in showing the dependence of the optical yield in generating spin-singlet oxygen on the experimental conditions. The adjustable variables can be tuned to maximize the population of the singlet oxygen hence the efficacy of the photodynamic therapy. Conclusion: The present model can be employed to fit and analyze the experimental data and possibly to assist researchers in optimizing the experimental conditions in photodynamic therapy.

  3. Atomic Oxygen Erosion Yield Dependence Upon Texture Development in Polymers

    Science.gov (United States)

    Banks, Bruce A.; Loftus, Ryan J.; Miller, Sharon K.

    2016-01-01

    The atomic oxygen erosion yield (volume of a polymer that is lost due to oxidation per incident atom) of polymers is typically assumed to be reasonably constant with increasing fluence. However polymers containing ash or inorganic pigments, tend to have erosion yields that decrease with fluence due to an increasing presence of protective particles on the polymer surface. This paper investigates two additional possible causes for erosion yields of polymers that are dependent upon atomic oxygen. These are the development of surface texture which can cause the erosion yield to change with fluence due to changes in the aspect ratio of the surface texture that develops and polymer specific atomic oxygen interaction parameters. The surface texture development under directed hyperthermal attack produces higher aspect ratio surface texture than isotropic thermal energy atomic oxygen attack. The fluence dependence of erosion yields is documented for low Kapton H (DuPont, Wilmington, DE) effective fluences for a variety of polymers under directed hyperthermal and isotropic thermal energy attack.

  4. 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

  5. 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.

  6. 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

  7. First-Principle Characterization for Singlet Fission Couplings.

    Science.gov (United States)

    Yang, Chou-Hsun; Hsu, Chao-Ping

    2015-05-21

    The electronic coupling for singlet fission, an important parameter for determining the rate, has been found to be too small unless charge-transfer (CT) components were introduced in the diabatic states, mostly through perturbation or a model Hamiltonian. In the present work, the fragment spin difference (FSD) scheme was generalized to calculate the singlet fission coupling. The largest coupling strength obtained was 14.8 meV for two pentacenes in a crystal structure, or 33.7 meV for a transition-state structure, which yielded a singlet fission lifetime of 239 or 37 fs, generally consistent with experimental results (80 fs). Test results with other polyacene molecules are similar. We found that the charge on one fragment in the S1 diabatic state correlates well with FSD coupling, indicating the importance of the CT component. The FSD approach is a useful first-principle method for singlet fission coupling, without the need to include the CT component explicitly.

  8. Singlet-triplet annihilation in single LHCII complexes

    NARCIS (Netherlands)

    Gruber, J.M.; Chmeliov, J.; Kruger, T.P.J.; Valkunas, L.; van Grondelle, R.

    2015-01-01

    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

  9. Singlet Oxygen Production by Illuminated Road Dust and Winter Street Sweepings

    Science.gov (United States)

    Schneider, S.; Gan, L.; Gao, S.; Hoy, K. S.; Kwasny, J. R.; Styler, S. A.

    2017-12-01

    Road dust is an important urban source of primary particulate matter, especially in cities where sand and other traction materials are applied to roadways in winter. Although the composition and detrimental health effects of road dust are reasonably well characterized, little is currently known regarding its chemical behaviour. Motivated by our previous work, in which we showed that road dust is a photochemical source of singlet oxygen (1O2), we investigated 1O2 production by bulk winter street sweepings and by road dust collected in a variety of urban, industrial, and suburban locations in both autumn and spring. In all cases, the production of 1O2 by road dust was greater than that by Arizona test dust and desert-sourced dust, which highlights the unique photochemical environment afforded by this substrate. Mechanistically, we observed correlations between 1O2 production and the UV absorbance properties of dust extracts, which suggests the involvement of chromophoric dissolved organic matter in the observed photochemistry. Taken together, this work provides evidence that road dust-mediated photochemistry may influence the environmental lifetime of pollutants that react via 1O2-mediated pathways, including polycyclic aromatic hydrocarbons.

  10. Factors influencing the regioselectivity of the oxidation of asymmetric secondary amines with singlet oxygen.

    Science.gov (United States)

    Ushakov, Dmitry B; Plutschack, Matthew B; Gilmore, Kerry; Seeberger, Peter H

    2015-04-20

    Aerobic amine oxidation is an attractive and elegant process for the α functionalization of amines. However, there are still several mechanistic uncertainties, particularly the factors governing the regioselectivity of the oxidation of asymmetric secondary amines and the oxidation rates of mixed primary amines. Herein, it is reported that singlet-oxygen-mediated oxidation of 1° and 2° amines is sensitive to the strength of the α-C-H bond and steric factors. Estimation of the relative bond dissociation energy by natural bond order analysis or by means of one-bond C-H coupling constants allowed the regioselectivity of secondary amine oxidations to be explained and predicted. In addition, the findings were utilized to synthesize highly regioselective substrates and perform selective amine cross-couplings to produce imines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Eclipta yellow vein virus enhances chlorophyll destruction, singlet oxygen production and alters endogenous redox status in Andrographis paniculata.

    Science.gov (United States)

    Khan, Asifa; Luqman, Suaib; Masood, Nusrat; Singh, Dhananjay Kumar; Saeed, Sana Tabanda; Samad, Abdul

    2016-07-01

    The infection of Eclipta yellow vein virus [EcYVV-IN, Accession No. KC476655], recently reported for the first time, on Andrographis paniculata was studied for redox-mediated alteration mechanism in infected plants. A. paniculata, an important medicinal plant, is used in traditional Indian, Chinese and modern system of medicine. Andrographolide, one of the foremost components of this plant, is known for its varied pharmacological properties. Our investigation provides insight into the effect of virus-induced changes in the singlet oxygen quenching due to the alteration in pigment content (chlorophyll and carotenoids) as well as activation of plant secondary metabolism along with defense activation leading to changes in enzymatic and non-enzymatic redox status. Due to infection, a reduction in carotenoid content was observed which leads to reduced quenching of singlet oxygen. An increased level of enzymatic (SOD and APX) and non-enzymatic antioxidant (DPPH, FRAP, RP, NO, TAC and TP) activities were also observed in virus-infected plants with a positive correlation (>0.9). However, CAT activity was diminished which could be either due to its proteolytic degradation or inactivation by superoxide anions (O(2-.)), NO or peroxynitrite radicals. A significant (p < 0.05) increase in total phenolic content was observed in the infected plants while no considerable difference was seen in the total flavonoid content. Our results highlighted the alteration in redox status caused by virus-induced biotic stress on the plants and could be useful for understanding the after effects of viral infection This study could also be helpful in developing biomimetic methods for improving the production of secondary metabolites of pharmaceutical importance. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  12. Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II.

    Directory of Open Access Journals (Sweden)

    Vinay Pathak

    Full Text Available Singlet oxygen (1O2 is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII. Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex.

  13. Singlet oxygen and ROS in a new light: low-dose subcellular photodynamic treatment enhances proliferation at the single cell level.

    Science.gov (United States)

    Blázquez-Castro, Alfonso; Breitenbach, Thomas; Ogilby, Peter R

    2014-09-01

    Two-photon excitation of a sensitizer with a focused laser beam was used to create a spatially-localized subcellular population of reactive oxygen species, ROS, in single HeLa cells. The sensitizer used was protoporphyrin IX, PpIX, endogenously derived from 5-aminolevulinic acid delivered to the cells. Although we infer that singlet oxygen, O2(a(1)Δg), is one ROS produced upon irradiation of PpIX under these conditions, it is possible that the superoxide ion, O2(-˙), may also play a role in this system. With a "high" dose of PpIX-sensitized ROS, the expected death of the cell was observed. However, under "low dose" conditions, clear signs of cell proliferation were observed. The present results facilitate studies of ROS-mediated signalling in imaging-based single cell experiments.

  14. Protection by DABCO against inactivation of transforming DNA by near-ultraviolet light: action spectra and implications for involvement of singlet oxygen

    International Nuclear Information System (INIS)

    Peak, J.G.; Peak, M.J.; Foote, C.S.

    1981-01-01

    Diazobicyclo (2.2.2) octane (DABCO) protects the genetic activity of purified transforming Bacillus subtilis DNA against inactivation by near-, but not far-, UV light. The maximum dose-modifying factor is 0.4, at 0.1 M DABCO. Maximal protection is at about 350 nm and no protection occurs below 313 nm. The spectrum for protection is similar to that described for 2-aminoethylisothiouronium bromide hydrobromide. The relevance of these observations with regard to the role of singlet oxygen in near-UV effects is discussed. (author)

  15. 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.

  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. [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

  17. Oxygen toxicity

    Directory of Open Access Journals (Sweden)

    C. A. van der Westhuizen

    1990-07-01

    Full Text Available Oxygen has been discovered about 200 years ago. Since then the vital physiological involvement of oxygen in various biologi­cal processes, mainly energy production, has been established. However, in the body molecular oxygen can be converted to toxic oxygen metabolites such as superoxide anion, hydrogen peroxide, the hydroxyl radical and singlet oxygen. These toxic metabolites are produced mainly in the mitochondria, plasma membranes and endoplasmic reticulum.

  18. Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

    KAUST Repository

    Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; McCulloch, Iain; Rumbles, Garry; Johnson, Justin C.

    2017-01-01

    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.

  19. 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.

  20. 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 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.

  1. 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.

  2. Decontamination of chemical-warfare agent simulants by polymer surfaces doped with the singlet oxygen generator zinc octaphenoxyphthalocyanine.

    Science.gov (United States)

    Gephart, Raymond T; Coneski, Peter N; Wynne, James H

    2013-10-23

    Using reactive singlet oxygen (1O2), the oxidation of chemical-warfare agent (CWA) simulants has been demonstrated. The zinc octaphenoxyphthalocyanine (ZnOPPc) complex was demonstrated to be an efficient photosensitizer for converting molecular oxygen (O2) to 1O2 using broad-spectrum light (450-800 nm) from a 250 W halogen lamp. This photosensitization produces 1O2 in solution as well as within polymer matrices. The oxidation of 1-naphthol to naphthoquinone was used to monitor the rate of 1O2 generation in the commercially available polymer film Hydrothane that incorporates ZnOPPc. Using electrospinning, nanofibers of ZnOPPc in Hydrothane and polycarbonate were formed and analyzed for their ability to oxidize demeton-S, a CWA simulant, on the surface of the polymers and were found to have similar reactivity as their corresponding films. The Hydrothane films were then used to oxidize CWA simulants malathion, 2-chloroethyl phenyl sulfide (CEPS), and 2-chloroethyl ethyl sulfide (CEES). Through this oxidation process, the CWA simulants are converted into less toxic compounds, thus decontaminating the surface using only O2 from the air and light.

  3. 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 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.

  4. Singlet oxygen autoxidation of vegetable oils: evidences for lack of synergy between β-carotene and tocopherols.

    Science.gov (United States)

    Smyk, Bogdan

    2015-09-01

    The synergy between β-carotene and tocopherols--antioxidants protecting oils from oxidation, was analyzed in a model system. The model used stripped borage and evening primrose oils. A chlorophyll extract, β-carotene and one of the tocopherols were added together or separately to the oils. Oil oxidation was initiated by singlet oxygen that was produced by chlorophylls irradiated with the use of a xenon lamp equipped with the cut-off 600 nm filter. Experiments were carried out at two mole ratios of tocopherols to β-carotene, i.e. at 1:1 and 23:1. Analyses were performed using absorption and fluorescence spectra in the UV+Vis region. The results demonstrated an antagonistic action of the antioxidants. The protective effect of unsaturated fatty acids was significantly better in the case of β-carotene compared to the tocopherols. Furthermore, tocopherols were less effective in protecting the oils in the presence of β-carotene than without it. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Slow light enhanced singlet exciton fission solar cells with a 126% yield of electrons per photon

    International Nuclear Information System (INIS)

    Thompson, Nicholas J.; Congreve, Daniel N.; Baldo, Marc A.; Goldberg, David; Menon, Vinod M.

    2013-01-01

    Singlet exciton fission generates two triplet excitons per absorbed photon. It promises to increase the power extracted from sunlight without increasing the number of photovoltaic junctions in a solar cell. We demonstrate solar cells with an external quantum efficiency of 126% by enhancing absorption in thin films of the singlet exciton fission material pentacene. The device structure exploits the long photon dwell time at the band edge of a distributed Bragg reflector to achieve enhancement over a broad range of angles. Measuring the reflected light from the solar cell establishes a lower bound of 137% for the internal quantum efficiency

  6. Slow light enhanced singlet exciton fission solar cells with a 126% yield of electrons per photon

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Nicholas J.; Congreve, Daniel N.; Baldo, Marc A., E-mail: vmenon@qc.cuny.edu, E-mail: baldo@mit.edu [Energy Frontier Research Center for Excitonics, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Goldberg, David; Menon, Vinod M., E-mail: vmenon@qc.cuny.edu, E-mail: baldo@mit.edu [Department of Physics, Queens College and Graduate Center, The City University of New York, Flushing, New York 11367 (United States)

    2013-12-23

    Singlet exciton fission generates two triplet excitons per absorbed photon. It promises to increase the power extracted from sunlight without increasing the number of photovoltaic junctions in a solar cell. We demonstrate solar cells with an external quantum efficiency of 126% by enhancing absorption in thin films of the singlet exciton fission material pentacene. The device structure exploits the long photon dwell time at the band edge of a distributed Bragg reflector to achieve enhancement over a broad range of angles. Measuring the reflected light from the solar cell establishes a lower bound of 137% for the internal quantum efficiency.

  7. 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

  8. Modeling the oxygen microheterogeneity of tumors for photodynamic therapy dosimetry

    Science.gov (United States)

    Pogue, Brian W.; Paulsen, Keith D.; O'Hara, Julia A.; Hoopes, P. Jack; Swartz, Harold

    2000-03-01

    Photodynamic theory of tumors uses optical excitation of a sensitizing drug within tissue to produce large deposits of singlet oxygen, which are thought to ultimately cause the tumor destruction. Predicting dose deposition of singlet oxygen in vivo is challenging because measurement of this species in vivo is not easily achieved. But it is possible to follow the concentration of oxygen in vivo, and so measuring the oxygen concentration transients during PDT may provide a viable method of estimating the delivered dose of singlet oxygen. However modeling the microscopic heterogeneity of the oxygen distribution within a tumor is non-trivial, and predicting the microscopic dose deposition requires further study, but this study present the framework and initial calibration needed or modeling oxygen transport in complex geometries. Computational modeling with finite elements provides a versatile structure within which oxygen diffusion and consumption can be modeled within realistic tissue geometries. This study develops the basic tools required to simulate a tumor region, and examines the role of (i) oxygen supply and consumption rates, (ii) inter- capillary spacing, (iii) photosensitizer distribution, and (iv) differences between simulated tumors and those derived directly from histology. The result of these calculations indicate that realistic tumor tissue capillary networks can be simulated using the finite element method, without excessive computational burden for 2D regions near 1 mm2, and 3D regions near 0.1mm3. These simulations can provide fundamental information about tissue and ways to implement appropriate oxygen measurements. These calculations suggest that photodynamic therapy produces the majority of singlet oxygen in and near the blood vessels, because these are the sites of highest oxygen tension. These calculations support the concept that tumor vascular regions are the major targets for PDT dose deposition.

  9. Absolute quantum yield measurements for the formation of oxygen ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. The dynamics of formation of oxygen atoms after UV photoexcitation of .... The SO2 pressure in the cell was typically 30–55 mTorr (monitored by an MKS .... With this value the quantum yield for O(3P) formation could be calculated to.

  10. Atomic Oxygen Erosion Yield Predictive Tool for Spacecraft Polymers in Low Earth Orbit

    Science.gov (United States)

    Bank, Bruce A.; de Groh, Kim K.; Backus, Jane A.

    2008-01-01

    A predictive tool was developed to estimate the low Earth orbit (LEO) atomic oxygen erosion yield of polymers based on the results of the Polymer Erosion and Contamination Experiment (PEACE) Polymers experiment flown as part of the Materials International Space Station Experiment 2 (MISSE 2). The MISSE 2 PEACE experiment accurately measured the erosion yield of a wide variety of polymers and pyrolytic graphite. The 40 different materials tested were selected specifically to represent a variety of polymers used in space as well as a wide variety of polymer chemical structures. The resulting erosion yield data was used to develop a predictive tool which utilizes chemical structure and physical properties of polymers that can be measured in ground laboratory testing to predict the in-space atomic oxygen erosion yield of a polymer. The properties include chemical structure, bonding information, density and ash content. The resulting predictive tool has a correlation coefficient of 0.914 when compared with actual MISSE 2 space data for 38 polymers and pyrolytic graphite. The intent of the predictive tool is to be able to make estimates of atomic oxygen erosion yields for new polymers without requiring expensive and time consumptive in-space testing.

  11. 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

    . The spiking pattern was altered significantly, reflected by changes in spike threshold, frequency and tendency for fast APs to be followed by a plateau phase. These effects were correlated with the intensity and/or duration of illumination. Since we have previously documented that the lifetime and diffusion...... range of singlet oxygen are very small, its effects will be restricted. The intra-membrane generated 1O2 alters the composition of the lipid and also proteins or channels. This is reflected both in the immediate response to low irradiation-dose and in formation of long plateaus, which could be caused...

  12. 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

    The radiation chemistry of oxygen discharges is better-studied system. The discharges were made by irradiation with high energy helium and lithium ions created by a neutron-induced reaction in boron (10). A detailed numerical model and a simplified analytical model of oxygen radiolysis have been developed to interpret the data. A summary of the data on the ozone yield from irradiation of He-O2, Ne-O2 and Ar-O2 is presented. Dose rates are also indicated. The present work appears to be the first to measure the steady state ozone concentration in noble gas-oxygen discharges and the effect of SF6 on this steady state concentration. 106 refs

  13. 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.

  14. MISSE 2 PEACE Polymers Experiment Atomic Oxygen Erosion Yield Error Analysis

    Science.gov (United States)

    McCarthy, Catherine E.; Banks, Bruce A.; deGroh, Kim, K.

    2010-01-01

    Atomic oxygen erosion of polymers in low Earth orbit (LEO) poses a serious threat to spacecraft performance and durability. To address this, 40 different polymer samples and a sample of pyrolytic graphite, collectively called the PEACE (Polymer Erosion and Contamination Experiment) Polymers, were exposed to the LEO space environment on the exterior of the International Space Station (ISS) for nearly 4 years as part of the Materials International Space Station Experiment 1 & 2 (MISSE 1 & 2). The purpose of the PEACE Polymers experiment was to obtain accurate mass loss measurements in space to combine with ground measurements in order to accurately calculate the atomic oxygen erosion yields of a wide variety of polymeric materials exposed to the LEO space environment for a long period of time. Error calculations were performed in order to determine the accuracy of the mass measurements and therefore of the erosion yield values. The standard deviation, or error, of each factor was incorporated into the fractional uncertainty of the erosion yield for each of three different situations, depending on the post-flight weighing procedure. The resulting error calculations showed the erosion yield values to be very accurate, with an average error of 3.30 percent.

  15. Atomic Oxygen Erosion Yield Prediction for Spacecraft Polymers in Low Earth Orbit

    Science.gov (United States)

    Banks, Bruce A.; Backus, Jane A.; Manno, Michael V.; Waters, Deborah L.; Cameron, Kevin C.; deGroh, Kim K.

    2009-01-01

    The ability to predict the atomic oxygen erosion yield of polymers based on their chemistry and physical properties has been only partially successful because of a lack of reliable low Earth orbit (LEO) erosion yield data. Unfortunately, many of the early experiments did not utilize dehydrated mass loss measurements for erosion yield determination, and the resulting mass loss due to atomic oxygen exposure may have been compromised because samples were often not in consistent states of dehydration during the pre-flight and post-flight mass measurements. This is a particular problem for short duration mission exposures or low erosion yield materials. However, as a result of the retrieval of the Polymer Erosion and Contamination Experiment (PEACE) flown as part of the Materials International Space Station Experiment 2 (MISSE 2), the erosion yields of 38 polymers and pyrolytic graphite were accurately measured. The experiment was exposed to the LEO environment for 3.95 years from August 16, 2001 to July 30, 2005 and was successfully retrieved during a space walk on July 30, 2005 during Discovery s STS-114 Return to Flight mission. The 40 different materials tested (including Kapton H fluence witness samples) were selected specifically to represent a variety of polymers used in space as well as a wide variety of polymer chemical structures. The MISSE 2 PEACE Polymers experiment used carefully dehydrated mass measurements, as well as accurate density measurements to obtain accurate erosion yield data for high-fluence (8.43 1021 atoms/sq cm). The resulting data was used to develop an erosion yield predictive tool with a correlation coefficient of 0.895 and uncertainty of +/-6.3 10(exp -25)cu cm/atom. The predictive tool utilizes the chemical structures and physical properties of polymers to predict in-space atomic oxygen erosion yields. A predictive tool concept (September 2009 version) is presented which represents an improvement over an earlier (December 2008) version.

  16. 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.

  17. Singlet fission in pentacene dimers

    Science.gov (United States)

    Zirzlmeier, Johannes; Lehnherr, Dan; Coto, Pedro B.; Chernick, Erin T.; Casillas, Rubén; Basel, Bettina S.; Thoss, Michael; Tykwinski, Rik R.; Guldi, Dirk M.

    2015-01-01

    Singlet fission (SF) has the potential to supersede the traditional solar energy conversion scheme by means of boosting the photon-to-current conversion efficiencies beyond the 30% Shockley–Queisser limit. Here, we show unambiguous and compelling evidence for unprecedented intramolecular SF within regioisomeric pentacene dimers in room-temperature solutions, with observed triplet quantum yields reaching as high as 156 ± 5%. Whereas previous studies have shown that the collision of a photoexcited chromophore with a ground-state chromophore can give rise to SF, here we demonstrate that the proximity and sufficient coupling through bond or space in pentacene dimers is enough to induce intramolecular SF where two triplets are generated on one molecule. PMID:25858954

  18. Novel approaches to singlet oxygen photosensitization in the nano- and bio-era

    OpenAIRE

    Planas Marquès, Oriol

    2017-01-01

    En aquesta tesis es detallen noves aproximacions nano- i biomoleculars amb l’objectiu de millorar la fotosensibilització i detecció d’oxigen singlet en medi biològic. En primer lloc es presenta una nova reacció fluoro- i cromogènica pel marcatge de proteïnes i nanopartícules amb derivats de porficè. Concretament, la reacció de porficens isotiocianat amb amines primàries i secundaries generen 2-aminotiazolo[4,5-c]poricè derivats amb un desplaçament concomitant en els seus espectres d’absor...

  19. 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

    Energy Technology Data Exchange (ETDEWEB)

    Vagin, N. P.; Ionin, A. A., E-mail: aion@sci.lebedev.ru; Kochetov, I. V.; Napartovich, A. P.; Sinitsyn, D. V., E-mail: dsinit@sci.lebedev.ru; Yuryshev, N. N. [Russian Academy of Sciences, Lebedev Physical Institute (Russian Federation)

    2017-03-15

    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{sub 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.

  20. 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.

  1. 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

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

    Science.gov (United States)

    Giménez, Rodrigo E; Vargová, Veronika; Rey, Valentina; Turbay, M Beatriz Espeche; Abatedaga, Inés; Morán Vieyra, Faustino E; Paz Zanini, Verónica I; Mecchia Ortiz, Juan H; Katz, Néstor E; Ostatná, Veronika; Borsarelli, Claudio D

    2016-05-01

    Singlet molecular oxygen ((1)O2) contributes to protein damage triggering biophysical and biochemical changes that can be related with aging and oxidative stress. Serum albumins, such as bovine serum albumin (BSA), are abundant proteins in blood plasma with different biological functions. This paper presents a kinetic and spectroscopic study of the (1)O2-mediated oxidation of BSA using the tris(2,2'-bipyridine)ruthenium(II) cation [Ru(bpy)3](2+) as sensitizer. BSA quenches efficiently (1)O2 with a total (chemical+physical interaction) rate constant kt(BSA)=7.3(±0.4)×10(8)M(-1)s(-1), where the chemical pathway represented 37% of the interaction. This efficient quenching by BSA indicates the participation of several reactive residues. MALDI-TOF MS analysis of intact BSA confirmed that after oxidation by (1)O2, the mass protein increased the equivalent of 13 oxygen atoms. Time-resolved emission spectra analysis of BSA established that Trp residues were oxidized to N'-formylkynurenine, being the solvent-accessible W134 preferentially oxidized by (1)O2 as compared with the buried W213. MS confirmed oxidation of at least two Tyr residues to form dihydroxyphenylalanine, with a global reactivity towards (1)O2 six-times lower than for Trp residues. Despite the lack of MS evidences, kinetic and chemical analysis also suggested that residues other than Trp and Tyr, e.g. Met, must react with (1)O2. Modeling of the 3D-structure of BSA indicated that the oxidation pattern involves a random distribution of (1)O2 into BSA; allowing also the interaction of (1)O2 with buried residues by its diffusion from the bulk solvent through interconnected internal hydrophilic and hydrophobic grooves. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. 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

  4. 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

  5. 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

  6. 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.

  7. Improved photocatalytic degradation of Orange G using hybrid nanofibers

    Energy Technology Data Exchange (ETDEWEB)

    Ledwaba, Mpho; Masilela, Nkosiphile; Nyokong, Tebello; Antunes, Edith, E-mail: ebeukes@uwc.ac.za [Rhodes University, Department of Chemistry (South Africa)

    2017-05-15

    Functionalised electrospun polyamide-6 (PA-6) nanofibres incorporating gadolinium oxide nanoparticles conjugated to zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) as the sensitizer were prepared for the photocatalytic degradation of Orange G. Fibres incorporating the phthalocyanine alone or a mixture of the nanoparticles and phthalocyanine were also generated. The singlet oxygen-generating ability of the sensitizer was shown to be maintained within the fibre mat, with the singlet oxygen quantum yields increasing upon incorporation of the magnetic nanoparticles. Consequently, the rate of the photodegradation of Orange G was observed to increase with an increase in singlet oxygen quantum yield. A reduction in the half-lives for the functionalised nanofibres was recorded in the presence of the magnetic nanoparticles, indicating an improvement in the efficiency of the degradation process.

  8. 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

  9. Light dependence of quantum yields for PSII charge separation and oxygen evolution in eucaryotic algae

    NARCIS (Netherlands)

    Flameling, I.A.; Kromkamp, J.C.

    1998-01-01

    Quantum yields of photosystem II (PSII) charge separation (Phi(P)) and oxygen production (Phi(O2)) were determined by simultaneous measurements of oxygen production and variable fluorescence in four different aquatic microalgae representing three different taxonomic groups: the freshwater alga

  10. 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.

  11. Experimental confirmation of photon-induced spin-flip transitions in helium via triplet metastable yield spectra

    International Nuclear Information System (INIS)

    Rubensson, Jan-Erik; Moise, Angelica; Richter, Robert; Mihelic, Andrej; Bucar, Klemen; Zitnik, Matjaz

    2010-01-01

    Doubly excited states below the N=2 ionization threshold are populated by exciting helium atoms in a supersonic beam with monochromatized synchrotron radiation. The fluorescence decay of these states triggers a radiative cascade back to the ground state with large probability to populate long lived singlet and triplet helium metastable states. The yield of metastables is measured using a multichannel plate detector after the beam has passed a singlet-quenching discharge lamp. The variation of the yield observed with the lamp switched on or off is related to the triplet-singlet mixing of the doubly excited states.

  12. Effects of calcium paste as a seed coat on growth, yield and ...

    African Journals Online (AJOL)

    MK

    2012-09-25

    Sep 25, 2012 ... damages plant cell through production of reactive oxygen species including superoxide, hydrogen peroxide, hydroxyl anions and singlet oxygen (Hameed et al.,. 2008). Efforts have ..... biochemical adaptation to conserve energy by stopping ... their involvement in cell respiration, photosynthesis, oxidative ...

  13. A spin exchange model for singlet fission

    Science.gov (United States)

    Yago, Tomoaki; Wakasa, Masanobu

    2018-03-01

    Singlet fission has been analyzed with the Dexter model in which electron exchange occurs between chromophores, conserving the spin for each electron. In the present study, we propose a spin exchange model for singlet fission. In the spin exchange model, spins are exchanged by the exchange interaction between two electrons. Our analysis with simple spin functions demonstrates that singlet fission is possible by spin exchange. A necessary condition for spin exchange is a variation in exchange interactions. We also adapt the spin exchange model to triplet fusion and triplet energy transfer, which often occur after singlet fission in organic solids.

  14. 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.

  15. Dependence of Initial Oxygen Concentration on Ozone Yield Using Inductive Energy Storage System Pulsed Power Generator

    Science.gov (United States)

    Go, Tomio; Tanaka, Yasushi; Yamazaki, Nobuyuki; Mukaigawa, Seiji; Takaki, Koichi; Fujiwara, Tamiya

    Dependence of initial oxygen concentration on ozone yield using streamer discharge reactor driven by an inductive energy storage system pulsed power generator is described in this paper. Fast recovery type diodes were employed as semiconductor opening switch to interrupt a circuit current within 100 ns. This rapid current change produced high-voltage short pulse between a secondary energy storage inductor. The repetitive high-voltage short pulse was applied to a 1 mm diameter center wire electrode placed in a cylindrical pulse corona reactor. The streamer discharge successfully occurred between the center wire electrode and an outer cylinder ground electrode of 2 cm inner diameter. The ozone was produced with the streamer discharge and increased with increasing pulse repetition rate. The ozone yield changed in proportion to initial oxygen concentration contained in the injected gas mixture at 800 ns forward pumping time of the current. However, the decrease of the ozone yield by decreasing oxygen concentration in the gas mixture at 180 ns forward pumping time of the current was lower than the decrease at 800 ns forward pumping time of the current. This dependence of the initial oxygen concentration on ozone yield at 180 ns forward pumping time is similar to that of dielectric barrier discharge reactor.

  16. 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

  17. Lithium-Oxygen Batteries: At a Crossroads?

    DEFF Research Database (Denmark)

    Vegge, Tejs; García Lastra, Juan Maria; Siegel, Donald Jason

    2017-01-01

    In this current opinion, we critically review and discuss some of the most important recent findings in the field of rechargeable lithium-oxygen batteries. We discuss recent discoveries like the evolution of reactive singlet oxygen and the use of organic additives to bypass reactive LiO2 reaction...... intermediates, and their possible implications on the potential for commercialization of lithium-oxygen batteries. Finally, we perform a critical assessment of lithium-superoxide batteries and the reversibility of lithium-hydroxide batteries....

  18. 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

  19. The formal combination of three singlet biradicaloid entities to a singlet hexaradicaloid metalloid Ge14[Si(SiMe3)3]5[Li(THF)2]3 cluster.

    Science.gov (United States)

    Schenk, Christian; Kracke, Andreas; Fink, Karin; Kubas, Adam; Klopper, Wim; Neumaier, Marco; Schnöckel, Hansgeorg; Schnepf, Andreas

    2011-03-02

    The reaction of GeBr with LiSi(SiMe(3))(3) leads to the metalloid cluster compound [(THF)(2)Li](3)Ge(14)[Si(SiMe(3))(3)](5) (1). After the introduction of a first cluster of this type, in which 14 germanium atoms form an empty polyhedron, [(THF)(2)Li](3)Ge(14)[Ge(SiMe(3))(3)](5) (2), we present here further investigations on 1 to obtain preliminary insight into its chemical and bonding properties. The molecular structure of 1 is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge(14) polyhedron is further examined by quantum chemical calculations, which indicate that three singlet biradicaloid entities formally combine to yield the singlet hexaradicaloid character of 1. Moreover, the initial reactions of 1 after elimination of the [Li(THF)(2)](+) groups by chelating ligands (e.g., TMEDA or 12-crown-4) are presented. Collision induced dissociation experiments in the gas phase, employing FT-ICR mass spectrometry, lead to the elimination of the singlet biradicaloid Ge(5)H(2)[Si(SiMe(3))(3)](2) cluster. The unique multiradicaloid bonding character of the metalloid cluster 1 might be used as a model for reactions and properties in the field of surface science and nanotechnology.

  20. Oxygen diffusion in bilayer polymer films

    DEFF Research Database (Denmark)

    Poulsen, Lars; Zebger, Ingo; Tofte, Jannik Pentti

    2004-01-01

    Experiments to quantify oxygen diffusion have been performed on polymer samples in which a film of poly(ethylene-co-norbornene) was cast onto a film of polystyrene which, in turn, was cast onto an oxygen-impermeable substrate. In the technique employed, the time evolution of oxygen transport...... 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...

  1. 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

  2. Spin nematics next to spin singlets

    Science.gov (United States)

    Yokoyama, Yuto; Hotta, Chisa

    2018-05-01

    We provide a route to generate nematic order in a spin-1/2 system. Unlike the well-known magnon-binding mechanism, our spin nematics requires neither the frustration effect nor spin polarization in a high field or in the vicinity of a ferromagnet, but instead appears next to the spin singlet phase. We start from a state consisting of a quantum spin-1/2 singlet dimer placed on each site of a triangular lattice, and show that interdimer ring exchange interactions efficiently dope the SU(2) triplets that itinerate and interact, easily driving a stable singlet state to either Bose-Einstein condensates or a triplet crystal, some hosting a spin nematic order. A variety of roles the ring exchange serves includes the generation of a bilinear-biquadratic interaction between nearby triplets, which is responsible for the emergent nematic order separated from the singlet phase by a first-order transition.

  3. Axially substituted silicon (IV) tetrapyrazinoporphyrazines: Synthesis, characterization and investigation of photophysicochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Chang Young; Park, Jong Min; Song, Cheol Jun; Jaung, Jae Yun, E-mail: jjy1004@hanyang.ac.kr

    2016-02-15

    A series of silicon tetrapyrazinoporphyrazine (SiPz) complexes, conjugated with various substituents at their axial positions, were synthesized into non-aggregated structures in organic solvents. The UV–vis spectra of the SiPz complexes maintained a strong and sharp Q-band, which is an archetypal characteristic of non-aggregated phthalocyanines (Pcs), in various organic solvents under high concentrations. In addition, the SiPz complexes with axial alkyl groups had high fluorescence quantum yields and singlet oxygen quantum yields. However, the SiPz complexes with axial aniline groups had very low fluorescence quantum yields and singlet oxygen quantum yields due to the quenching ability of the aniline group.

  4. 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.; Wang, Hanting; Gutié rrez, Leonardo A.; Romero-Maraccini, Ofelia C.; Niu, Xi-Zhi; Gin, Karina; Croue, Jean-Philippe; Nguyen, Thanh Ha

    2013-01-01

    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.

  5. 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.

  6. Complex singlet extension of the standard model

    International Nuclear Information System (INIS)

    Barger, Vernon; McCaskey, Mathew; Langacker, Paul; Ramsey-Musolf, Michael; Shaughnessy, Gabe

    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.

  7. Measuring oxygen yields of a thermal conversion/elemental analyzer-isotope ratio mass spectrometer for organic and inorganic materials through injection of CO.

    Science.gov (United States)

    Yin, Xijie; Chen, Zhigang

    2014-12-01

    The thermal conversion/elemental analyzer-isotope ratio mass spectrometer (TC/EA-IRMS) is widely used to measure the δ(18) O value of various substances. A premise for accurate δ(18) O measurement is that the oxygen in the sample can be converted into carbon monoxide (CO) quantitatively or at least proportionally. Therefore, a precise method to determine the oxygen yield of TC/EA-IRMS measurements is needed. Most studies have used the CO peak area obtained from a known amount of a solid reference material (for example, benzoic acid) to calibrate the oxygen yield of the sample. Although it was assumed that the oxygen yield of the solid reference material is 100%, no direct evidence has been provided. As CO is the analyte gas for δ(18) O measurement by IRMS, in this study, we use a six-port valve to inject CO gas into the TC/EA. The CO is carried to the IRMS by the He carrier gas and the CO peak area is measured by the IRMS. The CO peak area thus obtained from a known amount of the injected CO is used to calibrate the oxygen yield of the sample. The oxygen yields of commonly used organic and inorganic reference materials such as benzoic acid (C6 H5 COOH), silver phosphate (Ag3 PO4 ), calcium carbonate (CaCO3 ) and silicon dioxide (SiO2 ) are investigated at different reactor temperatures and sample sizes. We obtained excellent linear correlation between the peak area for the injected CO and its oxygen atom amount. C6 H5 COOH has the highest oxygen yield, followed by Ag3 PO4 , CaCO3 and SiO2 . The oxygen yields of TC/EA-IRMS are less than 100% for both organic and inorganic substances, but the yields are relatively stable at the specified reactor temperature and for a given quantity of sample. Copyright © 2014 John Wiley & Sons, Ltd.

  8. 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

  9. 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.

  10. Magnetic excitons in singlet-ground-state ferromagnets

    DEFF Research Database (Denmark)

    Birgeneau, R.J.; Als-Nielsen, Jens Aage; Bucher, E.

    1971-01-01

    The authors report measurements of the dispersion of singlet-triplet magnetic excitons as a function of temperature in the singlet-ground-state ferromagnets fcc Pr and Pr3Tl. Well-defined excitons are observed in both the ferromagnetic and paramagnetic regions, but with energies which are nearly...

  11. Tetra- and octa-[4-(2-hydroxyethyl)phenoxy bearing novel metal-free and zinc(II) phthalocyanines: Synthesis, characterization and investigation of photophysicochemical properties

    Energy Technology Data Exchange (ETDEWEB)

    Köksoy, Baybars [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, 41400 Gebze, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Department of Chemistry, 34722 Kadıköy, Istanbul (Turkey)

    2015-05-15

    In this study, four novel phthalonitriles (1–4) and their corresponding metal-free (5–8) and zinc(II) phthalocyanine derivatives (9–12) bearing 4-(hydroxyethyl)phenoxy groups were synthesized. These novel compounds were characterized by IR, elemental analyses, {sup 1}H-NMR, UV–vis, and MALDI-TOF spectral data. Furthermore, photophysical (fluorescence quantum yields and lifetimes) and photochemical properties (singlet oxygen generation and photodegradation quantum yields) of these phthalocyanines were investigated in dimethylsulfoxide. The studied zinc(II) phthalocyanines generated highly singlet oxygen which is very important for the photodynamic therapy (PDT) of cancer. The fluorescence quenching behaviour of the newly synthesized phthalocyanine compounds were also investigated using 1,4-benzoquinone. - Highlights: • Octa and tetra 4-(hydroxyethyl)phenoxy substituted metal-free and zinc(II) phthalocyanines. • Study of photophysicochemical properties of eight new phthalocyanines. • Highly singlet oxygen generation for novel zinc(II) phthalocyanine photosensitizers.

  12. 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.)

  13. 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.)

  14. Oxygen-independent direct deoxyribonucleic acid backbone breakage caused by rose bengal and visible light

    Energy Technology Data Exchange (ETDEWEB)

    Peak, M J; Peak, J G; Foote, C S; Krinsky, N I

    1984-01-01

    An oxygen enhancement ratio of 10 for the induction of backbone single-strand breaks (SSBs) in purified deoxyribonucleic acid (DNA) by monochromatic 365 nm UV radiation was obtained. Similarly, a dose reduction factor of 10 was observed when the DNA was irradiated in the presence of 0.1 M diazabicyclo(2.2.2)octane (DABCO). To determine whether this breakage of DNA was due to the action of a reactive oxygen species such as singlet oxygen, we used the photosensitizing dye Rose Bengal and visible light as a system for generating singlet oxygen. Treatment of the DNA with Rose Bengal and 545 nm monochromatic light enhanced the rate of induction of SSBs six times, compared with the rate we obtained when the light was used alone. Elimination of oxygen or addition of 0.1 M DABCO during the 545 nm irradiation in the presence of Rose Bengal did not alter the enhancement of SSBs in the DNA caused by Rose Bengal and 545 nm radiation. The induction of SSBs in the DNA caused by irradiation of the DNA by 545 nm light in the presence of Rose Bengal was not enhanced by the use of D/sub 2/O instead of H/sub 2/O as a solvent. The results indicate that Rose Bengal plus visible light can cause biological damage without the intermediacy of reactive oxygen species, i.e. Rose Bengal and visible light can react directly with biological material, in reactions that appear to be type I photosensitized processes, independent of singlet oxygen as an intermediate.

  15. A laser flash photolysis and quantum chemical study of the fluorinated derivatives of singlet phenylnitrene.

    Science.gov (United States)

    Gritsan, N P; Gudmundsdóttir, A D; Tigelaar, D; Zhu, Z; Karney, W L; Hadad, C M; Platz, M S

    2001-03-07

    Laser flash photolysis (LFP, Nd:YAG laser, 35 ps, 266 nm, 10 mJ or KrF excimer laser, 10 ns, 249 nm, 50 mJ) of 2-fluoro, 4-fluoro, 3,5-difluoro, 2,6-difluoro, and 2,3,4,5,6-pentafluorophenyl azides produces the corresponding singlet nitrenes. The singlet nitrenes were detected by transient absorption spectroscopy, and their spectra are characterized by sharp absorption bands with maxima in the range of 300-365 nm. The kinetics of their decay were analyzed as a function of temperature to yield observed decay rate constants, k(OBS). The observed rate constant in inert solvents is the sum of k(R) + k(ISC) where k(R) is the absolute rate constant of rearrangement of singlet nitrene to an azirine and k(ISC) is the absolute rate constant of nitrene intersystem crossing (ISC). Values of k(R) and k(ISC) were deduced after assuming that k(ISC) is independent of temperature. Barriers to cyclization of 4-fluoro-, 3,5-difluoro-, 2-fluoro-, 2,6-difluoro-, and 2,3,4,5,6-pentafluorophenylnitrene in inert solvents are 5.3 +/- 0.3, 5.5 +/- 0.3, 6.7 +/- 0.3, 8.0 +/- 1.5, and 8.8 +/- 0.4 kcal/mol, respectively. The barrier to cyclization of parent singlet phenylnitrene is 5.6 +/- 0.3 kcal/mol. All of these values are in good quantitative agreement with CASPT2 calculations of the relative barrier heights for the conversion of fluoro-substituted singlet aryl nitrenes to benzazirines (Karney, W. L. and Borden, W. T. J. Am. Chem. Soc. 1997, 119, 3347). A single ortho-fluorine substituent exerts a small but significant bystander effect on remote cyclization that is not steric in origin. The influence of two ortho-fluorine substituents on the cyclization is pronounced. In the case of the singlet 2-fluorophenylnitrene system, evidence is presented that the benzazirine is an intermediate and that the corresponding singlet nitrene and benzazirine interconvert. Ab initio calculations at different levels of theory on a series of benzazirines, their isomeric ketenimines, and the transition

  16. Unitarity constraints in the standard model with a singlet scalar field

    International Nuclear Information System (INIS)

    Kang, Sin Kyu; Park, Jubin

    2015-01-01

    Motivated by the discovery of a new scalar field and amelioration of the electroweak vacuum stability ascribed to a singlet scalar field embedded in the standard model (SM), we examine the implication of the perturbative unitarity in the SM with a singlet scalar field. Taking into account the full contributions to the scattering amplitudes, we derive unitarity conditions on the scattering matrix which can be translated into bounds on the masses of the scalar fields. In the case that the singlet scalar field develops vacuum expectation value (VEV), we get the upper bound on the singlet scalar mass varying with the mixing between the singlet and Higgs scalars. On the other hand, the mass of the Higgs scalar can be constrained by the unitarity condition in the case that the VEV of the singlet scalar is not generated. Applying the upper bound on the Higgs mass to the scenario of the unitarized Higgs inflation, we discuss how the unitarity condition can constrain the Higgs inflation. The singlet scalar mass is not constrained by the unitarity itself when we impose Z 2 in the model because of no mixing with the Higgs scalar. But, regarding the singlet scalar field as a cold dark matter candidate, we derive upper bound on the singlet scalar mass by combining the observed relic abundance with the unitarity condition.

  17. 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.

  18. Hyperpolarized singlet NMR on a small animal imaging system

    DEFF Research Database (Denmark)

    Laustsen, Christoffer; Pileio, Giuseppe; Tayler, Michael C. D.

    2012-01-01

    Nuclear spin hyperpolarization makes a significant advance toward overcoming the sensitivity limitations of in vivo magnetic resonance imaging, particularly in the case of low-gamma nuclei. The sensitivity may be improved further by storing the hyperpolarization in slowly relaxing singlet...... populations of spin- 1/2 pairs. Here, we report hyperpolarized 13C spin order transferred into and retrieved from singlet spin order using a small animal magnetic resonance imaging scanner. For spins in sites with very similar chemical shifts, singlet spin order is sustained in high magnetic field without...... requiring strong radiofrequency irradiation. The demonstration of robust singlet-to-magnetization conversion, and vice versa, on a small animal scanner, is promising for future in vivo and clinical deployments....

  19. On the factors influencing the performance of solar reactors for water disinfection with photosensitized singlet oxygen.

    Science.gov (United States)

    Manjón, Francisco; Villén, Laura; García-Fresnadillo, David; Orellana, Guillermo

    2008-01-01

    Two solar reactors based on compound parabolic collectors (CPCs) were optimized for water disinfection by photosensitized singlet oxygen (1O2) production in the heterogeneous phase. Sensitizing materials containing Ru(II) complexes immobilized on porous silicone were produced, photochemically characterized, and successfully tested for the inactivation of up to 10(4) CFU mL(-1) of waterborne Escherichia coli (gram-negative) or Enterococcus faecalis (gram-positive) bacteria. The main factors determining the performance of the solar reactors are the type of photosensitizing material, the sensitizer loading, the CPC collector geometry (fin- vs coaxial-type), the fluid rheology, and the balance between concurrent photothermal--photolytic and 1O2 effects on the microorganisms' inactivation. In this way, at the 40 degrees N latitude of Spain, water can be disinfected on a sunny day (0.6-0.8 MJ m(-2) L(-1) accumulated solar radiation dose in the 360-700 nm range, typically 5-6 h of sunlight) with a fin-type reactor containing 0.6 m2 of photosensitizing material saturated with tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) (ca. 2.0 g m(-2)). The optimum rheological conditions require laminar-to-transitional water flow in both prototypes. The fin-type system showed better inactivation efficiency than the coaxial reactor due to a more important photolytic contribution. The durability of the sensitizing materials was tested and the operational lifetime of the photocatalyst is at least three months without any reduction in the bacteria inactivation efficiency. Solar water disinfection with 1O2-generating films is demonstrated to be an effective technique for use in isolated regions of developing countries with high yearly average sunshine.

  20. Robust singlet fission in pentacene thin films with tuned charge transfer interactions.

    Science.gov (United States)

    Broch, K; Dieterle, J; Branchi, F; Hestand, N J; Olivier, Y; Tamura, H; Cruz, C; Nichols, V M; Hinderhofer, A; Beljonne, D; Spano, F C; Cerullo, G; Bardeen, C J; Schreiber, F

    2018-03-05

    Singlet fission, the spin-allowed photophysical process converting an excited singlet state into two triplet states, has attracted significant attention for device applications. Research so far has focused mainly on the understanding of singlet fission in pure materials, yet blends offer the promise of a controlled tuning of intermolecular interactions, impacting singlet fission efficiencies. Here we report a study of singlet fission in mixtures of pentacene with weakly interacting spacer molecules. Comparison of experimentally determined stationary optical properties and theoretical calculations indicates a reduction of charge-transfer interactions between pentacene molecules with increasing spacer molecule fraction. Theory predicts that the reduced interactions slow down singlet fission in these blends, but surprisingly we find that singlet fission occurs on a timescale comparable to that in pure crystalline pentacene. We explain the observed robustness of singlet fission in such mixed films by a mechanism of exciton diffusion to hot spots with closer intermolecular spacings.

  1. Photophysical properties and localization of chlorins substituted with methoxy groups, hydroxyl groups and alkyl chains in liposome-like cellular membrane

    Energy Technology Data Exchange (ETDEWEB)

    Al-Omari, S [Department of Physics, Hashemite University, Zarqa 13115 (Jordan)

    2007-06-01

    Some of the photophysical properties (stationary absorbance and fluorescence, fluorescence decay times and singlet oxygen quantum yields) of chlorins substituted with methoxy groups, hydroxyl groups and hydrocarbonic chains were studied in ethanol and dipalmitoyl-phosphatidylcholine (DPPC) liposomes using steady-state and time-resolved fluorescence spectroscopies. The photophysical behaviors of the chlorins in liposomes like cellular membrane were compared with those obtained from chlorin-liposome systems delivered to Jurkat cells in order to select potent photosensitizers for the photodynamic treatment of cancer. The localization of the studied chlorins inside liposomes was found to depend strongly on the substituents of chlorins. Absorption spectra of chlorins embedded in DPPC-liposomes have been recorded in the temperature range of 20-70 deg. C. It is demonstrated that the location of the chlorin molecules depends on the phase state of the phospholipids. These observations are confirmed by the fluorescence lifetimes, singlet oxygen lifetimes and singlet oxygen quantum yields results.

  2. 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

  3. 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.

  4. 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.

  5. Ligand-based photooxidations of dithiomaltolato complexes of Ru(II) and Zn(II): photolytic CH activation and evidence of singlet oxygen generation and quenching.

    Science.gov (United States)

    Bruner, Britain; Walker, Malin Backlund; Ghimire, Mukunda M; Zhang, Dong; Selke, Matthias; Klausmeyer, Kevin K; Omary, Mohammad A; Farmer, Patrick J

    2014-08-14

    The complex [Ru(bpy)2(ttma)](+) (bpy = 2,2'-bipyridine; ttma = 3-hydroxy-2-methyl-thiopyran-4-thionate, 1, has previously been shown to undergo an unusual C-H activation of the dithiomaltolato ligand upon outer-sphere oxidation. The reaction generated alcohol and aldehyde products 2 and 3 from C-H oxidation of the pendant methyl group. In this report, we demonstrate that the same products are formed upon photolysis of 1 in presence of mild oxidants such as methyl viologen, [Ru(NH3)6](3+) and [Co(NH3)5Cl](2+), which do not oxidize 1 in the dark. This reactivity is engendered only upon excitation into an absorption band attributed to the ttma ligand. Analogous experiments with the homoleptic Zn(ttma)2, 4, also result in reduction of electron acceptors upon excitation of the ttma absorption band. Complexes 1 and 4 exhibit short-lived visible fluorescence and long-lived near-infrared phosphorescence bands. Singlet oxygen is both generated and quenched during aerobic excitation of 1 or 4, but is not involved in the C-H activation process.

  6. 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%.

  7. Microscopic theory of singlet exciton fission. III. Crystalline pentacene

    International Nuclear Information System (INIS)

    Berkelbach, Timothy C.; Reichman, David R.; Hybertsen, Mark S.

    2014-01-01

    We extend our previous work on singlet exciton fission in isolated dimers to the case of crystalline materials, focusing on pentacene as a canonical and concrete example. We discuss the proper interpretation of the character of low-lying excited states of relevance to singlet fission. In particular, we consider a variety of metrics for measuring charge-transfer character, conclusively demonstrating significant charge-transfer character in the low-lying excited states. The impact of this electronic structure on the subsequent singlet fission dynamics is assessed by performing real-time master-equation calculations involving hundreds of quantum states. We make direct comparisons with experimental absorption spectra and singlet fission rates, finding good quantitative agreement in both cases, and we discuss the mechanistic distinctions that exist between small isolated aggregates and bulk systems

  8. Microscopic theory of singlet exciton fission. III. Crystalline pentacene

    Energy Technology Data Exchange (ETDEWEB)

    Berkelbach, Timothy C., E-mail: tcb2112@columbia.edu; Reichman, David R., E-mail: drr2103@columbia.edu [Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027 (United States); Hybertsen, Mark S., E-mail: mhyberts@bnl.gov [Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973-5000 (United States)

    2014-08-21

    We extend our previous work on singlet exciton fission in isolated dimers to the case of crystalline materials, focusing on pentacene as a canonical and concrete example. We discuss the proper interpretation of the character of low-lying excited states of relevance to singlet fission. In particular, we consider a variety of metrics for measuring charge-transfer character, conclusively demonstrating significant charge-transfer character in the low-lying excited states. The impact of this electronic structure on the subsequent singlet fission dynamics is assessed by performing real-time master-equation calculations involving hundreds of quantum states. We make direct comparisons with experimental absorption spectra and singlet fission rates, finding good quantitative agreement in both cases, and we discuss the mechanistic distinctions that exist between small isolated aggregates and bulk systems.

  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. 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

  11. 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.

  12. Singlet axial constant from QCD sum rules

    International Nuclear Information System (INIS)

    Belitskij, A.V.; Teryaev, O.V.

    1995-01-01

    We analyze the singlet axial form factor of the proton for small momentum transferred in the framework of QCD sum rules using the interpolating nucleon current which explicitly accounts for the gluonic degrees of freedom. As the result we come to the quantitative prediction of the singlet axial constant. It is shown that the bilocal power corrections play the most important role in the analysis. 21 refs., 3 figs

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

    KAUST Repository

    Monge Palacios, Manuel

    2018-01-22

    Reactions of hydroxyl (OH) and hydroperoxyl (HO2) are important for governing the reactivity of combustion systems. We performed post-CCSD(T) ab initio calculations at the W3X-L//CCSD = FC/cc-pVTZ level to explore the triplet ground-state and singlet excited-state potential energy surfaces of the OH + HO2 → H2O + O2(3Σg−)/O2(1Δg) reactions. Using microcanonical and multistructural canonical transition state theories, we calculated the rate constant for the triplet and singlet channels over the temperature range 200–2500 K, represented by k(T) = 3.08 × 1012T0.07 exp(1151/RT) + 8.00 × 1012T0.32 exp(−6896/RT) and k(T) = 2.14 × 106T1.65 exp(−2180/RT) in cm3 mol−1 s−1, respectively. The branching ratios show that the yield of singlet excited oxygen is small (<0.5% below 1000 K). To ascertain the importance of singlet oxygen channel, our new kinetic information was implemented into the kinetic model for hydrogen combustion recently updated by Konnov (Combust. Flame, 2015, 162, 3755–3772). The updated kinetic model was used to perform H2O2 thermal decomposition simulations for comparison against shock tube experiments performed by Hong et al. (Proc. Combust. Inst., 2013, 34, 565–571), and to estimate flame speeds and ignition delay times in H2 mixtures. The simulation predicted a larger amount of O2(1Δg) in H2O2 decomposition than that predicted by Konnov\\'s original model. These differences in the O2(1Δg) yield are due to the use of a higher ab initio level and a more sophisticated methodology to compute the rate constant than those used in previous studies, thereby predicting a significantly larger rate constant. No effect was observed on the rate of the H2O2 decomposition and on the flame speeds and ignition delay times of different H2–oxidizer mixtures. However, if the oxidizer is seeded with O3, small differences appear in the flame speed. Given that O2(1Δg) is much more reactive than O2(3Σg−), we do not preclude an effect of the

  14. Singlet fermionic dark matter with Veltman conditions

    Science.gov (United States)

    Kim, Yeong Gyun; Lee, Kang Young; Nam, Soo-hyeon

    2018-07-01

    We reexamine a renormalizable model of a fermionic dark matter with a gauge singlet Dirac fermion and a real singlet scalar which can ameliorate the scalar mass hierarchy problem of the Standard Model (SM). Our model setup is the minimal extension of the SM for which a realistic dark matter (DM) candidate is provided and the cancellation of one-loop quadratic divergence to the scalar masses can be achieved by the Veltman condition (VC) simultaneously. This model extension, although renormalizable, can be considered as an effective low-energy theory valid up to cut-off energies about 10 TeV. We calculate the one-loop quadratic divergence contributions of the new scalar and fermionic DM singlets, and constrain the model parameters using the VC and the perturbative unitarity conditions. Taking into account the invisible Higgs decay measurement, we show the allowed region of new physics parameters satisfying the recent measurement of relic abundance. With the obtained parameter set, we predict the elastic scattering cross section of the new singlet fermion into target nuclei for a direct detection of the dark matter. We also perform the full analysis with arbitrary set of parameters without the VC as a comparison, and discuss the implication of the constraints by the VC in detail.

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

    Energy Technology Data Exchange (ETDEWEB)

    He, Weiwei; Zhao, Hongxiao; Jia, Huimin [Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province, Institute of Surface Micro and Nano Materials, Xuchang University, Henan 461000 (China); Yin, Jun-Jie [Center for Food Safety and Applied Nutrition, U.S. Food and Drug Administration, College Park, MD 20740 (United States); Zheng, Zhi, E-mail: zhengzhi99999@gmail.com [Key Laboratory of Micro-Nano Materials for Energy Storage and Conversion of Henan Province, Institute of Surface Micro and Nano Materials, Xuchang University, Henan 461000 (China)

    2014-05-01

    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.

  16. 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

  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. Delayed fluorescence of meso-tetraphenylporphyrin in acetone and in dimethylsulphoxide

    International Nuclear Information System (INIS)

    Korinek, M.; Klinger, P.; Dedic, R.; Psencik, J.; Svoboda, A.; Hala, J.

    2007-01-01

    Photodynamic therapy is based on photosensitisation of singlet oxygen by porphyrin-like molecules. We have performed a systematic study of delayed fluorescence of tetraphenylporphyrin in acetone (used as a spectroscopic standard) and in dimethylsulphoxide (clinically used solvent) to obtain spectra, kinetics, and quantum yields, including their dependencies on tetraphenylporphyrin concentration. In dimethylsulphoxide the repopulation of excited singlets and subsequent delayed fluorescence is caused by triplet-triplet quenching with rate constant of (2.2±1.0)x10 9 l mol -1 s -1 . However, repopulation of excited singlets in acetone is also caused by singlet oxygen reaction with triplet tetraphenylporphyrin causing monoexponential delayed fluorescence decay with the lifetime 0.3 μs. Due to much lower viscosity of acetone compared to dimethylsulphoxide, triplet-triplet quenching constant in acetone is much higher (1.7±0.7)x10 10 l mol -1 s -1 . The rate constant for the reaction of singlet oxygen with triplet of tetraphenylporphyrin is (2.0±0.8)x10 10 l mol -1 s -1 in acetone

  19. 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.

  20. 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.

  1. 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

  2. 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...

  3. Singlet fermionic dark matter with Veltman conditions

    OpenAIRE

    Kim, Yeong Gyun; Lee, Kang Young; Nam, Soo-hyeon

    2018-01-01

    We reexamine a renormalizable model of a fermionic dark matter with a gauge singlet Dirac fermion and a real singlet scalar which can ameliorate the scalar mass hierarchy problem of the Standard Model (SM). Our model setup is the minimal extension of the SM for which a realistic dark matter (DM) candidate is provided and the cancellation of one-loop quadratic divergence to the scalar masses can be achieved by the Veltman condition (VC) simultaneously. This model extension, although renormaliz...

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

    Science.gov (United States)

    Wang, Zhi-Wei; Steele, T. G.; Hanif, T.; Mann, R. B.

    2016-08-01

    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.

  5. 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.

  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. Singlet versus Triplet Excited State Mediated Photoinduced Dehalogenation Reactions of Itraconazole in Acetonitrile and Aqueous Solutions.

    Science.gov (United States)

    Zhu, Ruixue; Li, Ming-de; Du, Lili; Phillips, David Lee

    2017-04-06

    Photoinduced dehalogenation of the antifungal drug itraconazole (ITR) in acetonitrile (ACN) and ACN/water mixed solutions was investigated using femtosecond and nanosecond time-resolved transient absorption (fs-TA and ns-TA, respectively) and nanosecond time-resolved resonance Raman spectroscopy (ns-TR 3 ) experiments. An excited resonance energy transfer is found to take place from the 4-phenyl-4,5-dihydro-3H-1,2,4-triazol-3-one part of the molecule to the 1,3-dichlorobenzene part of the molecule when ITR is excited by ultraviolet light. This photoexcitation is followed by a fast carbon-halogen bond cleavage that leads to the generation of radical intermediates via either triplet and/or singlet excited states. It is found that the singlet excited state-mediated carbon-halogen cleavage is the predominant dehalogenation process in ACN solvent, whereas a triplet state-mediated carbon-halogen cleavage prefers to occur in the ACN/water mixed solutions. The singlet-to-triplet energy gap is decreased in the ACN/water mixed solvents and this helps facilitate an intersystem crossing process, and thus, the carbon-halogen bond cleavage happens mostly through an excited triplet state in the aqueous solutions examined. The ns-TA and ns-TR 3 results also provide some evidence that radical intermediates are generated through a homolytic carbon-halogen bond cleavage via predominantly the singlet excited state pathway in ACN but via mainly the triplet state pathway in the aqueous solutions. In strong acidic solutions, protonation at the oxygen and/or nitrogen atoms of the 1,2,4-triazole-3-one group appears to hinder the dehalogenation reactions. This may offer the possibility that the phototoxicity of ITR due to the generation of aryl or halogen radicals can be reduced by protonation of certain moieties in suitably designed ITR halogen-containing derivatives.

  8. The hydroxypyridinone iron chelator CP94 increases methyl-aminolevulinate-based photodynamic cell killing by increasing the generation of reactive oxygen species

    Directory of Open Access Journals (Sweden)

    Yuktee Dogra

    2016-10-01

    Full Text Available Methyl-aminolevulinate-based photodynamic therapy (MAL-PDT is utilised clinically for the treatment of non-melanoma skin cancers and pre-cancers and the hydroxypyridinone iron chelator, CP94, has successfully been demonstrated to increase MAL-PDT efficacy in an initial clinical pilot study. However, the biochemical and photochemical processes leading to CP94-enhanced photodynamic cell death, beyond the well-documented increases in accumulation of the photosensitiser protoporphyrin IX (PpIX, have not yet been fully elucidated. This investigation demonstrated that MAL-based photodynamic cell killing of cultured human squamous carcinoma cells (A431 occurred in a predominantly necrotic manner following the generation of singlet oxygen and ROS. Augmenting MAL-based photodynamic cell killing with CP94 co-treatment resulted in increased PpIX accumulation, MitoSOX-detectable ROS generation (probably of mitochondrial origin and necrotic cell death, but did not affect singlet oxygen generation. We also report (to our knowledge, for the first time the detection of intracellular PpIX-generated singlet oxygen in whole cells via electron paramagnetic resonance spectroscopy in conjunction with a spin trap.

  9. 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.

  10. Reactive oxygen species generation in aqueous solutions containing GdVO4:Eu3+ nanoparticles and their complexes with methylene blue

    Science.gov (United States)

    Hubenko, Kateryna; Yefimova, Svetlana; Tkacheva, Tatyana; Maksimchuk, Pavel; Borovoy, Igor; Klochkov, Vladimir; Kavok, Nataliya; Opolonin, Oleksander; Malyukin, Yuri

    2018-04-01

    It this letter, we report the study of free radicals and reactive oxygen species (ROS) generation in water solutions containing gadolinium orthovanadate GdVO4:Eu3+ nanoparticles (VNPs) and their complexes with methylene blue (MB) photosensitizer. The catalytic activity was studied under UV-Vis and X-ray irradiation by three methods (conjugated dienes test, OH· radical, and singlet oxygen detection). It has been shown that the VNPs-MB complexes reveal high efficiency of ROS generation under UV-Vis irradiation associated with both high efficiency of OH· radicals generation by VNPs and singlet oxygen generation by MB due to nonradiative excitation energy transfer from VNPs to MB molecules. Contrary to that under X-ray irradiation, the strong OH . radicals scavenging by VNPs has been observed.

  11. 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

  12. 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.

  13. Singlet oxygen reactivity in water-rich solvent mixtures

    Directory of Open Access Journals (Sweden)

    Cristina Sousa

    2008-01-01

    Full Text Available The 3-methylindole (3MI oxygenation sensitized by psoralen (PSO has been investigated in 100%, 20% and 5% O2-saturated water/dioxane (H2O/Dx mixtures. The lowering of the ¹O2* chemical rate when water (k chem∆3MI = 1.4 × 109 M-1 s-1 is replaced by deuterated water (k chem∆3MI = 1.9 × 108 M-1 s-1 suggests that hydrogen abstraction is involved in the rate determining step. A high dependence of the chemical rate constant on water concentration in H2O/Dx mixtures was found showing that water molecules are absolutely essential for the success of the 3MI substrate oxidation by ¹O2* in water-rich solvent mixtures.

  14. 2HDM portal for Singlet-Doublet Dark Matter

    OpenAIRE

    Arcadi, Giorgio

    2018-01-01

    We present an extensive analysis of a model in which the (Majorana) Dark Matter candidate is a mixture between a SU(2) singlet and two SU(2) doublets. This kind of setup takes the name of singlet-doublet model. We will investigate in detail an extension of this model in which the Dark Matter sector interactions with a 2-doublet Higgs sector enforcing the complementarity between Dark Matter phenomenology and searches of extra Higgs bosons.

  15. Unified model for singlet fission within a non-conjugated covalent pentacene dimer

    Science.gov (United States)

    Basel, Bettina S.; Zirzlmeier, Johannes; Hetzer, Constantin; Phelan, Brian T.; Krzyaniak, Matthew D.; Reddy, S. Rajagopala; Coto, Pedro B.; Horwitz, Noah E.; Young, Ryan M.; White, Fraser J.; Hampel, Frank; Clark, Timothy; Thoss, Michael; Tykwinski, Rik R.; Wasielewski, Michael R.; Guldi, Dirk M.

    2017-01-01

    When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted ∼50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. Using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures. PMID:28516916

  16. Synthesis and photophysicochemical studies of a water soluble conjugate between folic acid and zinc tetraaminophthalocyanine

    International Nuclear Information System (INIS)

    Khoza, Phindile; Antunes, Edith; Chen, Ji-Yao; Nyokong, Tebello

    2013-01-01

    This work reports on the synthesis of zinc tetraaminophthalocyanine (ZnTAPc) functionalized with folic acid (FA), forming ZnTAPcFA. The conjugate between FA and ZnTAPc was soluble in water whereas ZnTAPc alone is not. The structure of ZnTAPcFA conjugate was elucidated by 1 H NMR, MALDI-TOF mass and FTIR spectra. Photophysical and photochemical studies of ZnTAPcFA were conducted in DMSO. The increase in fluorescence quantum yield of the conjugate was accompanied by a decrease in the triplet and singlet oxygen quantum yields. The changes in triplet quantum and singlet oxygen quantum yields were marginal when ZnTAPc was simply mixed with FA without a chemical bond. - Highlights: ► A conjugate between folic acid and a zinc tetraaminophthalocyanine was formed. ► The conjugate is water soluble even though the phthalocyanine alone is not. ► The fluorescence quantum yield of the conjugate was enhanced compared to the phthalocyanine alone. ► Triplet quantum yields decreased for the conjugate

  17. Mechanism of dark decomposition of iodine donor in the active medium of a pulsed chemical oxygen - iodine laser

    International Nuclear Information System (INIS)

    Andreeva, Tamara L; Kuznetsova, S V; Maslov, A I; Sorokin, Vadim N

    2002-01-01

    A scheme is proposed that describes the dark decomposition of iodide - the donor of iodine - and the relaxation of singlet oxygen in the chlorine-containing active medium of a pulsed chemical oxygen - iodine laser (COIL). For typical compositions of the active media of pulsed COILs utilising CH 3 I molecules as iodine donors, a branching chain reaction of the CH 3 I decomposition accompanied by the efficient dissipation of singlet oxygen is shown to develop even at the stage of filling the active volume. In the active media with CF 3 I as the donor, a similar chain reaction is retarded due to the decay of CF 3 radicals upon recombination with oxygen. The validity of this mechanism is confirmed by a rather good agreement between the results of calculations and the available experimental data. The chain decomposition of alkyliodides accompanied by an avalanche production of iodine atoms represents a new way of efficient chemical production of iodine for a COIL. (active media)

  18. Exact exchange-correlation potentials of singlet two-electron systems

    Science.gov (United States)

    Ryabinkin, Ilya G.; Ospadov, Egor; Staroverov, Viktor N.

    2017-10-01

    We suggest a non-iterative analytic method for constructing the exchange-correlation potential, v XC ( r ) , of any singlet ground-state two-electron system. The method is based on a convenient formula for v XC ( r ) in terms of quantities determined only by the system's electronic wave function, exact or approximate, and is essentially different from the Kohn-Sham inversion technique. When applied to Gaussian-basis-set wave functions, the method yields finite-basis-set approximations to the corresponding basis-set-limit v XC ( r ) , whereas the Kohn-Sham inversion produces physically inappropriate (oscillatory and divergent) potentials. The effectiveness of the procedure is demonstrated by computing accurate exchange-correlation potentials of several two-electron systems (helium isoelectronic series, H2, H3 + ) using common ab initio methods and Gaussian basis sets.

  19. Singlet Extensions of the MSSM with ℤ4R Symmetry

    International Nuclear Information System (INIS)

    Ratz, Michael; Vaudrevange, Patrick K. S.

    2015-01-01

    We discuss singlet extensions of the MSSM with ℤ 4 R symmetry. We show that holomorphic zeros can avoid a potentially large coefficient of the term linear in the singlet. The emerging model has both an effective μ term and a supersymmetric mass term for the singlet μ N which are controlled by the gravitino mass. The μ term turns out to be suppressed against μ N by about one or two orders of magnitude. We argue that this class of models might provide us with a solution to the little hierarchy problem of the MSSM

  20. Reactions of atomic oxygen with the chlorate ion and the perchlorate ion

    Science.gov (United States)

    Anan'ev, Vladimir; Miklin, Mikhail; Kriger, Ludmila

    2014-06-01

    The reactions of the chlorate ion with atomic oxygen formed under photolysis of the nitrate ion introduced to potassium chlorate crystal by co-crystallization were studied by optical and infrared absorption spectroscopy. The perchlorate ion was found to form in solids as product of addition reaction of singlet atomic oxygen, formed under dissociation of the peroxynitrite ion - the product of isomerization of the excited nitrate ion. Triplet atomic oxygen does not react with the chlorate ion. The atomic oxygen formed under photolysis of the nitrate ion introduced to potassium perchlorate crystal by co-crystallization does not react with the perchlorate ion.

  1. WIMP Dark Matter and Unitarity-Conserving Inflation via a Gauge Singlet Scalar

    International Nuclear Information System (INIS)

    Kahlhoefer, Felix; McDonald, John

    2015-07-01

    A gauge singlet scalar with non-minimal coupling to gravity can drive inflation and later freeze out to become cold dark matter. We explore this idea by revisiting inflation in the singlet direction (S-inflation) and Higgs Portal Dark Matter in light of the Higgs discovery, limits from LUX and observations by Planck. We show that large regions of parameter space remain viable, so that successful inflation is possible and the dark matter relic abundance can be reproduced. Moreover, the scalar singlet can stabilise the electroweak vacuum and at the same time overcome the problem of unitarity-violation during inflation encountered by Higgs Inflation, provided the singlet is a real scalar. The 2-σ Planck upper bound on n s imposes that the singlet mass is below 2 TeV, so that almost the entire allowed parameter range can be probed by XENON1T.

  2. 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

  3. 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.)

  4. Analysis of γ-ray irradiated pasteurized agaricus (Agaricus blazei Murill) by ESR in oxygen-free atmosphere

    International Nuclear Information System (INIS)

    Kemeya, Hiromi; Ukai, Mitsuko

    2007-01-01

    Agaricus (Agaricus blazei Murill) is one of a popular crude drug in Japan and East Asia countries. The crude drugs originating from natural raw products are easy to be contaminated by microorganism. Radiation method has been introduced as the sterilization technology for crude drugs. ESR has been used for the detection of radicals in irradiated drugs. Using ESR, we detected radical species in Agaricus before and after the gamma ray pasteurization. The ESR spectrum consists of a broad sextet centered at g=2.0, a singlet at same g-value and a singlet at g=4.0. We found that relaxation times of radicals in Agaricus varied by the presence of oxygen. Upon substitution of air by Ar, i.e., the absent of oxygen in the ESR sample tube, the T 1 value became 10 times larger than the presence of oxygen. Accordingly, the progressive saturation curve indicates more immediate saturation under the Ar than air atmosphere. Radicals, produced by the γ-ray irradiation to Agaricus, are very sensitive to oxygen. We concluded that ESR spectrum of irradiated Agaricus sample in the absence of oxygen is useful for the detection of dose level of γ-ray irradiation. (author)

  5. 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

  6. Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission.

    Science.gov (United States)

    Hart, Stephanie M; Silva, W Ruchira; Frontiera, Renee R

    2018-02-07

    Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes.

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

    KAUST Repository

    Dimitrov, Stoichko; Schroeder, Bob; Nielsen, Christian; Bronstein, Hugo; Fei, Zhuping; McCulloch, Iain; Heeney, Martin; Durrant, James

    2016-01-01

    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

  8. 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.

  9. Singlet Fission via an Excimer-Like Intermediate in 3,6-Bis(thiophen-2-yl)diketopyrrolopyrrole Derivatives.

    Science.gov (United States)

    Mauck, Catherine M; Hartnett, Patrick E; Margulies, Eric A; Ma, Lin; Miller, Claire E; Schatz, George C; Marks, Tobin J; Wasielewski, Michael R

    2016-09-14

    Singlet fission (SF) in polycrystalline thin films of four 3,6-bis(thiophen-2-yl)diketopyrrolopyrrole (TDPP) chromophores with methyl (Me), n-hexyl (C6), triethylene glycol (TEG), and 2-ethylhexyl (EH) substituents at the 2,5-positions is found to involve an intermediate excimer-like state. The four different substituents yield four distinct intermolecular packing geometries, resulting in variable intermolecular charge transfer (CT) interactions in the solid. SF from the excimer state of Me, C6, TEG, and EH takes place in τSF = 22, 336, 195, and 1200 ps, respectively, to give triplet yields of 200%, 110%, 110%, and 70%, respectively. The transient spectra of the excimer-like state and its energetic proximity to the lowest excited singlet state in these derivatives suggests that this state may be the multiexciton (1)(T1T1) state that precedes formation of the uncorrelated triplet excitons. The excimer decay rates correlate well with the SF efficiencies and the degree of intermolecular donor-acceptor interactions resulting from π-stacking of the thiophene donor of one molecule with the DPP core acceptor in another molecule as observed in the crystal structures. Such interactions are found to also increase with the SF coupling energies, as calculated for each derivative. These structural and spectroscopic studies afford a better understanding of the electronic interactions that enhance SF in chromophores having strong intra- and intermolecular CT character.

  10. Photochemical characterization of water samples from Minnesota and Vermont sites with malformed frogs: potential influence of photosensitization by singlet molecular oxygen (1O2) and free radicals on aquatic toxicity

    International Nuclear Information System (INIS)

    Bilski, P.; Burkhart, J.G.; Chignell, C.F.

    2003-01-01

    Environmental pollutants activated by UV sunlight may have contributed to the recent decline in frog populations and the concomitant increase in malformations in the USA and abroad. UV radiation is able to mutate DNA and to initiate photosensitization processes that generate mutagenic and biologically disruptive oxygen transients. We have examined water from selected sites in Minnesota and Vermont using singlet molecular oxygen ( 1 O 2 ), detected by its phosphorescence and free radicals detected by spin trapping, as markers for photosensitization. Water from a pond in Minnesota with malformed frogs, which also causes malformations in the laboratory, photosensitized more 1 O 2 , even though it absorbed less UV light compared to water from a site that did not cause malformations. This suggested that unknown natural or pollutant agents were present, and that photosensitization may be involved. Although UV irradiation of the two Minnesota water samples in the presence of the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) revealed the presence of the DMPO/·OH, DMPO/·H(e aq - ) and DMPO/·C(unknown) adducts there were no qualitative or quantitative differences between them. We also examined water samples from several sites in Vermont, and compared them by measuring the quantum yield of 1 O 2 photosensitization. While all the Vermont samples produced a small amount of 1 O 2 , there was no clear correlation with the incidence of frog malformations. However, the samples differed strongly in absorption spectra and the ability to quench 1 O 2 . These factors may determine how much UV light is absorbed and converted into chemical reactions. Our results show that photochemical characterization of 1 O 2 photosensitization is possible in untreated natural water samples. Photosensitization falls into the category of global factors that may be closely associated with the effects of UV irradiation of the Earth's environments. Thus, photosensitization might be an important

  11. Correlation among Singlet-Oxygen Quenching, Free-Radical Scavenging, and Excited-State Intramolecular-Proton-Transfer Activities in Hydroxyflavones, Anthocyanidins, and 1-Hydroxyanthraquinones.

    Science.gov (United States)

    Nagaoka, Shin-Ichi; Bandoh, Yuki; Nagashima, Umpei; Ohara, Keishi

    2017-10-26

    Singlet-oxygen ( 1 O 2 ) quenching, free-radical scavenging, and excited-state intramolecular proton-transfer (ESIPT) activities of hydroxyflavones, anthocyanidins, and 1-hydroxyanthraquinones were studied by means of laser, stopped-flow, and steady-state spectroscopies. In hydroxyflavones and anthocyanidins, the 1 O 2 quenching activity positively correlates to the free-radical scavenging activity. The reason for this correlation can be understood by considering that an early step of each reaction involves electron transfer from the unfused phenyl ring (B-ring), which is singly bonded to the bicyclic chromen or chromenylium moiety (A- and C-rings). Substitution of an electron-donating OH group at B-ring enhances the electron transfer leading to activation of the 1 O 2 quenching and free-radical scavenging. In 3-hydroxyflavones, the OH substitution at B-ring reduces the activity of ESIPT within C-ring, which can be explained in terms of the nodal-plane model. As a result, the 1 O 2 quenching and free-radical scavenging activities negatively correlate to the ESIPT activity. A catechol structure at B-ring is another factor that enhances the free-radical scavenging in hydroxyflavones. In contrast to these hydroxyflavones, 1-hydroxyanthraquinones having an electron-donating OH substituent adjacent to the O-H---O═C moiety susceptible to ESIPT do not show a simple correlation between their 1 O 2 quenching and ESIPT activities, because the OH substitution modulates these reactions.

  12. Spin-Triplet Pairing Induced by Spin-Singlet Interactions in Noncentrosymmetric Superconductors

    Science.gov (United States)

    Matsuzaki, Tomoaki; Shimahara, Hiroshi

    2017-02-01

    In noncentrosymmetric superconductors, we examine the effect of the difference between the intraband and interband interactions, which becomes more important when the band splitting increases. We define the difference ΔVμ between their coupling constants, i.e., that between the intraband and interband hopping energies of intraband Cooper pairs. Here, the subscript μ of ΔVμ indicates that the interactions scatter the spin-singlet and spin-triplet pairs when μ = 0 and μ = 1,2,3, respectively. It is shown that the strong antisymmetric spin-orbit interaction reverses the target spin parity of the interaction: it converts the spin-singlet and spin-triplet interactions represented by ΔV0 and ΔVμ>0 into effective spin-triplet and spin-singlet pairing interactions, respectively. Hence, for example, triplet pairing can be induced solely by the singlet interaction ΔV0. We name the pairing symmetry of the system after that of the intraband Cooper pair wave function, but with an odd-parity phase factor excluded. The pairing symmetry must then be even, even for the triplet component, and the following results are obtained. When ΔVμ is small, the spin-triplet p-wave interactions induce spin-triplet s-wave and spin-triplet d-wave pairings in the regions where the repulsive singlet s-wave interaction is weak and strong, respectively. When ΔV0 is large, a repulsive interband spin-singlet interaction can stabilize spin-triplet pairing. When the Rashba interaction is adopted for the spin-orbit interaction, the spin-triplet pairing interactions mediated by transverse magnetic fluctuations do not contribute to triplet pairing.

  13. On the behaviour of non-singlet structure functions at small x

    International Nuclear Information System (INIS)

    Bluemlein, J.

    1995-10-01

    The resummation of O(α s l+1 ln 2l x) terms in the evolution kernels of non-singlet combinations of unpolarized and polarized structure functions is investigated. The agreement with complete calculations up to order α s 2 is demonstrated, and the leading small-x contributions to the three-loop non-singlet splitting functions P ± are derived. The additional contributions due to the resummed terms are studied numerically for the most important non-singlet structure functions. They are found to be about 1% or smaller in the kinematical regions accessible at present and in the forseeable future. (orig.)

  14. Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

    Science.gov (United States)

    Asgharzadeh, Somaie; Vahedpour, Morteza

    2018-06-01

    Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

  15. MC-PDFT can calculate singlet-triplet splittings of organic diradicals

    Science.gov (United States)

    Stoneburner, Samuel J.; Truhlar, Donald G.; Gagliardi, Laura

    2018-02-01

    The singlet-triplet splittings of a set of diradical organic molecules are calculated using multiconfiguration pair-density functional theory (MC-PDFT), and the results are compared with those obtained by Kohn-Sham density functional theory (KS-DFT) and complete active space second-order perturbation theory (CASPT2) calculations. We found that MC-PDFT, even with small and systematically defined active spaces, is competitive in accuracy with CASPT2, and it yields results with greater accuracy and precision than Kohn-Sham DFT with the parent functional. MC-PDFT also avoids the challenges associated with spin contamination in KS-DFT. It is also shown that MC-PDFT is much less computationally expensive than CASPT2 when applied to larger active spaces, and this illustrates the promise of this method for larger diradical organic systems.

  16. A comparative kinetic and mechanistic study between tetrahydrozoline and naphazoline toward photogenerated reactive oxygen species.

    Science.gov (United States)

    Criado, Susana; García, Norman A

    2010-01-01

    Kinetic and mechanistic aspects of the vitamin B2 (riboflavin [Rf])-sensitized photo-oxidation of the imidazoline derivates (IDs) naphazoline (NPZ) and tetrahydrozoline (THZ) were investigated in aqueous solution. The process appears as important on biomedical grounds, considering that the vitamin is endogenously present in humans, and IDs are active components of ocular medicaments of topical application. Under aerobic visible light irradiation, a complex picture of competitive interactions between sensitizer, substrates and dissolved oxygen takes place: the singlet and triplet ((3)Rf*) excited states of Rf are quenched by the IDs: with IDs concentrations ca. 5.0 mM and 0.02 mM Rf, (3)Rf* is quenched by IDs, in a competitive fashion with dissolved ground state oxygen. Additionally, the reactive oxygen species: O(2)((1)Delta(g)), O(2)(*-), HO(*) and H(2)O(2), generated from (3)Rf* and Rf(*-), were detected with the employment of time-resolved methods or specific scavengers. Oxygen uptake experiments indicate that, for NPZ, only H(2)O(2) was involved in the photo-oxidation. In the case of THZ, O(2)(*-), HO(*) and H(2)O(2) were detected, whereas only HO(*) was unambiguously identified as THZ oxidative agents. Upon direct UV light irradiation NPZ and THZ generate O(2)((1)Delta(g)), with quantum yields of 0.2 (literature value, employed as a reference) and 0.08, respectively, in acetonitrile.

  17. Effects of Crystal Morphology on Singlet Exciton Fission in Diketopyrrolopyrrole Thin Films.

    Science.gov (United States)

    Hartnett, Patrick E; Margulies, Eric A; Mauck, Catherine M; Miller, Stephen A; Wu, Yilei; Wu, Yi-Lin; Marks, Tobin J; Wasielewski, Michael R

    2016-02-25

    Singlet exciton fission (SF) is a promising strategy for increasing photovoltaic efficiency, but in order for SF to be useful in solar cells, it should take place in a chromophore that is air-stable, highly absorptive, solution processable, and inexpensive. Unlike many SF chromophores, diketopyrrolopyrrole (DPP) conforms to these criteria, and here we investigate SF in DPP for the first time. SF yields in thin films of DPP derivatives, which are widely used in organic electronics and photovoltaics, are shown to depend critically on crystal morphology. Time-resolved spectroscopy of three DPP derivatives with phenyl (3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, PhDPP), thienyl (3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, TDPP), and phenylthienyl (3,6-di(5-phenylthiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, PhTDPP) aromatic substituents in 100-200 nm thin films reveals that efficient SF occurs only in TDPP and PhTDPP (τSF = 220 ± 20 ps), despite the fact that SF is most exoergic in PhDPP. This result correlates well with the greater degree of π-overlap and closer π-stacking in TDPP (3.50 Å) and PhTDPP (3.59 Å) relative to PhDPP (3.90 Å) and demonstrates that SF in DPP is highly sensitive to the electronic coupling between adjacent chromophores. The triplet yield in PhTDPP films is determined to be 210 ± 35% by the singlet depletion method and 165 ± 30% by the energy transfer method, showing that SF is nearly quantitative in these films and that DPP derivatives are a promising class of SF chromophores for enhancing photovoltaic performance.

  18. Photophysical, Photochemical, and BQ Quenching Properties of Zinc Phthalocyanines with Fused or Interrupted Extended Conjugation

    Directory of Open Access Journals (Sweden)

    Gülşah Gümrükçü

    2014-01-01

    Full Text Available The effects of substituents and solvents on the photophysical and photochemical parameters of zinc(II phthalocyanines containing four Schiff’s base substituents attached directly and through phenyleneoxy-bridges on peripheral positions are reported. The group effects on peripheral position and the continual and intermittent conjugation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen, and fluorescence quantum yields of these compounds in dimethylsulfoxide (DMSO, dimethylformamide (DMF, and tetrahydrofurane (THF. Among the different substituents, phthalocyanines with cinnamaldimine moieties (1c and 2c have the highest singlet oxygen quantum yields (ΦΔ and those with nitro groups (1a and 2a have the highest fluorescence quantum yields in all the solvents used. The fluorescence of the substituted zinc(II phthalocyanine complexes is effectively quenched by 1,4-benzoquinone (BQ in these solvents.

  19. Singlet-paired coupled cluster theory for open shells

    Science.gov (United States)

    Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

    2016-06-01

    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.

  20. 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.

  1. Monte Carlo modeling of in vivo protoporphyrin IX fluorescence and singlet oxygen production during photodynamic therapy for patients presenting with superficial basal cell carcinomas

    Science.gov (United States)

    Valentine, Ronan M.; Brown, C. Tom A.; Moseley, Harry; Ibbotson, Sally; Wood, Kenny

    2011-04-01

    We present protoporphyrin IX (PpIX) fluorescence measurements acquired from patients presenting with superficial basal cell carcinoma during photodynamic therapy (PDT) treatment, facilitating in vivo photobleaching to be monitored. Monte Carlo (MC) simulations, taking into account photobleaching, are performed on a three-dimensional cube grid, which represents the treatment geometry. Consequently, it is possible to determine the spatial and temporal changes to the origin of collected fluorescence and generated singlet oxygen. From our clinical results, an in vivo photobleaching dose constant, β of 5-aminolaevulinic acid-induced PpIX fluorescence is found to be 14 +/- 1 J/cm2. Results from our MC simulations suggest that an increase from our typical administered treatment light dose of 75-150 J/cm2 could increase the effective PDT treatment initially achieved at a depth of 2.7-3.3 mm in the tumor, respectively. Moreover, this increase reduces the surface PpIX fluorescence from 0.00012 to 0.000003 of the maximum value recorded before treatment. The recommendation of administrating a larger light dose, which advocates an increase in the treatment time after surface PpIX fluorescence has diminished, remains valid for different sets of optical properties and therefore should have a beneficial outcome on the total treatment effect.

  2. Photodegradation of polymer-dispersed perylene di-imide dyes

    Science.gov (United States)

    Tanaka, Nobuaki; Barashkov, Nikolay; Heath, Jerry; Sisk, Wade N.

    2006-06-01

    Polymer-dispersed perylene di-imide dye photodegradation is investigated by monitoring the fluorescence intensity as a function of 532 nm laser pulses. Anaerobically irradiated polymer-dye films exhibited an accelerated decrease in fluorescence intensity, which was partially recovered upon exposure to oxygen. Decelerated photodegradation rates were observed for perylene di-imide ethanol solutions upon the addition of a singlet oxygen quenching antioxidant. These observations suggest reversible photoreduction and type II photo-oxidation as important photodegradation mechanisms. Type II photo-oxidation for perylene red 532 nm irradiation is supported by a singlet oxygen quantum yield of 0.09±0.03, determined via detection of time-resolved O2 (a1Δg —> X3∑g-) infrared phosphorescence.

  3. 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

  4. Synthesis and photophysicochemical studies of a water soluble conjugate between folic acid and zinc tetraaminophthalocyanine

    Energy Technology Data Exchange (ETDEWEB)

    Khoza, Phindile; Antunes, Edith [Department of Chemistry, Rhodes University, PO Box 94, Grahamstown (South Africa); Chen, Ji-Yao [State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai 200433 (China); Nyokong, Tebello, E-mail: t.nyokong@ru.ac.za [Department of Chemistry, Rhodes University, PO Box 94, Grahamstown (South Africa)

    2013-02-15

    This work reports on the synthesis of zinc tetraaminophthalocyanine (ZnTAPc) functionalized with folic acid (FA), forming ZnTAPcFA. The conjugate between FA and ZnTAPc was soluble in water whereas ZnTAPc alone is not. The structure of ZnTAPcFA conjugate was elucidated by {sup 1}H NMR, MALDI-TOF mass and FTIR spectra. Photophysical and photochemical studies of ZnTAPcFA were conducted in DMSO. The increase in fluorescence quantum yield of the conjugate was accompanied by a decrease in the triplet and singlet oxygen quantum yields. The changes in triplet quantum and singlet oxygen quantum yields were marginal when ZnTAPc was simply mixed with FA without a chemical bond. - Highlights: Black-Right-Pointing-Pointer A conjugate between folic acid and a zinc tetraaminophthalocyanine was formed. Black-Right-Pointing-Pointer The conjugate is water soluble even though the phthalocyanine alone is not. Black-Right-Pointing-Pointer The fluorescence quantum yield of the conjugate was enhanced compared to the phthalocyanine alone. Black-Right-Pointing-Pointer Triplet quantum yields decreased for the conjugate.

  5. 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.

  6. Colour-singlet exchange and tests of models of diffractive DIS

    International Nuclear Information System (INIS)

    Williams, J.C.

    2000-03-01

    Diffractive deep-inelastic scattering events observed at the HERA electron-proton collider are interpreted as an interaction involving a virtual photon scattering off a colour-singlet state within the proton. Models which attempt to describe the colour-singlet exchanged in diffractive interactions range from the purely phenomenological Donnachie-Landshoff form factor approach to the QCD-motivated gluon-exchange models and the scalar-pomeron model. It is important to find ways to test these models. In this thesis colour-singlet exchange models of diffractive DIS are compared with cross section and structure function data from the H1 detector. H1 select diffractive data by requiring there to be a large angle between the forward proton direction and any other significant detector activity. This pseudo-rapidity gap cut extracts colour-singlet exchange events from the standard DIS data sample. For a wide range of the parameter space covered by the HERA experiments, however, the pseudo-rapidity gap cuts restrict the final-state phase space available for diffractive scattering. One consequence is that pseudo-rapidity gap cuts can be used to select diffractive events in which the colour-singlet only couples to off-shell partons. To leading order in the strong coupling constant, the diffractive final state consists of a quark-antiquark pair. Higher-order events include diffractive production of quark-antiquark-gluon states. In the region where pseudo-rapidity gap cuts restrict the accessible phase space, the cuts reject low transverse momentum quark-antiquark diffractive events. Pseudo-rapidity gap data selection cuts also allow selection of an enhanced 3-jet data sample. The structure function and transverse momentum distribution data can be described by either a two-gluon model or by the Donnachie-Landshoff model, both models requiring a significant contribution from quark-antiquark-gluon diffractive final states to fit the full kinematic range of the diffractive data

  7. Riboflavin as a photosensitizer. Effects on human health and food quality.

    Science.gov (United States)

    Cardoso, Daniel R; Libardi, Silvia H; Skibsted, Leif H

    2012-05-01

    Riboflavin, vitamin B₂, and flavins (as riboflavin building blocks or degradation products) are efficient photosensitizers inducing oxidative damage to light-exposed tissue and food by substrate-dependent mechanisms, for which protection is offered by specific nutrients. Phenolic and N-heterocyclic amino acids and their peptides and proteins deactivate triplet-excited state riboflavin in diffusion controlled processes, efficiently competing with deactivation by oxygen, resulting in direct (so called Type I) protein degradation through electron transfer or proton-coupled electron transfer. In light-exposed tissue, such often long lived protein radicals may as primary photoproducts initiate lipid and vitamin oxidation. In contrast, for lipid systems, oxygen deactivation of triplet-excited state riboflavin, resulting in formation of singlet oxygen, is under aerobic conditions faster than direct deactivation by lipids, which otherwise under anaerobic conditions occurs as hydrogen atom transfer from polyunsaturated lipids to triplet riboflavin. Singlet oxygen adds to unsaturated lipids and forms lipid hydroperoxides as primary lipid oxidation products or oxidizes proteins (Type II mechanism). Carotenoids seem not to deactivate triplet riboflavin, while chromanols like vitamin E and plant polyphenols are efficient in such deactivation yielding protection of proteins and lipids by these phenols. Indirect protection against the triplet reactivity of riboflavin is further important for polyphenols as riboflavin singlet excited state quenchers in effectively preventing riboflavin intersystem crossing to yield the reactive triplet state. Riboflavin photosensitization becomes critical for degradation of proteins, unsaturated lipids, and folate, thiamine, ascorbate and other vitamins during light exposure of food during storage. For skin, eye and other tissue exposed to high intensity light, dietary polyphenols like flavonoids are important in direct protection against

  8. Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone

    Science.gov (United States)

    Lopaev, D. V.; Malykhin, E. M.; Zyryanov, S. M.

    2011-01-01

    Ozone production in an oxygen glow discharge in a quartz tube was studied in the pressure range of 10-50 Torr. The O3 density distribution along the tube diameter was measured by UV absorption spectroscopy, and ozone vibrational temperature TV was found comparing the calculated ab initio absorption spectra with the experimental ones. It has been shown that the O3 production mainly occurs on a tube surface whereas ozone is lost in the tube centre where in contrast the electron and oxygen atom densities are maximal. Two models were used to analyse the obtained results. The first one is a kinetic 1D model for the processes occurring near the tube walls with the participation of the main particles: O(3P), O2, O2(1Δg) and O3 molecules in different vibrational states. The agreement of O3 and O(3P) density profiles and TV calculated in the model with observed ones was reached by varying the single model parameter—ozone production probability (\\gamma_{O_{3}}) on the quartz tube surface on the assumption that O3 production occurs mainly in the surface recombination of physisorbed O(3P) and O2. The phenomenological model of the surface processes with the participation of oxygen atoms and molecules including singlet oxygen molecules was also considered to analyse \\gamma_{O_{3}} data obtained in the kinetic model. A good agreement between the experimental data and the data of both models—the kinetic 1D model and the phenomenological surface model—was obtained in the full range of the studied conditions that allowed consideration of the ozone surface production mechanism in more detail. The important role of singlet oxygen in ozone surface production was shown. The O3 surface production rate directly depends on the density of physisorbed oxygen atoms and molecules and can be high with increasing pressure and energy inputted into plasma while simultaneously keeping the surface temperature low enough. Using the special discharge cell design, such an approach opens up the

  9. Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone

    International Nuclear Information System (INIS)

    Lopaev, D V; Malykhin, E M; Zyryanov, S M

    2011-01-01

    Ozone production in an oxygen glow discharge in a quartz tube was studied in the pressure range of 10-50 Torr. The O 3 density distribution along the tube diameter was measured by UV absorption spectroscopy, and ozone vibrational temperature T V was found comparing the calculated ab initio absorption spectra with the experimental ones. It has been shown that the O 3 production mainly occurs on a tube surface whereas ozone is lost in the tube centre where in contrast the electron and oxygen atom densities are maximal. Two models were used to analyse the obtained results. The first one is a kinetic 1D model for the processes occurring near the tube walls with the participation of the main particles: O( 3 P), O 2 , O 2 ( 1 Δ g ) and O 3 molecules in different vibrational states. The agreement of O 3 and O( 3 P) density profiles and T V calculated in the model with observed ones was reached by varying the single model parameter-ozone production probability (γ O 3 ) on the quartz tube surface on the assumption that O 3 production occurs mainly in the surface recombination of physisorbed O( 3 P) and O 2 . The phenomenological model of the surface processes with the participation of oxygen atoms and molecules including singlet oxygen molecules was also considered to analyse γ O 3 data obtained in the kinetic model. A good agreement between the experimental data and the data of both models-the kinetic 1D model and the phenomenological surface model-was obtained in the full range of the studied conditions that allowed consideration of the ozone surface production mechanism in more detail. The important role of singlet oxygen in ozone surface production was shown. The O 3 surface production rate directly depends on the density of physisorbed oxygen atoms and molecules and can be high with increasing pressure and energy inputted into plasma while simultaneously keeping the surface temperature low enough. Using the special discharge cell design, such an approach opens up

  10. Effects of the cryptochrome CryB from Rhodobacter sphaeroides on global gene expression in the dark or blue light or in the presence of singlet oxygen.

    Directory of Open Access Journals (Sweden)

    Sebastian Frühwirth

    Full Text Available Several regulators are controlling the formation of the photosynthetic apparatus in the facultatively photosynthetic bacterium Rhodobacter sphaeroides. Among the proteins affecting photosynthesis gene expression is the blue light photoreceptor cryptochrome CryB. This study addresses the effect of CryB on global gene expression. The data reveal that CryB does not only influence photosynthesis gene expression but also genes for the non-photosynthetic energy metabolism like citric acid cycle and oxidative phosphorylation. In addition several genes involved in RNA processing and in transcriptional regulation are affected by a cryB deletion. Although CryB was shown to undergo a photocycle it does not only affect gene expression in response to blue light illumination but also in response to singlet oxygen stress conditions. While there is a large overlap in these responses, some CryB-dependent effects are specific for blue-light or photooxidative stress. In addition to protein-coding genes some genes for sRNAs show CryB-dependent expression. These findings give new insight into the function of bacterial cryptochromes and demonstrate for the first time a function in the oxidative stress response.

  11. 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.

  12. Photochemical Dynamics of Intramolecular Singlet Fission

    Science.gov (United States)

    Lin, Zhou; Iwasaki, Hikari; Van Voorhis, Troy

    2017-06-01

    Singlet fission (SF) converts a singlet exciton (S_1) into a pair of triplet ones (T_1) via a ``multi-exciton'' (ME) intermediate: S_1 \\longleftrightarrow ^1ME \\longleftrightarrow ^1(T_1T_1) \\longrightarrow 2T_1. In exothermic cases, e.g., crystalline pentacene or its derivatives, the quantum yield of SF can reach 200%. With SF doubling the electric current generated by an incident high-energy photon, the solar conversion efficiency in pentacene-based organic photovoltaics (OPVs) can exceed the Shockley-Queisser limit of 33.7%. The ME state is popularly considered to be a dimeric state with significant charge transfer (CT) character that is strongly coupled to both S_1 and ^1(T_1T_1), while this local model lacks strong support from full quantum dynamics studies. Intramolecular SF (ISF) occurring to covalently-bound dimers in the solution phase is an excellent model for a straightforward dynamics simulation of local excitons. In the present study, we investigate the ISF mechanisms for three covalently-bound dimers of pentacene derivatives, including ortho-, meta-, and para-bis(6,13-bis(triisopropylsilylethynyl)pentacene)benzene, in non-protic solvents. Specifically, we propagate the real-time, non-adiabatic quantum mechanical/molecular mechanical (QM/MM) dynamics on the potential energy surfaces associated with the states of S_1, ^1(T_1T_1) and CT. We explore how the energies of these ISF-relevant states and the non-adiabatic couplings between each other fluctuate with time and the instantaneous molecular configuration (e.g., intermonomer distance and orientation). We also quantitatively compare Condon and non-Condon ISF dynamics with solution-phase spectroscopic data. Our results allow us to understand the roles of CT energy levels in the ISF mechanism and propose a design strategy to maximize ISF efficiency. M. B. Smith and J. Michl, Chem. Rev. 110, 6891 (2010). W. Shockley and H. J. Queisser, J. Appl. Phys. 32, 510 (1961). T. C. Berkelbach, M. S. Hybertsen

  13. 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

  14. First-Principles Quantum Dynamics of Singlet Fission: Coherent versus Thermally Activated Mechanisms Governed by Molecular π Stacking

    Science.gov (United States)

    Tamura, Hiroyuki; Huix-Rotllant, Miquel; Burghardt, Irene; Olivier, Yoann; Beljonne, David

    2015-09-01

    Singlet excitons in π -stacked molecular crystals can split into two triplet excitons in a process called singlet fission that opens a route to carrier multiplication in photovoltaics. To resolve controversies about the mechanism of singlet fission, we have developed a first principles nonadiabatic quantum dynamical model that reveals the critical role of molecular stacking symmetry and provides a unified picture of coherent versus thermally activated singlet fission mechanisms in different acenes. The slip-stacked equilibrium packing structure of pentacene derivatives is found to enhance ultrafast singlet fission mediated by a coherent superexchange mechanism via higher-lying charge transfer states. By contrast, the electronic couplings for singlet fission strictly vanish at the C2 h symmetric equilibrium π stacking of rubrene. In this case, singlet fission is driven by excitations of symmetry-breaking intermolecular vibrations, rationalizing the experimentally observed temperature dependence. Design rules for optimal singlet fission materials therefore need to account for the interplay of molecular π -stacking symmetry and phonon-induced coherent or thermally activated mechanisms.

  15. Photochemical characterization of water samples from Minnesota and Vermont sites with malformed frogs: potential influence of photosensitization by singlet molecular oxygen ({sup 1}O{sub 2}) and free radicals on aquatic toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Bilski, P.; Burkhart, J.G.; Chignell, C.F

    2003-11-19

    Environmental pollutants activated by UV sunlight may have contributed to the recent decline in frog populations and the concomitant increase in malformations in the USA and abroad. UV radiation is able to mutate DNA and to initiate photosensitization processes that generate mutagenic and biologically disruptive oxygen transients. We have examined water from selected sites in Minnesota and Vermont using singlet molecular oxygen ({sup 1}O{sub 2}), detected by its phosphorescence and free radicals detected by spin trapping, as markers for photosensitization. Water from a pond in Minnesota with malformed frogs, which also causes malformations in the laboratory, photosensitized more {sup 1}O{sub 2}, even though it absorbed less UV light compared to water from a site that did not cause malformations. This suggested that unknown natural or pollutant agents were present, and that photosensitization may be involved. Although UV irradiation of the two Minnesota water samples in the presence of the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) revealed the presence of the DMPO/{center_dot}OH, DMPO/{center_dot}H(e{sub aq}{sup -}) and DMPO/{center_dot}C(unknown) adducts there were no qualitative or quantitative differences between them. We also examined water samples from several sites in Vermont, and compared them by measuring the quantum yield of {sup 1}O{sub 2} photosensitization. While all the Vermont samples produced a small amount of {sup 1}O{sub 2}, there was no clear correlation with the incidence of frog malformations. However, the samples differed strongly in absorption spectra and the ability to quench {sup 1}O{sub 2}. These factors may determine how much UV light is absorbed and converted into chemical reactions. Our results show that photochemical characterization of {sup 1}O{sub 2} photosensitization is possible in untreated natural water samples. Photosensitization falls into the category of global factors that may be closely associated with the effects of

  16. Singlet channel coupling in deuteron elastic scattering at intermediate energies

    International Nuclear Information System (INIS)

    Al-Khalili, J.S.; Tostevin, J.A.; Johnson, R.C.

    1990-01-01

    Intermediate energy deuteron elastic scattering is investigated in a three-body model incorporating relativistic kinematics. The effects of deuteron breakup to singlet spin intermediate states, on the elastic scattering observables for the 58 Ni(d vector, d) 58 Ni reaction at 400 and 700 MeV, are studied quantitatively. The singlet-breakup contributions to the elastic amplitude are estimated within an approximate two-step calculation. The calculation makes an adiabatic approximation in the intermediate states propagator which allows the use of closure over the np intermediate states continuum. The singlet channel coupling is found to produce large effects on the calculated reaction tensor analysing power A yy , characteristic of a dynamically induced second-rank tensor interaction. By inspection of the calculated breakup amplitudes we show this induced interaction to be of the T L tensor type. (orig.)

  17. Signatures for exotic quark singlets from superstrings

    International Nuclear Information System (INIS)

    Barger, V.; Deshpande, N.G.; Gunion, J.F.

    1986-09-01

    We consider various scenarios, at Superconducting Super Collider energy and luminosity, for detection of the extra colored, weak isospin singlet, charge -1/3 heavy fermion resulting from E 6 compactification in superstring theories

  18. Development of QCD jets emitted by color-singlet sources

    International Nuclear Information System (INIS)

    Ellis, R.K.; Gunion, J.F.; Kalinowski, J.; Webber, B.R.

    1985-01-01

    We compare the angular-ordering approximation to QCD jet development with full calculations to order αsub(s) in the following cases: emission of quark jets by a color-singlet vector source (as in e + e - annihilation) and emission of gluon jets by a color-singlet scalar (Fsup(a)sub(μν)Fsup(aμν)) source. In contrast to the case of a color-octet (gluon) source, we find that the approximation is good in those regions of phase space where the next-to-leading corrections to the amplitude are large. (orig.)

  19. 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.

  20. Stereoselectivity in ene reactions with 1O2: matrix effects in polymer supports, photo-oxygenation of organic salts and asymmetric synthesis.

    Science.gov (United States)

    Griesbeck, Axel G; Bartoschek, Anna; Neudörfl, Jörg; Miara, Claus

    2006-01-01

    The ene reaction of chiral allylic alcohols is applied as a tool for the investigation of intrapolymer effects by means of the stereoselectivity of the singlet-oxygen addition. The diastereo selectivity strongly depends on the structure of the polymer, the substrate loading degree and also on the degree of conversion demonstrating additional supramolecular effects evolving during the reaction. The efficiency and the stability of polymer-bound sensitizers were evaluated by the ene reaction of singlet oxygen with citronellol. The ene reaction with chiral ammonium salts of tiglic acid was conducted under solution phase conditions or in polystyrene beads under chiral contact ion-pair conditions. The products thus obtained precipitate during the photoreaction as ammonium salts. Moderate asymmetric induction was observed for this procedure for the first time.

  1. Singlet exciton fission in polycrystalline pentacene: from photophysics toward devices.

    Science.gov (United States)

    Wilson, Mark W B; Rao, Akshay; Ehrler, Bruno; Friend, Richard H

    2013-06-18

    Singlet exciton fission is the process in conjugated organic molecules bywhich a photogenerated singlet exciton couples to a nearby chromophore in the ground state, creating a pair of triplet excitons. Researchers first reported this phenomenon in the 1960s, an event that sparked further studies in the following decade. These investigations used fluorescence spectroscopy to establish that exciton fission occurred in single crystals of several acenes. However, research interest has been recently rekindled by the possibility that singlet fission could be used as a carrier multiplication technique to enhance the efficiency of photovoltaic cells. The most successful architecture to-date involves sensitizing a red-absorbing photoactive layer with a blue-absorbing material that undergoes fission, thereby generating additional photocurrent from higher-energy photons. The quest for improved solar cells has spurred a drive to better understand the fission process, which has received timely aid from modern techniques for time-resolved spectroscopy, quantum chemistry, and small-molecule device fabrication. However, the consensus interpretation of the initial studies using ultrafast transient absorption spectroscopy was that exciton fission was suppressed in polycrystalline thin films of pentacene, a material that would be otherwise expected to be an ideal model system, as well as a viable candidate for fission-sensitized photovoltaic devices. In this Account, we review the results of our recent transient absorption and device-based studies of polycrystalline pentacene. We address the controversy surrounding the assignment of spectroscopic features in transient absorption data, and illustrate how a consistent interpretation is possible. This work underpins our conclusion that singlet fission in pentacene is extraordinarily rapid (∼80 fs) and is thus the dominant decay channel for the photoexcited singlet exciton. Further, we discuss our demonstration that triplet excitons

  2. Oxygen input and oxygen yield of tanks of great depth in theory and practice; Theorie und Praxis von Sauerstoffeintrag und -ertrag bei groesseren Beckentiefen

    Energy Technology Data Exchange (ETDEWEB)

    Poepel, H.J.; Wagner, M. [Technische Hochschule Darmstadt (Germany). Inst. fuer Wasserversorgung, Abwasserbeseitigung und Raumplanung; Weidmann, F.

    1999-07-01

    Activated sludge tanks are nowadays planned and built with greater depths (8.00 to 12.00 m) than hitherto (4.00 to 6.00 m); some are already in operation. For such depths there exist no confirmed dimensioning approaches. The fundamentals of oxygen transfer in deep tanks are pointed out and a model for calculating the influence of depth is set up. It is confirmed via an extensive test program with variation of water depth, the rate of density of membrane aerators, and air volume flows. It permits converting oxygen supply parameters of an aeration system established for a certain blow-in depth to a given alternative depth. For oxygen yield, too, relations are developed, which indicate gross yield for different compressor types (sliding vane rotary compressor, turbo compressor, screw-type compressor) as a function of blow-in-depth, air volume flow and rate of density with great accuracy. (orig.) [German] Belebungsbecken werden heute tiefer (8,00 bis 12,00 m) als bisher (4,00 bis 6,00 m) geplant, gebaut und bereits betrieben. Fuer diese Tiefen liegen keine gesicherten Bemesssungsansaetze vor. Die Grundlagen des Sauerstoffuebergangs in tiefen Becken werden dargelegt und ein Modell zur Berechnung des Tiefeneinflusses erstellt. Ueber ein ausfuehrliches Versuchsprogramm mit Variation der Wassertiefe, der Belegungsdichte mit Membranbelueftern und der Luftvolumenstroeme wird das Modell bestaetigt. Damit koennen Sauerstoffzufuhrparametern eines Belueftungssystems, die fuer eine bestimmte Einblastiefe bekannt sind, auf beliebige andere Tiefen umgerechnet werden. Auch fuer den Sauerstoffertrag werden Beziehungen entwickelt, die den Bruttoertrag fuer unterschiedliche Verdichterarten (Drehkolben-, Turbo- und Schraubenverdichter) in Abhaengigkeit von Einblastiefe, Luftvolumenstrom und Belegungsdichte mit grosser Genauigkeit festlegen. (orig.)

  3. 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)

  4. Quenching of porous silicon photoluminescence by molecular oxygen and dependence of this phenomenon on storing media and method of preparation of pSi photosensitizer

    Science.gov (United States)

    Balaguer, María; Matveeva, Eugenia

    2010-10-01

    The quenching of porous silicon photoluminescence (pSi PL) by molecular oxygen has been studied in different storing media in an attempt to clarify the mechanism of the energy transfer from the silicon photosensitizer to the oxygen acceptor. Luminescent materials have been prepared by two methods: electrochemical anodizing and chemical etching. Different structural forms were used: porous layers on silicon wafer and two kinds of differently prepared powder. Dry air and liquid water were employed as storing media; quenching behaviour was under observation until total degradation of quenching properties. Singlet oxygen molecules generation through energy transfer from photoluminescent pSi was the only photosensitizing mechanism observed under dry gas conditions. This PL quenching process was preferentially developed at 760 nm (1.63 eV) that corresponds to the formation of the 1Σ singlet oxygen state. Oxidation of the pSi photosensitizer was the main factor that led to its total deactivation in a time scale of few weeks. Regarding water medium, different photosensitizing behaviour was observed. In watery conditions, two preferred energy levels were found: the one detected in dry gas and another centred at approximately 2.2 eV (550 nm). Formation of reactive oxygen species (ROS) different from singlet oxygen, such as superoxide anion or superoxide radical, can be responsible for the second one. This second quenching process developed gradually after the initial contact of pSi photosensitizer with water and then degraded. The process lasted only several hours. Therefore, functionalization of the pSi photosensitizer is probably required to stabilize its PL and quenching properties in the watery physiological conditions required for biomedical applications.

  5. Quenching of porous silicon photoluminescence by molecular oxygen and dependence of this phenomenon on storing media and method of preparation of pSi photosensitizer

    Energy Technology Data Exchange (ETDEWEB)

    Balaguer, Maria, E-mail: mabara@itq.upv.e [Technical University of Valencia, Nanophotonics Technology Center (Spain); Matveeva, Eugenia, E-mail: eumat@em-silicon.co [EM-Silicon Nano-Technologies, S.L. (Spain)

    2010-10-15

    The quenching of porous silicon photoluminescence (pSi PL) by molecular oxygen has been studied in different storing media in an attempt to clarify the mechanism of the energy transfer from the silicon photosensitizer to the oxygen acceptor. Luminescent materials have been prepared by two methods: electrochemical anodizing and chemical etching. Different structural forms were used: porous layers on silicon wafer and two kinds of differently prepared powder. Dry air and liquid water were employed as storing media; quenching behaviour was under observation until total degradation of quenching properties. Singlet oxygen molecules generation through energy transfer from photoluminescent pSi was the only photosensitizing mechanism observed under dry gas conditions. This PL quenching process was preferentially developed at 760 nm (1.63 eV) that corresponds to the formation of the {sup 1{Sigma}} singlet oxygen state. Oxidation of the pSi photosensitizer was the main factor that led to its total deactivation in a time scale of few weeks. Regarding water medium, different photosensitizing behaviour was observed. In watery conditions, two preferred energy levels were found: the one detected in dry gas and another centred at approximately 2.2 eV (550 nm). Formation of reactive oxygen species (ROS) different from singlet oxygen, such as superoxide anion or superoxide radical, can be responsible for the second one. This second quenching process developed gradually after the initial contact of pSi photosensitizer with water and then degraded. The process lasted only several hours. Therefore, functionalization of the pSi photosensitizer is probably required to stabilize its PL and quenching properties in the watery physiological conditions required for biomedical applications.

  6. Standard Model with a real singlet scalar and inflation

    Energy Technology Data Exchange (ETDEWEB)

    Enqvist, Kari; Nurmi, Sami; Tenkanen, Tommi; Tuominen, Kimmo, E-mail: kari.enqvist@helsinki.fi, E-mail: sami.nurmi@helsinki.fi, E-mail: tommi.tenkanen@helsinki.fi, E-mail: kimmo.i.tuominen@helsinki.fi [University of Helsinki and Helsinki Institute of Physics, P.O. Box 64, FI-00014, Helsinki (Finland)

    2014-08-01

    We study the post-inflationary dynamics of the Standard Model Higgs and a real singlet scalar s, coupled together through a renormalizable coupling λ{sub sh}h{sup 2}s{sup 2}, in a Z{sub 2} symmetric model that may explain the observed dark matter abundance and/or the origin of baryon asymmetry. The initial values for the Higgs and s condensates are given by inflationary fluctuations, and we follow their dissipation and relaxation to the low energy vacua. We find that both the lowest order perturbative and the non-perturbative decays are blocked by thermal effects and large background fields and that the condensates decay by two-loop thermal effects. Assuming instant reheating at T=10{sup 16} GeV, the characteristic temperature for the Higgs condensate thermalization is found to be T{sub h} ∼ 10{sup 14} GeV, whereas s thermalizes typically around T{sub s} ∼ 10{sup 6} GeV. By that time, the amplitude of the singlet is driven very close to the vacuum value by the expansion of the universe, unless the portal coupling takes a value λ{sub sh}∼< 10{sup -7} and the singlet s never thermalizes. With these values of the coupling, it is possible to slowly produce a sizeable fraction of the observed dark matter abundance via singlet condensate fragmentation and thermal Higgs scattering. Physics also below the electroweak scale can therefore be affected by the non-vacuum initial conditions generated by inflation.

  7. The low-lying electronic states of pentacene and their roles in singlet fission.

    Science.gov (United States)

    Zeng, Tao; Hoffmann, Roald; Ananth, Nandini

    2014-04-16

    We present a detailed study of pentacene monomer and dimer that serves to reconcile extant views of its singlet fission. We obtain the correct ordering of singlet excited-state energy levels in a pentacene molecule (E (S1) pentacene, we use a well-developed diabatization scheme to characterize the six low-lying singlet states of a pentacene dimer that approximates the unit cell structure of crystalline pentacene. The local, single-excitonic diabats are not directly coupled with the important multiexcitonic state but rather mix through their mutual couplings with one of the charge-transfer configurations. We analyze the mixing of diabats as a function of monomer separation and pentacene rotation. By defining an oscillator strength measure of the coherent population of the multiexcitonic diabat, essential to singlet fission, we find this population can, in principle, be increased by small compression along a specific crystal direction.

  8. Photogeneration of reactive transient species upon irradiation of natural water samples: Formation quantum yields in different spectral intervals, and implications for the photochemistry of surface waters.

    Science.gov (United States)

    Marchisio, Andrea; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

    2015-04-15

    Chromophoric dissolved organic matter (CDOM) in surface waters is a photochemical source of several transient species such as CDOM triplet states ((3)CDOM*), singlet oxygen ((1)O2) and the hydroxyl radical (OH). By irradiation of lake water samples, it is shown here that the quantum yields for the formation of these transients by CDOM vary depending on the irradiation wavelength range, in the order UVB > UVA > blue. A possible explanation is that radiation at longer wavelengths is preferentially absorbed by the larger CDOM fractions, which show lesser photoactivity compared to smaller CDOM moieties. The quantum yield variations in different spectral ranges were definitely more marked for (3)CDOM* and OH compared to (1)O2. The decrease of the quantum yields with increasing wavelength has important implications for the photochemistry of surface waters, because long-wavelength radiation penetrates deeper in water columns compared to short-wavelength radiation. The average steady-state concentrations of the transients ((3)CDOM*, (1)O2 and OH) were modelled in water columns of different depths, based on the experimentally determined wavelength trends of the formation quantum yields. Important differences were found between such modelling results and those obtained in a wavelength-independent quantum yield scenario. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and 1O2 generation

    International Nuclear Information System (INIS)

    Pan, Jie; Jiang, Lijun; Chan, Chi-Fai; Tsoi, Tik-Hung; Shiu, Kwok-Keung; Kwong, Daniel W.J.; Wong, Wing-Tak; Wong, Wai-Kwok; Wong, Ka-Leung

    2017-01-01

    Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

  10. Update on scalar singlet dark matter

    NARCIS (Netherlands)

    Cline, J.M.; Scott, P.; Kainulainen, K.; Weniger, C.

    2013-01-01

    One of the simplest models of dark matter is where a scalar singlet field S comprises some or all of the dark matter and interacts with the standard model through an vertical bar H vertical bar S-2(2) coupling to the Higgs boson. We update the present limits on the model from LHC searches for

  11. Photodissociation of van der Waals clusters of isoprene with oxygen, C{sub 5}H{sub 8}-O{sub 2}, in the wavelength range 213-277 nm

    Energy Technology Data Exchange (ETDEWEB)

    Vidma, Konstantin V.; Frederix, Pim W. J. M.; Parker, David H. [Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 ED Nijmegen (Netherlands); Baklanov, Alexey V. [Institute of Chemical Kinetics and Combustion, Institutskaja Street 3, Novosibirsk 630090 (Russian Federation) and Novosibirsk State University, Pirogova street 2, Novosibirsk 630090 (Russian Federation)

    2012-08-07

    observed channels corresponds to O atoms produced by photodissociation of molecular oxygen in the excited a {sup 1}{Delta}{sub g} and b {sup 1}{Sigma}{sub g}{sup +} singlet states as the precursors. This indicates the formation of singlet oxygen O{sub 2}(a {sup 1}{Delta}{sub g}) and O{sub 2}(b {sup 1}{Sigma}{sub g}{sup +}) after excitation of the C{sub 5}H{sub 8}-O{sub 2} complex. Cooperative excitation of the complex with a simultaneous change of the spin of both partners {sup 1}X-{sup 3}O{sub 2}+h{nu}{yields}{sup 3}X-{sup 1}O{sub 2}{yields}{sup 3}X +{sup 1}O{sub 2} is suggested as a source of singlet oxygen O{sub 2}(a {sup 1}{Delta}{sub g}) and O{sub 2}(b {sup 1}{Sigma}{sub g}{sup +}). This cooperative excitation is in agreement with little or no vibrational excitation of O{sub 2}(a {sup 1}{Delta}{sub g}), produced from the C{sub 5}H{sub 8}-O{sub 2} complex as studied in the current paper as well as from the C{sub 3}H{sub 6}-O{sub 2} and CH{sub 3}I-O{sub 2} complexes reported in our previous paper [Baklanov et al., J. Chem. Phys. 126, 124316 (2007)]. The formation of O{sub 2}(a {sup 1}{Delta}{sub g}) from C{sub 5}H{sub 8}-O{sub 2} was observed at {lambda}{sub pump}= 213-277 nm with the yield going down towards the long wavelength edge of this interval. This spectral profile is interpreted as the red-side wing of the band of a cooperative transition {sup 1}X-{sup 3}O{sub 2}+h{nu}{yields}{sup 3}X(T{sub 2})-{sup 1}O{sub 2}(a {sup 1}{Delta}{sub g}) in the C{sub 5}H{sub 8}-O{sub 2} complex.

  12. 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.

  13. Trap-induced photoconductivity in singlet fission pentacene diodes

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, Xianfeng, E-mail: qiaoxianfeng@hotmail.com; Zhao, Chen; Chen, Bingbing; Luan, Lin [WuHan National Laboratory for Optoelectronics and School of Optical and Electronic Information, Huazhong University of Science and Technology, Wu Han 430074 (China)

    2014-07-21

    This paper reports a trap-induced photoconductivity in ITO/pentacene/Al diodes by using current-voltage and magneto-conductance measurements. The comparison of photoconductivity between pentacene diodes with and without trap clearly shows that the traps play a critical role in generating photoconductivity. It shows that no observable photoconductivity is detected for trap-free pentacene diodes, while significant photoconductivity is observed in diodes with trap. This is because the initial photogenerated singlet excitons in pentacene can rapidly split into triplet excitons with higher binding energy prior to dissociating into free charge carriers. The generated triplet excitons react with trapped charges to release charge-carriers from traps, leading to a trap-induced photoconductivity in the single-layer pentacene diodes. Our studies elucidated the formation mechanisms of photoconductivity in pentacene diodes with extremely fast singlet fission rate.

  14. High oxygen partial pressure increases photodynamic effect on HeLa cell lines in the presence of chloraluminium phthalocyanine.

    Science.gov (United States)

    Bajgar, Robert; Kolarova, Hana; Bolek, Lukas; Binder, Svatopluk; Pizova, Klara; Hanakova, Adela

    2014-08-01

    Photodynamic therapy (PDT) is linked with oxidative damage of biomolecules causing significant impairment of essential cellular functions that lead to cell death. It is the reason why photodynamic therapy has found application in treatment of different oncological, cardiovascular, skin and eye diseases. Efficacy of PDT depends on combined action of three components; sensitizer, light and oxygen. In the present study, we examined whether higher partial pressure of oxygen increases lethality in HeLa cell lines exposed to light in the presence of chloraluminium phthalocyanine disulfonate (ClAlPcS2). ClAlPcS2- sensitized HeLa cells incubated under different oxygen conditions were exposed to PDT. Production of singlet oxygen ((1)O2) and other forms of reactive oxygen species (ROS) as well as changes in mitochondrial membrane potential were determined by appropriately sensitive fluorescence probes. The effect of PDT on HeLa cell viability under different oxygen conditions was quantified using the standard methylthiazol tetrazolium (MTT) test. At the highest oxygen concentration of 28 ± 2 mg/l HeLa cells were significantly more sensitive to light-activated ClAlPcS2 (EC50=0.29 ± 0.05 μM) in comparison to cells incubated at lower oxygen concentrations of 8 ± 0.5 and 0.5 ± 0.1 mg/l, where the half maximal effective concentration was 0.42 ± 0.06 μM and 0.94 ± 0.14 μM, respectively. Moreover, we found that the higher presence of oxygen is accompanied with higher production of singlet oxygen, a higher rate of type II photodynamic reactions, and a significant drop in the mitochondrial membrane potential. These results demonstrate that the photodynamic effect in cervical cancer cells utilizing ClAlPcS2 significantly depends on oxygen level. Copyright© 2014 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  15. Analyzing of singlet fermionic dark matter via the updated direct detection data

    Energy Technology Data Exchange (ETDEWEB)

    Ettefaghi, M.M.; Moazzemi, R. [University of Qom, Department of Physics, Qom (Iran, Islamic Republic of)

    2017-05-15

    We revisit the parameter space of singlet fermionic cold dark matter model in order to determine the role of the mixing angle between the standard model Higgs and a new singlet one. Furthermore, we restudy the direct detection constraints with the updated and new experimental data. As an important conclusion, this model is completely excluded by recent XENON100, PandaX II and LUX data. (orig.)

  16. 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.

  17. 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)

  18. The nature of singlet excitons in oligoacene molecular crystals

    KAUST Repository

    Yamagata, H.; Norton, J.; Hontz, E.; Olivier, Y.; Beljonne, D.; Brédas, J. L.; Silbey, R. J.; Spano, F. C.

    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.

  19. 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.......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....

  20. Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and {sup 1}O{sub 2} generation

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Jie; Jiang, Lijun; Chan, Chi-Fai [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Tsoi, Tik-Hung [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Shiu, Kwok-Keung; Kwong, Daniel W.J. [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Wong, Wai-Kwok, E-mail: wkwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

    2017-04-15

    Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

  1. Explicit role of dynamical and nondynamical electron correlation on singlet-triplet splitting in carbenes

    International Nuclear Information System (INIS)

    Seal, Prasenjit; Chakrabarti, Swapan

    2007-01-01

    Density functional theoretical studies have been performed on carbene systems to determine the singlet-triplet splitting and also to explore the role of electron correlation. Using an approximate method of separation of dynamical and nondynamical correlation, it is found that dynamical and nondynamical electron correlation stabilizes the singlet state relative to the triplet for halo carbenes in both BLYP and B3LYP methods. Calculations performed on higher homologues of methylene suggest that beyond CH(CH 3 ), both the electron correlations have leveling effect in stabilizing the singlet state relative to the triplet. It has also been observed while dynamical electron correlation fails to provide any substantial degree of stabilization to the singlet states of higher homologues of methylene in B3LYP method, an opposite trend is observed for nondynamical counterpart. Among the larger systems studied (9-triptycyl)(α-naphthyl)-carbene has the highest stability of the triplet state whereas bis-imidazol-2-ylidenes has the most stable singlet state. Interestingly, the values of the dynamical electron correlation for each state of each system studied are different for the two methods used. The reason behind this apparent discrepancy lies in the fact that the coefficients of the LYP part in B3LYP and BLYP functionals are different

  2. Porous Silicon Nanoparticle Photosensitizers for Singlet Oxygen and Their Phototoxicity Against Cancer Cells

    Science.gov (United States)

    Xiao, Ling; Gu, Luo; Howell, Stephen B.; Sailor, Michael J.

    2011-01-01

    Porous Si nanoparticles, prepared from electrochemically etched single crystal Si wafers, function as photosensitizers to generate 1O2 in ethanol and in aqueous media. The preparation conditions for the porous Si nanoparticles were optimized to maximize (1) the yield of material; (2) its quantum yield of 1O2 production; and (3) its in vitro degradation properties. The optimal formulation was determined to consist of nanoparticles 146 ± 7 nm in diameter, with nominal pore sizes of 12 ± 4 nm. The quantum yield for 1O2 production is 0.10 ± 0.02 in ethanol and 0.17 ± 0.01 in H2O. HeLa or NIH-3T3 cells treated with 100 µg/mL porous Si nanoparticles and exposed to 60 J/cm2 white light (infrared filtered, 100 mW/cm2 for 10 min) exhibit ~ 45% cell death, while controls containing no nanoparticles show 10% or 25% cell death, respectively. The dark control experiment yields < 10% cytotoxicity for either cell type. PMID:21452822

  3. Flavor-singlet baryons in the graded symmetry approach to partially quenched QCD

    Science.gov (United States)

    Hall, Jonathan M. M.; Leinweber, Derek B.

    2016-11-01

    Progress in the calculation of the electromagnetic properties of baryon excitations in lattice QCD presents new challenges in the determination of sea-quark loop contributions to matrix elements. A reliable estimation of the sea-quark loop contributions represents a pressing issue in the accurate comparison of lattice QCD results with experiment. In this article, an extension of the graded symmetry approach to partially quenched QCD is presented, which builds on previous theory by explicitly including flavor-singlet baryons in its construction. The formalism takes into account the interactions among both octet and singlet baryons, octet mesons, and their ghost counterparts; the latter enables the isolation of the quark-flow disconnected sea-quark loop contributions. The introduction of flavor-singlet states enables systematic studies of the internal structure of Λ -baryon excitations in lattice QCD, including the topical Λ (1405 ).

  4. Direct detection of singlet dark matter in classically scale-invariant standard model

    Directory of Open Access Journals (Sweden)

    Kazuhiro Endo

    2015-10-01

    Full Text Available Classical scale invariance is one of the possible solutions to explain the origin of the electroweak scale. The simplest extension is the classically scale-invariant standard model augmented by a multiplet of gauge singlet real scalar. In the previous study it was shown that the properties of the Higgs potential deviate substantially, which can be observed in the International Linear Collider. On the other hand, since the multiplet does not acquire vacuum expectation value, the singlet components are stable and can be dark matter. In this letter we study the detectability of the real singlet scalar bosons in the experiment of the direct detection of dark matter. It is shown that a part of this model has already been excluded and the rest of the parameter space is within the reach of the future experiment.

  5. Singlet deflected anomaly/gauge mediation

    International Nuclear Information System (INIS)

    Blas, J. de; Delgado, A.

    2012-01-01

    We study an extension of the standard anomaly/gauge mediation scenario where the messenger fields have direct interactions with an extra gauge singlet. This realizes a phenomenologically viable NMSSM-like scenario free of the μ-b μ problem. Current cosmological constraints imply a small size for the anomaly-mediation contributions, unless some source of R-parity violation is permitted. In the latter case the allowed regions in the parameter space can be substantially larger than in the corresponding gauge-mediation scenario.

  6. Oxygen consumption in EPDM irradiated under different oxygen pressures and at different LET

    International Nuclear Information System (INIS)

    Dely, N.; Ngono-Ravache, Y.; Ramillon, J.-M.; Balanzat, E.

    2005-01-01

    We conceived a novel set-up for measuring the radiochemical yields of oxygen consumption in polymers. The measurement is based on a sampling of the gas mixture with a mass spectrometer, before and after irradiation. We irradiated an ethylene, propylene and 1,4-hexadiene terpolymer (EPDM) with 1 MeV electron and 10.75 MeV/A carbon beams. Samples were irradiated under oxygen within a wide range of pressure (5-200 mbar). The yields under C irradiation are four times smaller than the yields under electron irradiation. This shows that radiooxidation is very sensitive to the linear energy transfer of the projectiles and hence to the heterogeneity of the energy deposition. The oxygen consumption yields do not vary significantly in the range of pressure investigated; even at 5 mbar, the kinetics is still governed by the bimolecular recombination of peroxy radicals

  7. High-yield production of biologically active recombinant protein in shake flask culture by combination of enzyme-based glucose delivery and increased oxygen transfer

    Directory of Open Access Journals (Sweden)

    Ukkonen Kaisa

    2011-12-01

    Full Text Available Abstract This report describes the combined use of an enzyme-based glucose release system (EnBase® and high-aeration shake flask (Ultra Yield Flask™. The benefit of this combination is demonstrated by over 100-fold improvement in the active yield of recombinant alcohol dehydrogenase expressed in E. coli. Compared to Terrific Broth and ZYM-5052 autoinduction medium, the EnBase system improved yield mainly through increased productivity per cell. Four-fold increase in oxygen transfer by the Ultra Yield Flask contributed to higher cell density with EnBase but not with the other tested media, and consequently the product yield per ml of EnBase culture was further improved.

  8. 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.

  9. 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...

  10. 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

  11. A rigorous nonorthogonal configuration interaction approach for the calculation of electronic couplings between diabatic states applied to singlet fission

    NARCIS (Netherlands)

    Wibowo, Meilani; Broer, Ria; Havenith, Remco W. A.

    2017-01-01

    For the design of efficient singlet fission chromophores, knowledge of the factors that govern the singlet fission rate is important. This rate is approximately proportional to the electronic coupling between the lowest (diabatic) spin singlet state that is populated following photoexcitation state

  12. Synthesis and Spectral Evaluation of Some Unsymmetrical Mesoporphyrinic Complexes

    Directory of Open Access Journals (Sweden)

    Rica Boscencu

    2012-06-01

    Full Text Available Synthesis and spectral evaluation of new zinc and copper unsymmetrical mesoporphyrinic complexes are reported. Zn(II-5-(4-acetoxy-3-methoxyphenyl-10,15,20-tris-(4-carboxymethylphenylporphyrin, Zn(II-5-[(3,4-methylenedioxyphenyl]-10,15,20-tris-(4-carboxymethylphenylporphyrin, Cu(II-5-(4-acetoxy-3-methoxyphenyl-10,15,20-tris-(4-carboxymethylphenylporphyrin and Cu(II-5-[(3,4-methylenedioxyphenyl]-10,15,20-tris-(4-carboxymethylphenylporphyrin were synthesized using microwave-assisted synthesis. The complexes were characterized by elemental analysis, FT-IR, UV-Vis, EPR and NMR spectroscopy, which fully confirmed their structure. The spectral absorption properties of the porphyrinic complexes were studied in solvents with different polarities. Fluorescence emission and singlet oxygen formation quantum yields were evaluated for the compounds under study, revealing high yields for the zinc derivatives. The copper complexes are not emissive and only display residual capacity for singlet oxygen formation.

  13. Prevention of alloimmunization by ultraviolet-B irradiation. Inactivation of leukocytes and the generation of active oxygen and radicals

    International Nuclear Information System (INIS)

    Takahashi, Tsuneo; Mogi, Yuko; Sekiguchi, Sadayoshi; Akasaka, Junichi; Kamo, Naoki; Kuwabara, Mikinori.

    1994-01-01

    UV-B irradiation of platelet concentrates (PC) has been tried in several institutes to inactivate leukocytes in PC and prevent alloimmunization on platelet transfusion. However, the mechanism of inactivation of leukocytes contaminating PC has not been fully understood. It is known that UV-B light is absorbed by photosensitizers in cells and produces active oxygen and radicals, such as singlet oxygen, superioxide anions and hydroxyl radicals. These active oxygen or radicals should injure cellular components and this could cause the suppression of cellular functions. In this study, we investigated the relationships among UV-B irradiation, free radical generation and leukocyte inactivation. We found the evidence that active oxygen and radicals were produced in peripheral blood mononuclear cells by UV-B irradiation. UV-B irradiation suppressed the stimulatory function of leukocytes in a mixed lymphocyte reaction (MLR), and the suppression depended on the dosage of UV-B. Even a low dosage of UV-B, 10 J/m 2 , could inhibit the MLR if the irradiated cells were incubated at 37degC for 24 hours before co-culture with responder cells. Treatments of cells with the exogenous singlet oxygen or superoxide anions also caused suppression of the stimulatory function in the MLR, inhibition of capping formation of HLA-DR antigens, and an increase of intracellular free Ca 2+ levels as did the UV-B treatment. These results indicate that the active oxygen or radicals generated in UV-B-irradiated leukocytes could be one of the causes of leukocyte inactivation. (author0

  14. Establishment and intra-/inter-laboratory validation of a standard protocol of reactive oxygen species assay for chemical photosafety evaluation.

    Science.gov (United States)

    Onoue, Satomi; Hosoi, Kazuhiro; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Matsuoka, Naoko; Nakamura, Kazuichi; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Seto, Yoshiki; Kato, Masashi; Yamada, Shizuo; Ohno, Yasuo; Kojima, Hajime

    2013-11-01

    A reactive oxygen species (ROS) assay was previously developed for photosafety evaluation of pharmaceuticals, and the present multi-center study aimed to establish and validate a standard protocol for ROS assay. In three participating laboratories, two standards and 42 coded chemicals, including 23 phototoxins and 19 nonphototoxic drugs/chemicals, were assessed by the ROS assay according to the standardized protocol. Most phototoxins tended to generate singlet oxygen and/or superoxide under UV-vis exposure, but nonphototoxic chemicals were less photoreactive. In the ROS assay on quinine (200 µm), a typical phototoxic drug, the intra- and inter-day precisions (coefficient of variation; CV) were found to be 1.5-7.4% and 1.7-9.3%, respectively. The inter-laboratory CV for quinine averaged 15.4% for singlet oxygen and 17.0% for superoxide. The ROS assay on 42 coded chemicals (200 µm) provided no false negative predictions upon previously defined criteria as compared with the in vitro/in vivo phototoxicity, although several false positives appeared. Outcomes from the validation study were indicative of satisfactory transferability, intra- and inter-laboratory variability, and predictive capacity of the ROS assay. Copyright © 2012 John Wiley & Sons, Ltd.

  15. Astrophysical constraints on singlet scalars at LHC

    Science.gov (United States)

    Hertzberg, Mark P.; Masoumi, Ali

    2017-04-01

    We consider the viability of new heavy gauge singlet scalar particles at colliders such as the LHC . Our original motivation for this study came from the possibility of a new heavy particle of mass ~ TeV decaying significantly into two photons at colliders, such as LHC, but our analysis applies more broadly. We show that there are significant constraints from astrophysics and cosmology on the simplest UV complete models that incorporate such new particles and its associated collider signal. The simplest and most obvious UV complete model that incorporates such signals is that it arises from a new singlet scalar (or pseudo-scalar) coupled to a new electrically charged and colored heavy fermion. Here we show that these new fermions (and anti-fermions) would be produced in the early universe, then form new color singlet heavy mesons with light quarks, obtain a non-negligible freeze-out abundance, and remain in kinetic equilibrium until decoupling. These heavy mesons possess interesting phenomenology, dependent on their charge, including forming new bound states with electrons and protons. We show that a significant number of these heavy states would survive for the age of the universe and an appreciable number would eventually be contained within the earth and solar system. We show that this leads to detectable consequences, including the production of highly energetic events from annihilations on earth, new spectral lines, and, spectacularly, the destabilization of stars. The lack of detection of these consequences rules out such simple UV completions, putting pressure on the viability of such new particles at LHC . To incorporate such a scalar would require either much more complicated UV completions or even further new physics that provides a decay channel for the associated fermion.

  16. Astrophysical constraints on singlet scalars at LHC

    Energy Technology Data Exchange (ETDEWEB)

    Hertzberg, Mark P.; Masoumi, Ali, E-mail: mark.hertzberg@tufts.edu, E-mail: ali@cosmos.phy.tufts.edu [Institute of Cosmology, Department of Physics and Astronomy, Tufts University, Medford, MA 02155 (United States)

    2017-04-01

    We consider the viability of new heavy gauge singlet scalar particles at colliders such as the LHC . Our original motivation for this study came from the possibility of a new heavy particle of mass ∼ TeV decaying significantly into two photons at colliders, such as LHC, but our analysis applies more broadly. We show that there are significant constraints from astrophysics and cosmology on the simplest UV complete models that incorporate such new particles and its associated collider signal. The simplest and most obvious UV complete model that incorporates such signals is that it arises from a new singlet scalar (or pseudo-scalar) coupled to a new electrically charged and colored heavy fermion. Here we show that these new fermions (and anti-fermions) would be produced in the early universe, then form new color singlet heavy mesons with light quarks, obtain a non-negligible freeze-out abundance, and remain in kinetic equilibrium until decoupling. These heavy mesons possess interesting phenomenology, dependent on their charge, including forming new bound states with electrons and protons. We show that a significant number of these heavy states would survive for the age of the universe and an appreciable number would eventually be contained within the earth and solar system. We show that this leads to detectable consequences, including the production of highly energetic events from annihilations on earth, new spectral lines, and, spectacularly, the destabilization of stars. The lack of detection of these consequences rules out such simple UV completions, putting pressure on the viability of such new particles at LHC . To incorporate such a scalar would require either much more complicated UV completions or even further new physics that provides a decay channel for the associated fermion.

  17. LHC signals for singlet neutrinos from a natural warped seesaw mechanism. II

    Science.gov (United States)

    Agashe, Kaustubh; Du, Peizhi; Hong, Sungwoo

    2018-04-01

    A natural seesaw mechanism for obtaining the observed size of SM neutrino masses can arise in a warped extra-dimensional/composite Higgs framework. In a previous paper, we initiated the study of signals at the LHC for the associated ˜TeV mass SM singlet neutrinos, within a canonical model of S U (2 )L×S U (2 )R×U (1 )B-L (LR) symmetry in the composite sector, as motivated by consistency with the EW precision tests. Here, we investigate LHC signals in a different region of parameter space for the same model, where production of singlet neutrinos can occur from particles beyond those in the usual LR models. Specifically, we assume that the composite (B -L ) gauge boson is lighter than all the others in the EW sector. We show that the composite (B -L ) gauge boson can acquire a significant coupling to light quarks simply via mixing with elementary hypercharge gauge boson. Thus, the singlet neutrino can be pair-produced via decays of the(B -L ) gauge boson, without a charged current counterpart. Furthermore, there is no decay for the (B -L ) gauge boson directly into dibosons, unlike for the usual case of WR± and Z'. Independently of the above extension of the EW sector, we analyze production of singlet neutrinos in decays of composite partners of S U (2 )L doublet leptons, which are absent in the usual LR models. In turn, these doublet leptons can be produced in composite WL decays. We show that the 4 -5 σ signal can be achieved for both cases described above for the following spectrum with 3000 fb-1 luminosity: 2-2.5 TeV composite gauge bosons, 1 TeV composite doublet lepton (for the second case) and 500-750 GeV singlet neutrino.

  18. Adler function, sum rules and Crewther relation of order O(αs4): The singlet case

    International Nuclear Information System (INIS)

    Baikov, P.A.; Chetyrkin, K.G.; Kühn, J.H.; Rittinger, J.

    2012-01-01

    The analytic result for the singlet part of the Adler function of the vector current in a general gauge theory is presented in five-loop approximation. Comparing this result with the corresponding singlet part of the Gross-Llewellyn Smith sum rule (Baikov et al., 2010 ), we successfully demonstrate the validity of the generalized Crewther relation for the singlet part. This provides a non-trivial test of both our calculations and the generalized Crewther relation. Combining the result with the already available non-singlet part of the Adler function (Baikov et al., 2008 , Baikov et al., 2010 ) we arrive at the complete O(α s 4 ) expression for the Adler function and, as a direct consequence, at the complete O(α s 4 ) correction to the e + e - annihilation into hadrons in a general gauge theory.

  19. 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.

  20. Constraints on singlet right-handed neutrinos coming from the Z0-width

    International Nuclear Information System (INIS)

    Escobar, C.O.; Peres, O.L.G.; Pleitez, V.

    1992-12-01

    The constraints on masses and missing angles imposed by the measured Z 0 invisible width, in a model in which a singlet right-handed neutrino mixes with all the Standard model neutrinos are studied. If neutrinos are massive an important question to be answered concerns the way the Z-pole observables constraint their masses and mixing parameters. In particular the measured Z-invisible width, Γ inv , implies that the number of families is compatible with three. On the other hand, it is well known that this number need not to be an integer number if right-handed neutrinos transformed as singlets under SU(2) L x U(1) Y are added to the particle content of the theory. Experimental searches for sequential neutron leptons beyond the three generations exclude stable Dirac neutrinos below 41.8 GeV and stable Majorana neutrinos below 34.8 GeV. For the unstable cases these values are 46,4 and 45.1 GeV respectively. However, it is worth stressing that these limits are valid for sequential leptons and do not apply to the case of singlets of right-handed neutrinos. Here we will consider the simplest extension of the standard electroweak model with the addition of the one right-handed singlet neutral fermion, resulting in 4 physical neutrinos two of them massless and two massive ones. (author)

  1. 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.

  2. Singlet oxygen sensitizing materials based on porous silicone: photochemical characterization, effect of dye reloading and application to water disinfection with solar reactors.

    Science.gov (United States)

    Manjón, Francisco; Santana-Magaña, Montserrat; García-Fresnadillo, David; Orellana, Guillermo

    2010-06-01

    Photogeneration of singlet molecular oxygen ((1)O(2)) is applied to organic synthesis (photooxidations), atmosphere/water treatment (disinfection), antibiofouling materials and in photodynamic therapy of cancer. In this paper, (1)O(2) photosensitizing materials containing the dyes tris(4,4'-diphenyl-2,2'-bipyridine)ruthenium(II) (1, RDB(2+)) or tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) (2, RDP(2+)), immobilized on porous silicone (abbreviated RDB/pSil and RDP/pSil), have been produced and tested for waterborne Enterococcus faecalis inactivation using a laboratory solar simulator and a compound parabolic collector (CPC)-based solar photoreactor. In order to investigate the feasibility of its reuse, the sunlight-exposed RDP/pSil sensitizing material (RDP/pSil-a) has been reloaded with RDP(2+) (RDP/pSil-r). Surprisingly, results for bacteria inactivation with the reloaded material have demonstrated a 4-fold higher efficiency compared to those of either RDP/pSil-a, unused RDB/pSil and the original RDP/pSil. Surface and bulk photochemical characterization of the new material (RDP/pSil-r) has shown that the bactericidal efficiency enhancement is due to aggregation of the silicone-supported photosensitizer on the surface of the polymer, as evidenced by confocal fluorescence lifetime imaging microscopy (FLIM). Photogenerated (1)O(2) lifetimes in the wet sensitizer-doped silicone have been determined to be ten times longer than in water. These facts, together with the water rheology in the solar reactor and the interfacial production of the biocidal species, account for the more effective disinfection observed with the reloaded photosensitizing material. These results extend and improve the operational lifetime of photocatalytic materials for point-of-use (1)O(2)-mediated solar water disinfection.

  3. 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

  4. 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.

  5. 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

    The use of hyperpolarization to enhance the sensitivity of MRI has so far been limited by the decay of the polarization through T1 relaxation. Recently, methods have been proposed that extend the lifetime of the hyperpolarization by storing the spin order in slowly relaxing singlet states....... 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...

  6. Interference effects of two scalar boson propagators on the LHC search for the singlet fermion DM

    Energy Technology Data Exchange (ETDEWEB)

    Ko, P., E-mail: pko@kias.re.kr; Li, Jinmian, E-mail: jmli@kias.re.kr

    2017-02-10

    A gauge invariant UV-completion for singlet fermion DM interacting with the standard model (SM) particles involves a new singlet scalar. Therefore the model contains two scalar mediators, mixtures of the SM Higgs boson and a singlet scalar boson. Collider phenomenology of the interference effect between these two scalar propagators is studied in this work. This interference effect can be either constructive or destructive in the DM production cross section depending on both singlet scalar and DM masses, and it will soften the final state jets in the full mass region. Applying the CMS mono-jet search to our model, we find the interference effect plays a very important role in the DM search sensitivity, and the DM production cross section of our model is more than one order of magnitude below the LHC sensitivity at current stage.

  7. Effects of molecular packing in organic crystals on singlet fission with ab initio many body perturbation theory

    Science.gov (United States)

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

    Multi-exciton generation processes, in which multiple charge carriers are generated from a single photon, are mechanisms of significant interest for achieving efficiencies beyond the Shockley-Queisser limit of conventional p-n junction solar cells. One well-studied multiexciton process is singlet fission, whereby a singlet decays into two spin-correlated triplet excitons. Here, we use a newly developed computational approach to calculate singlet-fission coupling terms and rates with an ab initio Green's function formalism based on many-body perturbation theory (MBPT) within the GW approximation and the Bethe-Salpeter equation approach. We compare results for crystalline pentacene and TIPS-pentacene and explore the effect of molecular packing on the singlet fission mechanism. This work is supported by the Department of Energy.

  8. Photochemical properties of Ysub(t) base in aqueous solution

    International Nuclear Information System (INIS)

    Paszyc, S.; Rafalska, M.

    1979-01-01

    Photoreactivity of Ysub(t) base (I) has been studied in aqueous solution (pH-6) saturated with oxygen. Two photoproducts (II,III), resulting from irradiation at lambda = 253.7 nm and lambda >= 290 nm were isolated and their structures determined. The quantum yield for Ysub(t) base disappearance (rho dis) is 0.002 (lambda = 313 nm). It was shown that dye- sensitised photo-oxidation of Ysub(t) base in aqueous solution occurs according to a Type I mechanism as well as with participation of singlet state oxygen. Quantum yields, fluorescence decay times and phosphorescence of Ysub(t) base have also been determined. (author)

  9. LHC signals for singlet neutrinos from a natural warped seesaw mechanism. I

    Science.gov (United States)

    Agashe, Kaustubh; Du, Peizhi; Hong, Sungwoo

    2018-04-01

    Recently, it was shown in K. Agashe et al. [Phys. Rev. D 94, 013001 (2016), 10.1103/PhysRevD.94.013001] that a straightforward implementation of the type I seesaw mechanism in a warped extra dimensional framework is in reality a natural realization of "inverse" seesaw; i.e., the Standard Model (SM) neutrino mass is dominantly generated by exchange of pseudo-Dirac TeV-mass SM singlet neutrinos. By the AdS /CFT correspondence, this scenario is dual to these singlet particles being composites of some new strong dynamics, along with the SM Higgs boson (and possibly the top quark), with the rest of the SM particles being mostly elementary. We study signals from production of these heavy neutrinos at the Large Hadron Collider (LHC). We focus on the scenario where the strong sector has a global S U (2 )L×S U (2 )R×U (1 )X symmetry; such a left-right (LR) structure being motivated by consistency with the electroweak (EW) precision tests. The singlet neutrinos are charged under S U (2 )R×U (1 )X symmetry, thus can be produced from WR± exchange, as in four-dimensional LR symmetric models. However, the direct coupling of light quarks to WR± is negligible, due to WR± also being composite (cf. four-dimensional LR models); nonetheless, a sizable coupling can be induced by mixings among the various types of W± bosons. Furthermore, WR± decays dominantly into the singlet and composite partner of charged lepton (cf. SM lepton itself in four-dimensional LR model). This heavy charged lepton, in turn, decays into SM lepton, plus Z /Higgs , thus the latter can be used for extra identification of the signal. For a benchmark scenario with WR± of mass 2 TeV and singlet neutrino of mass 750 GeV, we find that, in both the dilepton +dijet +Higgs and trilepton +Higgs channels, significant evidence can be seen at the 14 TeV LHC for an integrated luminosity of 300 fb-1 and that even discovery is possible with slightly more luminosity.

  10. 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 ...

  11. Generování plynného singletového kyslíku pro interakční experimenty

    Czech Academy of Sciences Publication Activity Database

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

    2016-01-01

    Roč. 110, č. 1 (2016), s. 11-17 ISSN 0009-2770 R&D Projects: GA ČR GAP102/12/0723 Institutional support: RVO:68378271 Keywords : singlet oxygen * chemical generators of singlet oxygen * discharge generator of singlet oxygen Subject RIV: BH - Optics, Masers, Lasers Impact factor: 0.387, year: 2016

  12. TRANSFER

    African Journals Online (AJOL)

    This paper reports on further studies on long range energy transfer between curcumine as donor and another thiazine dye, thionine, which is closely related to methylene blue as energy harvester (Figure 1). Since thionine is known to have a higher quantum yield of singlet oxygen sensitization than methylene blue [8], it is ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Alanne, Tommi [CP" 3-Origins, University of Southern Denmark,Campusvej 55, DK-5230 Odense M (Denmark); Kainulainen, Kimmo [Department of Physics, University of Jyväskylä,P.O. Box 35 (YFL), FI-40014 Jyväskylä (Finland); Helsinki Institute of Physics, University of Helsinki,P.O. Box 64, FI-00014 Helsinki (Finland); Tuominen, Kimmo [Department of Physics, University of Helsinki,P.O. Box 64, FI-00014 Helsinki (Finland); Helsinki Institute of Physics, University of Helsinki,P.O. Box 64, FI-00014 Helsinki (Finland); Vaskonen, Ville [Department of Physics, University of Jyväskylä,P.O. Box 35 (YFL), FI-40014 Jyväskylä (Finland); Helsinki Institute of Physics, University of Helsinki,P.O. Box 64, FI-00014 Helsinki (Finland)

    2016-08-25

    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. In particular, the constraints from the electron and neutron electric dipole moments are less constraining here than in pure two-Higgs-doublet model (2HDM). The two-step, first-order transition in 2HDSM, induced by the singlet field, may lead to strong supercooling and low nucleation temperatures in comparison with the critical temperature, T{sub n}≪T{sub c}, which can significantly alter the usual phase-transition pattern in 2HD models with T{sub n}≈T{sub c}. 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.

  14. 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.)

  15. Acceleration of Singlet Fission in an Aza-Derivative of TIPS-Pentacene.

    Science.gov (United States)

    Herz, Julia; Buckup, Tiago; Paulus, Fabian; Engelhart, Jens; Bunz, Uwe H F; Motzkus, Marcus

    2014-07-17

    The influence of the carbon to nitrogen substitution on the photoinduced dynamics of TIPS-pentacene was investigated by ultrafast transient absorption measurements on spin-coated thin films in the visible and in the near-infrared spectral region. A global target analysis was performed to provide a detailed picture of the excited-state dynamics. We found that the chemical modification has a high impact on the triplet formation and leads to shorter dynamics; hence it speeds up the singlet fission process. A faster relaxation from the singlet into the triplet manifold implies a higher efficiency because other relaxation channels are avoided. The air-stable aza-derivatives have the potential to exceed the energy conversion efficiency of TIPS-pentacene.

  16. Sterile Neutrinos, Dark Matter, and Pulsar Velocities in Models with a Higgs Singlet

    International Nuclear Information System (INIS)

    Kusenko, Alexander

    2006-01-01

    We identify the range of parameters for which the sterile neutrinos can simultaneously explain the cosmological dark matter and the observed velocities of pulsars. To satisfy all cosmological bounds, the relic sterile neutrinos must be produced sufficiently cold. This is possible in a class of models with a gauge-singlet Higgs boson coupled to the neutrinos. Sterile dark matter can be detected by the x-ray telescopes. The presence of the singlet in the Higgs sector can be tested at the CERN Large Hadron Collider

  17. Generation of deviation parameters for amino acid singlets, doublets ...

    Indian Academy of Sciences (India)

    We present a new method, secondary structure prediction by deviation parameter (SSPDP) for predicting the secondary structure of proteins from amino acid sequence. Deviation parameters (DP) for amino acid singlets, doublets and triplets were computed with respect to secondary structural elements of proteins based on ...

  18. Antitumor effects evaluation of a novel porphyrin derivative in photodynamic therapy.

    Science.gov (United States)

    Li, Jian-Wei; Wu, Zhong-Ming; Magetic, Davor; Zhang, Li-Jun; Chen, Zhi-Long

    2015-12-01

    In this paper, the antitumor activity of a novel porphyrin-based photosensitizer 5,10,15,20-tetrakis[(5-diethylamino)pentyl] porphyrin (TDPP) was reported in vitro and in vivo. The photophysical and cellular properties of TDPP were investigated. The singlet oxygen generation quantum yield of TDPP was detected; it showed a high singlet oxygen quantum yield of 0.52. The intracellular distribution of photosensitizer was detected with laser scanning confocal microscopy. The efficiency of TDPP-photodynamic therapy (PDT) in vitro was analyzed by 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay and in situ trypan blue exclusion test. Treated with a 630-nm laser, TDPP can kill cultured human esophageal cancer cell line (Eca-109) cells and reduce the growth of Eca-109 xenograft tumors significantly in BABL/c nude mice. And histopathological study was also used to confirm the antitumor effect. It has the perspective to be developed as a new antitumor drug in photodynamic therapy and deserves further investigation.

  19. Scheme for generating the singlet state of three atoms trapped in distant cavities coupled by optical fibers

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dong-Yang [Department of Physics, College of Science, Yanbian University, Yanji, Jilin 133002 (China); Wen, Jing-Ji [College of Foundation Science, Harbin University of Commerce, Harbin, Heilongjiang 150028 (China); Bai, Cheng-Hua; Hu, Shi; Cui, Wen-Xue [Department of Physics, College of Science, Yanbian University, Yanji, Jilin 133002 (China); Wang, Hong-Fu, E-mail: hfwang@ybu.edu.cn [Department of Physics, College of Science, Yanbian University, Yanji, Jilin 133002 (China); Zhu, Ai-Dong [Department of Physics, College of Science, Yanbian University, Yanji, Jilin 133002 (China); Zhang, Shou, E-mail: szhang@ybu.edu.cn [Department of Physics, College of Science, Yanbian University, Yanji, Jilin 133002 (China)

    2015-09-15

    An effective scheme is proposed to generate the singlet state with three four-level atoms trapped in three distant cavities connected with each other by three optical fibers, respectively. After a series of appropriate atom–cavity interactions, which can be arbitrarily controlled via the selective pairing of Raman transitions and corresponding optical switches, a three-atom singlet state can be successfully generated. The influence of atomic spontaneous decay, photon leakage of cavities and optical fibers on the fidelity of the state is numerically simulated showing that the three-atom singlet state can be generated with high fidelity by choosing the experimental parameters appropriately.

  20. Supramolecular structures for photochemical energy conversion. Technical progress report, 1993--1996

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-06-01

    This research project is concerned with the design, synthesis and study by photochemical and spectroscopic methods of complex molecular devices that mimic some important aspects of photosynthetic electron and energy transfer. Properly engineered molecules of this type can functionally mimic photosynthetic light harvesting (singlet-singlet energy transfer between chromophores), photoprotection from light-initiated singlet oxygen damage (triplet-triplet energy transfer from chlorophylls to carotenoid polyenes), and, most importantly, photoinduced multistep electron transfer to generate charge-separated states that preserve some of the photon energy as chemical potential. During the last three years, progress has been made on several fronts, all of which are related to the overall goal. A biomimetic system based on carotenoid-porphyrin-quinone triads has been constructed that demonstrates photoinduced transmembrane charge separation which in turn drives transmembrane proton transfer. Another investigation has focused on the use of proton transfer reactions to stabilize the initial products of photoinduced electron transfer and thereby increase the yield of long-lived charge separation. A third study has investigated the influence of rigid molecular geometries and short donor-acceptor separations on photoinduced electron transfer reactions. Finally, generation and quenching of singlet molecular oxygen by chlorophyll aggregates has been studied. All four studies are described and results are discussed.

  1. Gaugino mass without singlets

    International Nuclear Information System (INIS)

    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

  2. Singlet-triplet fission of carotenoid excitation in light-harvesting LH2 complexes of purple phototrophic bacteria.

    Science.gov (United States)

    Klenina, I B; Makhneva, Z K; Moskalenko, A A; Gudkov, N D; Bolshakov, M A; Pavlova, E A; Proskuryakov, I I

    2014-03-01

    The current generally accepted structure of light-harvesting LH2 complexes from purple phototrophic bacteria conflicts with the observation of singlet-triplet carotenoid excitation fission in these complexes. In LH2 complexes from the purple bacterium Allochromatium minutissimum, a drop in the efficiency of carotenoid triplet generation is demonstrated, which correlates with the extent of selective photooxidation of bacteriochlorophylls absorbing at ~850 nm. We conclude that singlet-triplet fission of carotenoid excitation proceeds with participation of these excitonically coupled bacteriochlorophylls. In the framework of the proposed mechanism, the contradiction between LH2 structure and photophysical properties of carotenoids is eliminated. The possibility of singlet-triplet excitation fission involving a third mediator molecule was not considered earlier.

  3. 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.

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

    KAUST Repository

    Filatov, Mikhail A.; Etzold, Fabian; Gehrig, Dominik; Laquai, Fré dé ric; Busko, Dmitri; Landfester, Katharina; Baluschev, Stanislav

    2015-01-01

    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.

  5. Quantifying the influence of the epidermal optical properties on laser treatment parameters

    CSIR Research Space (South Africa)

    Karsten, AE

    2013-05-01

    Full Text Available . The formation of highly reactive singlet oxygen in the cells leads to cell death through apoptosis or necrosis9,11,12. Due to the short lifetime of the singlet oxygen in biological systems only molecules close to the PS are affected. The half...-lifetime of singlet oxygen is less than 40 ns, and the radius of the action of singlet oxygen is in the order of 20 nm13. PDT is a localised treatment, having less of an adverse effect on the healthy cells not irradiated by the light source. PDT has been approved...

  6. Singlet exciton interactions in crystalline naphthalene

    International Nuclear Information System (INIS)

    Heisel, F.; Miehe, J.A.; Sipp, B.

    1978-01-01

    The decay of prompt fluorescence in crystalline naphthalene at 300 K, excited by picosecond 266 nm pulse, has been studied as a function of excitation intensity. Experimental decay curves can be fitted only when the exponential distribution in depth of excitation and the radial (gaussian) intensity profile of the excitation are both taken into account. From analysis of decay at early time ( -10 cm 3 s -1 . If the reaction is diffusion-limited, this rate implies an average singlet diffusivity Dsub(S)=(2+-1)10 -4 cm 2 s -1

  7. 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.

  8. 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

  9. Applied Biological and Physicochemical Activity of Isoquinoline Alkaloids: Oxoisoaporphine and Boldine

    Directory of Open Access Journals (Sweden)

    María Eliana Hidalgo

    2012-09-01

    Full Text Available The aim of this study was to determine the electronic influence of substituent groups and annelated rings such as oxazole-oxazinone on the physicochemical and photoprotection, antioxidant capacity, toxicity and singlet oxygen photosensitization biological properties of isoquinoline alkaloid frameworks. Thus, oxoisoaporphine derivatives 1–5 and 3-azaoxoisoaporphine (6, some of them with phenolic structures, did not present any antioxidant capacity, possibly either by formation of keto-enol tautomerism species or the formation of unstable free radicals. Due to the singlet oxygen quantum yields (FD near to unity, and greater photostability than phenalenone, oxoisoaporphines 4–6 may be considered as photosensitizers for singlet oxygen production and can be used as new universal study tools. The biological application as antibacterial agents is an important and possible tool in the study of compounds with low cytotoxicity and high reactivity in antineoplastic chemotherapy. On the other hand, when boldine and its annelated derivatives B1–4 are irradiated, a photoprotector effect is observed (SPF = 2.35, even after 30 minutes of irradiation. They also act as photoprotectors in cell fibroblast cultures. No hemolysis was detected for boldine hydrochloride and its salts without irradiation. In solutions irradiated before incubation (at concentrations over 200 ppm photoproducts were toxic to the nauplii of Artemia salina.

  10. Finite-bias conductance anomalies at a singlet-triplet crossing

    DEFF Research Database (Denmark)

    Stevanato, Chiara; Leijnse, Martin Christian; Flensberg, Karsten

    2012-01-01

    at the crossing. Here we show that, in addition, level crossings can give rise to a nearly vertical step-edge, ridge or even a Fano-like ridge-valley feature in the dierential conductance inside the relevant Coulomb diamond. We study a gate-tunable quasidegeneracy between singlet and triplet ground states...

  11. Technicolor Models with Color-Singlet Technifermions and their Ultraviolet Extensions

    DEFF Research Database (Denmark)

    Ryttov, Thomas; Shrock, Robert

    2011-01-01

    for the technifermions and additional color-singlet, technisinglet fermions arising from the necessity of avoiding stable bound states with exotic electric charges. Precision electroweak constraints on these models are also discussed. We determine some general properties of extended technicolor theories containing...

  12. Second-order contributions to the structure functions in deep inelastic scattering III The singlet

    CERN Document Server

    González-Arroyo, A

    1980-01-01

    For pt.II see ibid., vol.159, p.512 (1979). Pointlike QCD predictions for the singlet part of the structure functions are given up to next- to-leading order of perturbation theory. This generalises the result obtained in pt.I (see ibid., vol.153, p.161, 1979) which deals with the non-singlet case. An interesting by-product is an exact and simple analytical expression for the anomalous dimension matrix to second non-trivial order in the QCD coupling constant. (18 refs).

  13. The next-next-to-leading QCD approximation for non-singlet moments of deep inelastic structure functions

    International Nuclear Information System (INIS)

    Larin, S.A.; Ritbergen, T. van; Vermaseren, J.A.M.

    1993-12-01

    We obtain the analytic next-next-to-leading perturbative QCD corrections in the leading twist approximation for the moments N = 2, 4, 6, 8 of the non-singlet deep inelastic structure functions F 2 and F L . We calculate the three-loop anomalous dimensions of the corresponding non-singlet operators and the three-loop coefficient functions of the structure function F L . (orig.)

  14. 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.

  15. 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....

  16. Peccei-Quinn invariant singlet extended SUSY with anomalous U(1) gauge symmetry

    Energy Technology Data Exchange (ETDEWEB)

    Im, Sang Hui; Seo, Min-Seok [Center for Theoretical Physics of the Universe, Institute for Basic Science (IBS),Daejeon 305-811 (Korea, Republic of)

    2015-05-13

    Recent discovery of the SM-like Higgs boson with m{sub h}≃125 GeV motivates an extension of the minimal supersymmetric standard model (MSSM), which involves a singlet Higgs superfield with a sizable Yukawa coupling to the doublet Higgs superfields. We examine such singlet-extended SUSY models with a Peccei-Quinn (PQ) symmetry that originates from an anomalous U(1){sub A} gauge symmetry. We focus on the specific scheme that the PQ symmetry is spontaneously broken at an intermediate scale v{sub PQ}∼√(m{sub SUSY}M{sub Pl}) by an interplay between Planck scale suppressed operators and tachyonic soft scalar mass m{sub SUSY}∼√(D{sub A}) induced dominantly by the U(1){sub A}D-term D{sub A}. This scheme also results in spontaneous SUSY breaking in the PQ sector, generating the gaugino masses M{sub 1/2}∼√(D{sub A}) when it is transmitted to the MSSM sector by the conventional gauge mediation mechanism. As a result, the MSSM soft parameters in this scheme are induced mostly by the U(1){sub A}D-term and the gauge mediated SUSY breaking from the PQ sector, so that the sparticle masses can be near the present experimental bounds without causing the SUSY flavor problem. The scheme is severely constrained by the condition that a phenomenologically viable form of the low energy operators of the singlet and doublet Higgs superfields is generated by the PQ breaking sector in a way similar to the Kim-Nilles solution of the μ problem, and the resulting Higgs mass parameters allow the electroweak symmetry breaking with small tan β. We find two minimal models with two singlet Higgs superfields, satisfying this condition with a relatively simple form of the PQ breaking sector, and briefly discuss some phenomenological aspects of the model.

  17. Reliable Prediction with Tuned Range-Separated Functionals of the Singlet-Triplet Gap in Organic Emitters for Thermally Activated Delayed Fluorescence (TADF)

    KAUST Repository

    Sun, Haitao

    2015-07-09

    The thermally activated delayed fluorescence (TADF) mechanism has recently attracted much interest in the field of organic light-emitting diodes (OLEDs). TADF relies on the presence of a very small energy gap between the lowest singlet and triplet excited states. Here, we demonstrate that time-dependent density functional theory (TD-DFT) in the Tamm-Dancoff Approximation can be very successful in the calculations of the lowest singlet and triplet excitation energies and the corresponding singlet-triplet gap when using nonempirically tuned range-separated functionals. Such functionals provide very good estimates in a series of 17 molecules used in TADF-based OLED devices, with mean absolute deviations of 0.15 eV for the vertical singlet excitation energies and 0.09 eV [0.07 eV] for the adiabatic [vertical] singlet-triplet energy gaps as well as low relative errors and high correlation coefficients compared to the corresponding experimental values. They significantly outperform conventional functionals, a feature which is rationalized on the basis of the amount of exact-exchange included and the delocalization error. The present work provides a reliable theoretical tool for the prediction and development of novel TADF-based materials with low singlet-triplet energetic splittings.

  18. 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.

  19. The next-next-to-leading QCD approximation for non-singlet moments of deep inelastic structure functions

    Energy Technology Data Exchange (ETDEWEB)

    Larin, S.A.; Ritbergen, T. van; Vermaseren, J.A.M.

    1993-12-01

    We obtain the analytic next-next-to-leading perturbative QCD corrections in the leading twist approximation for the moments N = 2, 4, 6, 8 of the non-singlet deep inelastic structure functions F{sub 2} and F{sub L}. We calculate the three-loop anomalous dimensions of the corresponding non-singlet operators and the three-loop coefficient functions of the structure function F{sub L}. (orig.).

  20. 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.

  1. 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.

  2. Photophysical Properties of Pheophorbide-a Derivatives and Their Photodynamic Therapeutic Effects on a Tumor Cell Line In Vitro

    Directory of Open Access Journals (Sweden)

    Kang-Kyun Wang

    2014-01-01

    Full Text Available Pheophorbide-a derivatives have been reported to be potential photosensitizers for photodynamic therapy (PDT. In this study, photophysics of pheophorbide-a derivatives (PaDs were investigated along with their photodynamic tumoricidal effect in vitro. PaDs were modified by changing the coil length and/or making the hydroxyl group (–OH substitutions. Their photophysical properties were studied by steady-state and time-resolved spectroscopic methods. The photodynamic tumoricidal effect was evaluated in the mouse breast cancer cell line (EMT6. Lifetime and quantum yield of fluorescence and quantum yields of triplet state and singlet oxygen were studied to determine the dynamic energy flow. The coil length of the substituted alkyl group did not significantly affect the spectroscopic properties. However, the substitution with the hydroxyl group increased the quantum yields of the triplet state and the singlet oxygen due to the enhanced intersystem crossing. In order to check the application possibility as a photodynamic therapy agent, the PaDs with hydroxyl group were studied for the cellular affinity and the photodynamic tumoricidal effect of EMT6. The results showed that the cellular affinity and the photodynamic tumoricidal effect of PaDs with the hydroxyl group depended on the coil-length of the substituted alkyl group.

  3. 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

  4. Mechanistic and Kinetic Study of Singlet O2 Oxidation of Methionine by On-Line Electrospray Ionization Mass Spectrometry.

    Science.gov (United States)

    Liu, Fangwei; Lu, Wenchao; Yin, Xunlong; Liu, Jianbo

    2016-01-01

    We report a reaction apparatus developed to monitor singlet oxygen ((1)O2) reactions in solution using on-line ESI mass spectrometry and spectroscopy measurements. (1)O2 was generated in the gas phase by the reaction of H2O2 with Cl2, detected by its emission at 1270 nm, and bubbled into aqueous solution continuously. (1)O2 concentrations in solution were linearly related to the emission intensities of airborne (1)O2, and their absolute scales were established based on a calibration using 9,10-anthracene dipropionate dianion as an (1)O2 trapping agent. Products from (1)O2 oxidation were monitored by UV-Vis absorption and positive/negative ESI mass spectra, and product structures were elucidated using collision-induced dissociation-tandem mass spectrometry. To suppress electrical discharge in negative ESI of aqueous solution, methanol was added to electrospray via in-spray solution mixing using theta-glass ESI emitters. Capitalizing on this apparatus, the reaction of (1)O2 with methionine was investigated. We have identified methionine oxidation intermediates and products at different pH, and measured reaction rate constants. (1)O2 oxidation of methionine is mediated by persulfoxide in both acidic and basic solutions. Persulfoxide continues to react with another methionine, yielding methionine sulfoxide as end-product albeit with a much lower reaction rate in basic solution. Density functional theory was used to explore reaction potential energy surfaces and establish kinetic models, with solvation effects simulated using the polarized continuum model. Combined with our previous study of gas-phase methionine ions with (1)O2, evolution of methionine oxidation pathways at different ionization states and in different media is described.

  5. Line shape of magnetic excitations in singlet-ground-state systems

    International Nuclear Information System (INIS)

    Bak, P.

    1976-08-01

    The excitation spectrum in a paramagnetic singlet doublet system is calculated using a diagrammatic expansion technique, and the theoretical predictions are compared with experiments on praseodymium. The theory gives an accurate description of the dramatic temperature dependence of the energies and lineshapes for the exciton modes

  6. 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

  7. 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.

  8. 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.)

  9. Triplet energy transfer and triplet exciton recycling in singlet fission sensitized organic heterojunctions

    Science.gov (United States)

    Hamid, Tasnuva; Yambem, Soniya D.; Crawford, Ross; Roberts, Jonathan; Pandey, Ajay K.

    2017-08-01

    Singlet exciton fission is a process where an excited singlet state splits into two triplets, thus leading to generation of multiple excitons per absorbed photon in organic semiconductors. Herein, we report a detailed exciton management approach for multiexciton harvesting over a broadband region of the solar spectrum in singlet fission sensitized organic photodiodes. Through systematic studies on the model cascade of pentacene/rubrene/C60, we found that efficient photocurrent generation from pentacene can still occur despite the presence of a >10nm thick interlayer of rubrene in between the pentacene/C60 heterojunction. Our results show that thin rubrene interlayers of thickness pentacene despite having a reasonably thick rubrene interlayer, that too with higher triplet energy (T1=1.12 eV) than pentacene (T1= 0.86 eV), makes its operation a rather interesting result. We discuss the role of rubrene interlayer film discontinuity, triplet exciton reflection from rubrene interlayer and triplet energy transfer from rubrene to pentacene layer followed by diffusion of triplet excitons through rubrene as plausible mechanisms that would enable triplet excitons from pentacene to generate significant photocurrent in a multilayer organic heterojunction.

  10. Pentacene Dimers as a Critical Tool for the Investigation of Intramolecular Singlet Fission.

    Science.gov (United States)

    Hetzer, Constantin; Guldi, Dirk M; Tykwinski, Rik R

    2018-01-11

    Singlet fission (SF) involves the spontaneous splitting of a photoexcited singlet state into a pair of triplets, and it holds great promise toward the realization of more efficient solar cells. Although the process of SF has been known since the 1960s, debate regarding the underlying mechanism continues to this day, especially for molecular materials. A number of different chromophores have been synthesized and studied in order to better understand the process of SF. These previous reports have established that pentacene and its derivatives are especially well-suited for the study of SF, since the energetic requirement E(S 1 )≥2E(T 1 ) is fulfilled rendering the process exothermic and unidirectional. Dimeric pentacene derivatives, in which individual pentacene chromophores are tethered by a "spacer", have emerged as the system of choice toward exploring the mechanism of intramolecular singlet fission (iSF). The dimeric structure, and in particular the spacer, allows for controlling and tuning the distance, geometric relationship, and electronic coupling between the two pentacene moieties. This Minireview describes recent advances using pentacene dimers for the investigation of iSF. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Photofunctional Co-Cr Alloy Generating Reactive Oxygen Species for Photodynamic Applications

    Directory of Open Access Journals (Sweden)

    Kang-Kyun Wang

    2013-01-01

    Full Text Available We report the fabrication of photofunctional Co-Cr alloy plate that is prepared by a simple modification process for photodynamic application. Photoinduced functionality is provided by the photosensitizer of hematoporphyrin (Hp that initially generates reactive oxygen species (ROS such as superoxide anion radical and singlet oxygen. The photosensitizer with carboxyl group was chemically bonded to the surface of the Co-Cr alloy plate by esterification reaction. Microstructure and elemental composition of the Co-Cr alloy plate were checked with scanning electron microscopy (SEM and energy dispersive X-ray spectrometer (EDS. Fabrication of the photofunctionality of the Co-Cr alloy plate was confirmed with X-ray photoelectron spectroscopy (XPS, reflectance UV-Vis absorption, and emission spectroscopy. Reactive oxygen generation from the photofunctional Co-Cr alloy plate was confirmed by using the decomposition reaction of 1,3-diphenylisobenzofuran (DPBF. The results suggest that the immobilized photosensitizer molecules on the surface of Co-Cr alloy plate still possess their optical and functional properties including reactive oxygen generation. To open the possibility for its application as a photodynamic material to biological system, the fabricated photofunctional Co-Cr alloy is applied to the decomposition of smooth muscle cells.

  12. On the Josephson effect between superconductors in singlet and triplet spin-pairing states

    International Nuclear Information System (INIS)

    Pals, J.A.; Haeringen, W. van

    1977-01-01

    An expression is derived for the Josephson current between two weakly coupled superconductors of which one or both have pairs in a spin-triplet state. It is shown that there can be no Josephson effect up to second order in the transition matrix elements between a superconductor with spin-triplet pairs and one with spin-singlet pairs if the coupling between the two superconductors can be described with a spin-conserving tunnel hamiltonian. This is shown to offer a possibility to investigate experimentally whether a particular superconductor has spin-triplet pairs by coupling it weakly to a well-known spin-singlet pairing superconductor. (Auth.)

  13. Dimensional reduction of the Standard Model coupled to a new singlet scalar field

    Energy Technology Data Exchange (ETDEWEB)

    Brauner, Tomáš [Faculty of Science and Technology, University of Stavanger,N-4036 Stavanger (Norway); Tenkanen, Tuomas V.I. [Department of Physics and Helsinki Institute of Physics,P.O. Box 64, FI-00014 University of Helsinki (Finland); Tranberg, Anders [Faculty of Science and Technology, University of Stavanger,N-4036 Stavanger (Norway); Vuorinen, Aleksi [Department of Physics and Helsinki Institute of Physics,P.O. Box 64, FI-00014 University of Helsinki (Finland); Weir, David J. [Faculty of Science and Technology, University of Stavanger,N-4036 Stavanger (Norway); Department of Physics and Helsinki Institute of Physics,P.O. Box 64, FI-00014 University of Helsinki (Finland)

    2017-03-01

    We derive an effective dimensionally reduced theory for the Standard Model augmented by a real singlet scalar. We treat the singlet as a superheavy field and integrate it out, leaving an effective theory involving only the Higgs and SU(2){sub L}×U(1){sub Y} gauge fields, identical to the one studied previously for the Standard Model. This opens up the possibility of efficiently computing the order and strength of the electroweak phase transition, numerically and nonperturbatively, in this extension of the Standard Model. Understanding the phase diagram is crucial for models of electroweak baryogenesis and for studying the production of gravitational waves at thermal phase transitions.

  14. 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.)

  15. 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.

  16. Effect of vanillin on methylene blue plus light-induced single-strand breaks in plasmid pBR322 DNA.

    Science.gov (United States)

    Kumar, S S; Ghosh, A; Devasagayam, T P; Chauhan, P S

    2000-09-20

    The ability of vanillin (4-hydroxy-3-methoxybenzaldehyde), a naturally occurring food flavouring agent, in inhibiting photosensitization-induced single-strand breaks (ssbs) in plasmid pBR322 DNA has been examined in an in vitro system, independent of DNA repair/replication processes. Photosensitization of DNA with methylene blue, visible light and oxygen, induced ssbs resulting in the production of open circular form (OC form) in a concentration-dependent manner. The yield of OC form induced by photosensitization was increased several-fold by deuteration of the buffer and was found to be inhibited by sodium azide, a scavenger of singlet oxygen (1O(2)). Vanillin, per se, did not induce but inhibited photosensitization-induced ssbs in plasmid DNA, at millimolar concentrations. The inhibitory effect of vanillin was both concentration- and time-dependent. On a molar basis, vanillin was, however, less effective than trolox, a water-soluble analogue of alpha-tocopherol. Photosensitization by methylene blue system generates singlet oxygen, as one of the major components of ROS. Therefore, interaction of singlet oxygen with vanillin was investigated. The rate constant of vanillin with 1O(2) was estimated to be 5.93x10(7)M(-1)s(-1) and that of sodium azide as 2. 7x10(8)M(-1)s(-1). The present investigations show that vanillin can protect against photosensitization-induced ssbs in the plasmid pBR322 DNA, and this effect may partly be due to its ability to scavenge 1O(2).

  17. 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

  18. Effects of disorder on atomic density waves and spin-singlet dimers in one-dimensional optical lattices

    International Nuclear Information System (INIS)

    Gao Xianlong

    2008-01-01

    Using the Bethe-ansatz density-functional theory, we study a one-dimensional Hubbard model of confined attractively interacting fermions in the presence of a uniformly distributed disorder. The strongly correlated Luther-Emery nature of the attractive one-dimensional Hubbard model is fully taken into account as the reference system in the density-functional theory. The effects of the disorder are investigated on the atomic density waves in the weak-to-intermediate attractive interaction and on the spin-singlet dimers of doubly occupied sites in the strongly attractive regime. It is found that atomic density waves are sensitive to the disorder and the spin-singlet dimers of doubly occupied sites are quite unstable against the disorder. We also show that a very weak disorder could smear the singularities in the stiffness, thus, suppresses the spin-singlet pairs

  19. Quantum Dot-Based Luminescent Oxygen Channeling Assay for Potential Application in Homogeneous Bioassays.

    Science.gov (United States)

    Zhuang, Si-Hui; Guo, Xin-Xin; Wu, Ying-Song; Chen, Zhen-Hua; Chen, Yao; Ren, Zhi-Qi; Liu, Tian-Cai

    2016-01-01

    The unique photoproperties of quantum dots are promising for potential application in bioassays. In the present study, quantum dots were applied to a luminescent oxygen channeling assay. The reaction system developed in this study was based on interaction of biotin with streptavidin. Carboxyl-modified polystyrene microspheres doped with quantum dots were biotinylated and used as acceptors. Photosensitizer-doped carboxyl-modified polystyrene microspheres were conjugated with streptavidin and used as donors. The results indicated that the singlet oxygen that was released from the donor beads diffused into the acceptor beads. The acceptor beads were then exited via thioxene, and were subsequently fluoresced. To avoid generating false positives, a high concentration (0.01 mg/mL) of quantum dots is required for application in homogeneous immunoassays. Compared to a conventional luminescent oxygen channeling assay, this quantum dots-based technique requires less time, and would be easier to automate and miniaturize because it requires no washing to remove excess labels.

  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. Determination of disconnected diagrams for flavor singlet matrix elements in full QCD

    International Nuclear Information System (INIS)

    Viehoff, J.

    1999-11-01

    Flavor-singlet phenomena play a fundamental role in the low energy regime of QCD. For observables which contain flavor-singlet currents, the impact of quantum fluctuations is reflected in terms of disconnected diagrams. In lattice calculations disconnected diagrams are directly accessible with stochastic estimator techniques. We review and improve the stochastic estimator techniques with complex Z2 noise and achieve clear evidence for contributions from disconnected diagrams in the pion-nucleon σ-term, σ πn , and the flavor-singlet axial coupling of the proton, G A 1 . The analysis is based on the SESAM gauge-field configurations with 2 flavors of dynamical Wilson fermions. Furthermore a set of configurations from the T χ L collaboration is analyzed as well. The lattice size is 16 3 x 32, respectively 24 3 x 40 for the T χ L configurations, with lattice spacing a ρ -1 ≅2.3 GeV and m π /m ρ =0.84-0.69. We find disconnected contributions for σ πN in the same order of magnitude as from the connected insertion and obtain σ πN =18(5) MeV. Furthermore we have determined the topological charge Q L on the gauge-field configurations with cooling techniques and with the Atiyah-Singer index-theorem in combination with SET. (orig.)

  2. Simultaneous monitoring of singlet and triplet exciton variations in solid organic semiconductors driven by an external static magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Baofu, E-mail: b.ding@ecu.edu.au; Alameh, Kamal, E-mail: k.alameh@ecu.edu.au [Electron Science Research Institute, Edith Cowan University, 270 Joondalup Drive, Joondalup, WA 6027 (Australia)

    2014-07-07

    The research field of organic spintronics has remarkably and rapidly become a promising research area for delivering a range of high-performance devices, such as magnetic-field sensors, spin valves, and magnetically modulated organic light emitting devices (OLEDs). Plenty of microscopic physical and chemical models based on exciton or charge interactions have been proposed to explain organic magneto-optoelectronic phenomena. However, the simultaneous observation of singlet- and triplet-exciton variations in an external magnetic field is still unfeasible, preventing a thorough theoretical description of the spin dynamics in organic semiconductors. Here, we show that we can simultaneously observe variations of singlet excitons and triplet excitons in an external magnetic field, by designing an OLED structure employing a singlet-exciton filtering and detection layer in conjunction with a separate triplet-exciton detection layer. This OLED structure enables the observation of a Lorentzian and a non-Lorentzian line-shape magnetoresponse for singlet excitons and triplet excitons, respectively.

  3. Simultaneous monitoring of singlet and triplet exciton variations in solid organic semiconductors driven by an external static magnetic field

    International Nuclear Information System (INIS)

    Ding, Baofu; Alameh, Kamal

    2014-01-01

    The research field of organic spintronics has remarkably and rapidly become a promising research area for delivering a range of high-performance devices, such as magnetic-field sensors, spin valves, and magnetically modulated organic light emitting devices (OLEDs). Plenty of microscopic physical and chemical models based on exciton or charge interactions have been proposed to explain organic magneto-optoelectronic phenomena. However, the simultaneous observation of singlet- and triplet-exciton variations in an external magnetic field is still unfeasible, preventing a thorough theoretical description of the spin dynamics in organic semiconductors. Here, we show that we can simultaneously observe variations of singlet excitons and triplet excitons in an external magnetic field, by designing an OLED structure employing a singlet-exciton filtering and detection layer in conjunction with a separate triplet-exciton detection layer. This OLED structure enables the observation of a Lorentzian and a non-Lorentzian line-shape magnetoresponse for singlet excitons and triplet excitons, respectively.

  4. Photo-oxidation of cells generates long-lived intracellular protein peroxides

    DEFF Research Database (Denmark)

    Wright, Adam; Hawkins, Clare Louise; Davies, Michael Jonathan

    2003-01-01

    Singlet oxygen is generated by several cellular, enzymatic, and chemical reactions as well as by exposure to UV or visible light in the presence of a sensitizer. Consequently, this oxidant has been proposed to be a damaging agent many pathologies. Proteins are major targets for singlet oxygen...... as a result of their abundance and high rate constants for reaction. In this study, we show that illumination of viable rose bengal-loaded THP-1 (human monocyte-like) cells with visible light gives rise to intracellular protein-derived peroxides. The peroxide yield increases with illumination time, requires....../2) about 4 h at 37 degrees C. 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 studies demonstrate that exposure of intact cells to visible light in the presence of a sensitizer leads...

  5. Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals

    Science.gov (United States)

    Garza, Alejandro J.; Sousa Alencar, Ana G.; Scuseria, Gustavo E.

    2015-12-01

    Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f0 actinyl series (UO22+, NpO23+, PuO24+), the isoelectronic NUN, and thorium (ThO, ThO2+) and nobelium (NoO, NoO2) oxides are studied.

  6. 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

  7. Superconductivity switch from spin-singlet to -triplet pairing in a topological superconducting junction

    Science.gov (United States)

    Tao, Ze; Chen, F. J.; Zhou, L. Y.; Li, Bin; Tao, Y. C.; Wang, J.

    2018-06-01

    The interedge coupling is the cardinal characteristic of the narrow quantum spin Hall (QSH) insulator, and thus could bring about exotic transport phenomena. Herein, we present a theoretical investigation of the spin-resolved Andreev reflection (AR) in a QSH insulator strip touching on two neighbouring ferromagnetic insulators and one s-wave superconductor. It is demonstrated that, due to the interplay of the interedge coupling and ferromagnetic configuration, there could be not only usual local ARs leading to the spin-singlet pairing with the incident electron and Andreev-reflected hole from different spin subbands, but also novel local ARs giving rise to the spin-triplet pairing from the same spin subband. However, only the latter exists in the absence of the interedge coupling, and therefore the two pairings in turn testify the helical spin texture of the edge states. By proper tuning of the band structures of the ferromagnetic layers, under the resonance bias voltage, the usual and novel local ARs of can be all exhibited, resulting in fully spin-polarized pure spin-singlet superconductivity and pure spin-triplet superconductivity, respectively, which suggests a superconductivity switch from spin-singlet to -triplet pairing by electrical control. The results can be experimentally confirmed by the tunneling conductance and the noise power.

  8. Variable ATP yields and uncoupling of oxygen consumption in human brain

    DEFF Research Database (Denmark)

    Gjedde, Albert; Aanerud, Joel; Peterson, Ericka

    2011-01-01

    normalized the metabolic rate to the population average of that region. Coefficients of variation ranged from 10 to 15% in the different regions of the human brain and the normalized regional metabolic rates ranged from 70% to 140% of the population average for each region, equal to a two-fold variation......The distribution of brain oxidative metabolism values among healthy humans is astoundingly wide for a measure that reflects normal brain function and is known to change very little with most changes of brain function. It is possible that the part of the oxygen consumption rate that is coupled...... to ATP turnover is the same in all healthy human brains, with different degrees of uncoupling explaining the variability of total oxygen consumption among people. To test the hypothesis that about 75% of the average total oxygen consumption of human brains is common to all individuals, we determined...

  9. Singlet and triplet states of trions in Zinc Selenide-based quantum wells probed by magnetic fields to 50 Tesla

    International Nuclear Information System (INIS)

    Astakhov, G.V.; Yakovlev, D.R.; Crooker, Scott A.; Barrick, Todd; Dzyubenko, A.B.; Sander, Thomas; Kochereshko, V.P.; Ossau, W.; Faschinger, W.; Waag, A.

    2002-01-01

    Singlet and triplet states of positively (X + ) and negatively (X - ) charged excitons in ZnSe-based quantum wells have been studied by means of photoluminescence in pulsed magnetic fields up to 50 T. The binding energy of the X - singlet state shows a monotonic increase with magnetic field with a tendency to saturation, while that of the X + slightly decreases. The triplet X + and X - states, being unbound at zero magnetic field, noticeably increase their binding energy in high magnetic fields. The experimental evidence for the interaction between the triplet and singlet states of lTions leading to their anticrossing in magnetic fields has been found.

  10. Flavor-singlet axial-vector current in quark model within background field

    International Nuclear Information System (INIS)

    Chen Kun; Yan Mulin

    1993-01-01

    The flavor-singlet axial-vector current is calculated in a quark model within pseudoscalar background-field through the Seeley-DeWitt coefficients. This current is responsible for the quark spin content of proton and is of O(1) in the large-N e expansion

  11. Singlet vs Nonsinglet Perturbative Renormalization factors of Staggered Fermion Bilinears

    Science.gov (United States)

    Panagopoulos, Haralambos; Spanoudes, Gregoris

    2018-03-01

    In this paper we present the perturbative computation of the difference between the renormalization factors of flavor singlet (Σfψ¯fΓψf', f : flavor index) and nonsinglet (ψ¯f1Γψf2,f1 ≠ f2) bilinear quark operators (where Γ = 𝟙, γ5, γ µ, γ5 γ µ, γ5 σµv on the lattice. The computation is performed to two loops and to lowest order in the lattice spacing, using Symanzik improved gluons and staggered fermions with twice stout-smeared links. The stout smearing procedure is also applied to the definition of bilinear operators. A significant part of this work is the development of a method for treating some new peculiar divergent integrals stemming from the staggered formalism. Our results can be combined with precise simulation results for the renormalization factors of the nonsinglet operators, in order to obtain an estimate of the renormalization factors for the singlet operators. The results have been published in Physical Review D [1].

  12. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

    Energy Technology Data Exchange (ETDEWEB)

    Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel; Hu, Yung-Jin; Lukens, Wayne W.; Bauer, Eric D.; Maron, Laurent; Eisenstein, Odile; Andersen, Richard A.

    2009-04-22

    Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory 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 f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

  13. 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.

  14. Reliable Prediction with Tuned Range-Separated Functionals of the Singlet-Triplet Gap in Organic Emitters for Thermally Activated Delayed Fluorescence (TADF)

    KAUST Repository

    Sun, Haitao; Zhong, Cheng; Bredas, Jean-Luc

    2015-01-01

    excited states. Here, we demonstrate that time-dependent density functional theory (TD-DFT) in the Tamm-Dancoff Approximation can be very successful in the calculations of the lowest singlet and triplet excitation energies and the corresponding singlet

  15. Sizable NSI from the SU(2){sub L} scalar doublet-singlet mixing and the implications in DUNE

    Energy Technology Data Exchange (ETDEWEB)

    Forero, David V. [Center for Neutrino Physics, Virginia Tech,Blacksburg, VA, 24061 (United States); Huang, Wei-Chih [Fakultät für Physik, Technische Universität Dortmund,Dortmund, 44221 (Germany)

    2017-03-03

    We propose a novel and simple mechanism where sizable effects of non-standard interactions (NSI) in neutrino propagation are induced from the mixing between an electrophilic second Higgs doublet and a charged singlet. The mixing arises from a dimensionful coupling of the scalar doublet and singlet to the standard model Higgs boson. In light of the small mass, the light mass eigenstate from the doublet-singlet mixing can generate much larger NSI than those induced by the heavy eigenstate. We show that a sizable NSI ε{sub eτ} (∼0.3) can be attained without being excluded by a variety of experimental constraints. Furthermore, we demonstrate that NSI can mimic effects of the Dirac CP phase in the neutrino mixing matrix but they can potentially be disentangled by future long-baseline neutrino experiments, such as the Deep Underground Neutrino Experiment (DUNE).

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

    Indian Academy of Sciences (India)

    Regge-like initial input and evolution of non-singlet structure functions from DGLAP equation up to next-next-to-leading order at low x and low Q. 2. NAYAN MANI NATH1,2,∗, MRINAL KUMAR DAS1 and JAYANTA KUMAR SARMA1. 1Department of Physics, Tezpur University, Tezpur 784 028, India. 2Department of Physics ...

  17. High Selectivity Oxygen Delignification

    Energy Technology Data Exchange (ETDEWEB)

    Arthur J. Ragauskas

    2005-09-30

    The overall objective of this program was to develop improved extended oxygen delignification (EOD) technologies for current U.S. pulp mill operations. This was accomplished by: (1) Identifying pulping conditions that optimize O and OO performance; (2) Identifying structural features of lignin that enhance reactivity towards EOD of high kappa pulps; (3) Identifying factors minimizing carbohydrate degradation and improve pulp strength of EOD high kappa pulps; (4) Developing a simple, reproducible method of quantifying yield gains from EOD; and (5) Developing process conditions that significantly reduce the capital requirements of EOD while optimizing the yield benefits. Key research outcomes included, demonstrating the use of a mini-O sequence such as (E+O)Dkf:0.05(E+O) or Dkf:0.05(E+O)(E+O) without interstage washing could capture approximately 60% of the delignification efficiency of a conventional O-stage without the major capital requirements associated with an O-stage for conventional SW kraft pulps. The rate of formation and loss of fiber charge during an O-stage stage can be employed to maximize net fiber charge. Optimal fiber charge development and delignification are two independent parameters and do not parallel each other. It is possible to utilize an O-stage to enhance overall cellulosic fiber charge of low and high kappa SW kraft pulps which is beneficial for physical strength properties. The application of NIR and multi-variant analysis was developed into a rapid and simple method of determining the yield of pulp from an oxygen delignification stage that has real-world mill applications. A focus point of this program was the demonstration that Kraft pulping conditions and oxygen delignification of high and low-kappa SW and HW pulps are intimately related. Improved physical pulp properties and yield can be delivered by controlling the H-factor and active alkali charge. Low AA softwood kraft pulp with a kappa number 30 has an average improvement of 2% in

  18. High orbital angular momentum states in H2 and D2. III. Singlet--triplet splittings, energy levels, and ionization potentials

    International Nuclear Information System (INIS)

    Jungen, C.; Dabrowski, I.; Herzberg, G.; Vervloet, M.

    1990-01-01

    The 5g--4 f Rydberg groups of H 2 and D 2 first studied in paper I have been obtained with a tenfold increase in resolution which made it possible to resolve the singlet from the triplet components. As a result we can now establish separately precise values for the energy levels in the triplet and singlet systems. For this purpose we have remeasured a number of transitions between the lower energy levels for which at present only old measurements are available. In particular we obtain accurate values for the energies of the lowest (stable) triplet state a 3 Σ + g relative to the singlet ground state, as well as of the ionization potential. The values obtained for the former are more accurate than obtained from singlet--triplet anticrossings while the latter are of similar accuracy as those reported recently by McCormack et al. [Phys. Rev. A 39, 2260 (1989)] and fit well within this accuracy with the most recent ab initio values

  19. Effects of scavengers of reactive oxygen and radical species on cell survival following photodynamic treatment in vitro: comparison to ionizing radiation

    International Nuclear Information System (INIS)

    Henderson, B.W.; Miller, A.C.

    1986-01-01

    The effects of various scavengers of reactive oxygen and/or radical species on cell survival in vitro of EMT6 and CHO cells following photodynamic therapy (PDT) or gamma irradiation were compared. None of the agents used exhibited major direct cytotoxicity. Likewise, none interfered with cellular porphyrin uptake, and none except tryptophan altered singlet oxygen production during porphyrin illumination. The radioprotector cysteamine (MEA) was equally effective in reducing cell damage in both modalities. In part, this protection seems to have been induced by oxygen consumption in the system due to MEA autoxidation under formation of H 2 O 2 . The addition of catalase, which prevents H 2 O 2 buildup, reduced the effect of MEA to the same extent in both treatments. Whether the remaining protection was due to MEA's radical-reducing action or some remaining oxygen limitation is unclear. The protective action of MEA was not mediated by a doubling of cellular glutathione levels, since addition of buthionine sulfoximine, which prevented glutathione increase, did not diminish the observed MEA protection. The hydroxyl radical scavenger mannitol also afforded protection in both, but it was approximately twice as effective in gamma irradiation as in PDT. This is consistent with the predominant role of OH radicals in ionizing radiation damage and their presumed minor involvement in PDT damage. Superoxide dismutase, a scavenger of O 2 , acted as a radiation protector but was not significantly effective in PDT. Catalase, which scavenges H 2 O 2 , was ineffective in both modalities. Tryptophan, an efficient singlet oxygen scavenger, reduced cell death through PDT by several orders of magnitude while being totally ineffective in gamma irradiation. These data reaffirm the predominant role of 1O2 in the photodynamic cell killing but also indicate some involvement of free radical species

  20. Singlet and triplet states of trions in ZuSe-based quantum wells probed by magnetic fields to 50 Tesla

    Energy Technology Data Exchange (ETDEWEB)

    Astakhov, G. V.; Yakovlev, D. R.; Crooker, S. A. (Scott A.); Barrick, T. (Todd); Dzyubenko, A. B.; Sander, Thomas; Kochereshko, V. P.; Ossau, W.; Faschinger, W.; Waag, A.

    2002-01-01

    Singlet and triplet states of positively (X{sup +}) and negatively (X{sup -}) charged excitons in ZnSe-based quantum wells have been studied by means of photoluminescence in pulsed magnetic fields up to 50 T. The binding energy of the X{sup -} singlet state shows a monotonic increase with magnetic field with a tendency to saturation, while that of the X{sup +} slightly decreases. The triplet X{sup +} and X{sup -} states, being unbound at zero magnetic field, noticeably increase their binding energy in high magnetic fields. The experimental evidence for the interaction between the triplet and singlet states of lTions leading to their anticrossing in magnetic fields has been found.

  1. 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)

  2. Chemistry of bifunctional photoprobes. 3 -- Correlation between the efficiency of CH insertion by photolabile chelating agents and lifetimes of singlet nitrenes by flash photolysis: First example of photochemical attachment of 99mTc-complex with human serum albumin

    International Nuclear Information System (INIS)

    Pandurangi, R.S.; Lusiak, P.; Kuntz, R.R.; Volkert, W.A.; Rogowski, J.; Platz, M.S.

    1998-01-01

    Systematic functionalization of perfluoroaryl azides with chelating agents capable of complexing transition metals produces a new class of bifunctional photolabile chelating agents (BFPCAs). The strategy is shield the azide functionality from the electronic and steric influence of the electron-rich metal Pd through ester and amide bridges raised CH insertion efficiency to unprecedented levels (>92%) in a model solvent (cyclohexane). In contrast, perfluoroaryl azides attached to chelating agents via hydrazones show no significant CH insertion in cyclohexane upon photolysis. Measurements of the lifetimes of the singlet nitrenes derived from these agents by flash photolysis techniques correlate well with the efficiency of CH insertion by demonstrating longer lifetimes (10--50 times) for singlet nitrenes derived from azidotetrafluorinated esters and amides compared with the related hydrazones, which failed to yield significant CH insertion. A representative BFPCA 12 is chelated to diagnostic radionuclide 99m Tc and covalently attached to human serum albumin via photochemical activation extending the favorable bimolecular insertion characteristics of BFPCA to tracer level concentrations in buffer conditions. Flash photolysis experiments correlate singlet nitrene lifetimes with the efficiency of intermolecular insertion reactions. This work provides new photo-cross-linking technology, useful in radiodiagnostics and radiotherapy in nuclear medicine

  3. O2(a1Δ) vibrational kinetics in oxygen-iodine laser

    Science.gov (United States)

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

    2018-04-01

    Kinetics of vibrationally-excited singlet oxygen O2(a1Δ,ν) in gas mixture O3/N2/CO2 was studied using a pulse laser technique. Molecules O2(a1Δ,ν) were produced by laser photolysis of ozone at 266 nm. The O3 molecules number density was followed using time-resolved absorption spectroscopy. It was found that an upper bound for the rate constant of chemical reaction O2(a1Δ,ν)+ O3 is about 10-15 cm3/s. The rate constants of O2(a1Δ,ν= 1, 2 and 3) quenching by CO2 are presented.

  4. 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

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

    Indian Academy of Sciences (India)

    Theoretical framework. In the present work, the dark matter candidate has two components S and S′ both of ... The scalar sector potential (for Higgs and two real singlet scalars) in this framework can then be written .... In this work we obtain the allowed values of model parameters (δ2, δ′2, MS and M′S) using three direct ...

  6. 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

  7. Magnetically robust non-fermi liquid behavior due to the competition between crystalline-electric field singlet and Kondo-Yosida singlet in f2-based heavy fermion systems

    International Nuclear Information System (INIS)

    Nishiyama, Shinya; Matsuura, Hiroyasu; Miyake, Kazumasa

    2011-01-01

    In f 2 -based heavy fermion systems with a tetragonal symmetry, we investigate the magnetic field dependence of a non-fermi liquid (NFL) which arises related to the quantum critical point (QCP) due to the competition between the crystalline-electric field (CEF) singlet and the Kondo-Yosida singlet states. On the basis of the Wilson numerical renormalization group method, we find that the magnetic field less than a characteristic magnetic field H z * does not affect the characteristic temperature T F * at which the specific heat takes a maximum value. Since such H z * increases as the deviation from the QCP increases, slightly off the QCP, there are parameter regions where NFL behaviors are robust at an observable temperature range T > T F *against a magnetic field of up to H z * which is far larger than T F *. Our result suggests that such robust NFL behaviors can arise also in systems with other CEF symmetries; e.g., magnetically robust NFL behaviors observed in UBe 13 may be understood on this basis.

  8. High Selectivity Oxygen Delignification

    Energy Technology Data Exchange (ETDEWEB)

    Lucian A. Lucia

    2005-11-15

    Project Objective: The objectives of this project are as follows: (1) Examine the physical and chemical characteristics of a partner mill pre- and post-oxygen delignified pulp and compare them to lab generated oxygen delignified pulps; (2) Apply the chemical selectivity enhancement system to the partner pre-oxygen delignified pulps under mill conditions (with and without any predetermined amounts of carryover) to determine how efficiently viscosity is preserved, how well selectivity is enhanced, if strength is improved, measure any yield differences and/or bleachability differences; and (3) Initiate a mill scale oxygen delignification run using the selectivity enhancement agent, collect the mill data, analyze it, and propose any future plans for implementation.

  9. Measuring a 10,000-fold enhancement of singlet molecular oxygen (1O2*) concentration on illuminated ice relative to the corresponding liquid solution

    Science.gov (United States)

    Bower, Jonathan P.; Anastasio, Cort

    2013-08-01

    Much attention has focused on the highly reactive hydroxyl radical in the oxidation of trace organic compounds on snow and ice (and subsequent release of volatile organics to the atmospheric boundary layer) but other oxidants are likely also important in this processing. Here we examine the ice chemistry of singlet molecular oxygen (1O2*), which can be significant in atmospheric water drops but has not been examined in ice or snow. To examine 1O2* on ice we illuminate laboratory ices containing Rose Bengal (RB) as the source of 1O2*, furfuryl alcohol (FFA) as the probe, and Na2SO4 to control the total solute concentration. We find that the 1O2*-mediated loss of FFA (and, thus, the 1O2* concentration) is up to 11,000 times greater on ice than in the equivalent liquid sample at the same photon flux. We attribute this large increase in the 1O2* steady-state concentration to the freeze-concentration of solutes into liquid-like regions (LLRs) in/on ice: compared to the initial solution, in the LLRs of ice the sources for 1O2* are highly concentrated, while the concentration of the dominant sink for 1O2* (i.e., water) remains largely unchanged. Similar to results expected in liquid solution, rates of FFA loss in ice depend on both the initial sensitizer concentration and temperature, providing evidence that these reactions occur in LLRs. However, we find that the enhancement in 1O2* concentrations on ice does not follow predictions from freezing-point depression, likely because experiments were conducted below the eutectic temperature for sodium sulfate, where all of the salt should have precipitated. We also explore a method for separating 1O2* and rad OH contributions to FFA oxidation in laboratory ices and show its application to two natural snow samples. We find that 1O2* concentrations in these snows are approximately 100 times higher than observed in polluted, mid-latitude fog waters, showing that the enhancement of 1O2* on ice is environmentally relevant and that

  10. Carotenoids, versatile components of oxygenic photosynthesis.

    Science.gov (United States)

    Domonkos, Ildikó; Kis, Mihály; Gombos, Zoltán; Ughy, Bettina

    2013-10-01

    Carotenoids (CARs) are a group of pigments that perform several important physiological functions in all kingdoms of living organisms. CARs serve as protective agents, which are essential structural components of photosynthetic complexes and membranes, and they play an important role in the light harvesting mechanism of photosynthesizing plants and cyanobacteria. The protection against reactive oxygen species, realized by quenching of singlet oxygen and the excited states of photosensitizing molecules, as well as by the scavenging of free radicals, is one of the main biological functions of CARs. X-ray crystallographic localization of CARs revealed that they are present at functionally and structurally important sites of both the PSI and PSII reaction centers. Characterization of a CAR-less cyanobacterial mutant revealed that while the absence of CARs prevents the formation of PSII complexes, it does not abolish the assembly and function of PSI. CAR molecules assist in the formation of protein subunits of the photosynthetic complexes by gluing together their protein components. In addition to their aforementioned indispensable functions, CARs have a substantial role in the formation and maintenance of proper cellular architecture, and potentially also in the protection of the translational machinery under stress conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. 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.

  12. A quantum protective mechanism in photosynthesis

    Science.gov (United States)

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

    2015-03-01

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

  13. Roles of binding energy and diffusion length of singlet and triplet excitons in organic heterojunction solar cells

    International Nuclear Information System (INIS)

    Narayan, Monishka Rita; Singh, Jai

    2012-01-01

    The influence of binding energy and diffusion length on the dissociation of excitons in organic solids is studied. The binding energy and excitonic Bohr radius of singlet and triplet excitons are calculated and compared using the dissociation energy of 0.3 eV, which is provided by the lowest unoccupied molecular orbital offset in heterojunction organic solar cells. A relation between the diffusion coefficient and diffusion length of singlet and triplet excitons is derived using the Foerster and Dexter transfer processes and are plotted as a function of the donor-acceptor separation. The diffusion length reduces nearly to a zero if the distance between donor and acceptor is increased to more than 1.5 nm. It is found that the donor-acceptor separation needs to be ≤ 1.5 nm for easy dissociation on singlet excitons leading to better conversion efficiency in heterojunction organic solar cells. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  14. Roles of binding energy and diffusion length of singlet and triplet excitons in organic heterojunction solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Narayan, Monishka Rita [Centre for Renewable Energy and Low Emission Technology, Charles Darwin University, Darwin, NT 0909 (Australia); Singh, Jai [School of Engineering and IT, Charles Darwin University, Darwin, NT 0909 (Australia)

    2012-12-15

    The influence of binding energy and diffusion length on the dissociation of excitons in organic solids is studied. The binding energy and excitonic Bohr radius of singlet and triplet excitons are calculated and compared using the dissociation energy of 0.3 eV, which is provided by the lowest unoccupied molecular orbital offset in heterojunction organic solar cells. A relation between the diffusion coefficient and diffusion length of singlet and triplet excitons is derived using the Foerster and Dexter transfer processes and are plotted as a function of the donor-acceptor separation. The diffusion length reduces nearly to a zero if the distance between donor and acceptor is increased to more than 1.5 nm. It is found that the donor-acceptor separation needs to be {<=} 1.5 nm for easy dissociation on singlet excitons leading to better conversion efficiency in heterojunction organic solar cells. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  15. 4-spin plaquette singlet state in the Shastry-Sutherland compound SrCu2(BO3)2

    Science.gov (United States)

    Zayed, M. E.; Rüegg, Ch.; Larrea J., J.; Läuchli, A. M.; Panagopoulos, C.; Saxena, S. S.; Ellerby, M.; McMorrow, D. F.; Strässle, Th.; Klotz, S.; Hamel, G.; Sadykov, R. A.; Pomjakushin, V.; Boehm, M.; Jiménez-Ruiz, M.; Schneidewind, A.; Pomjakushina, E.; Stingaciu, M.; Conder, K.; Rønnow, H. M.

    2017-10-01

    The study of interacting spin systems is of fundamental importance for modern condensed-matter physics. On frustrated lattices, magnetic exchange interactions cannot be simultaneously satisfied, and often give rise to competing exotic ground states. The frustrated two-dimensional Shastry-Sutherland lattice realized by SrCu2(BO3)2 (refs ,) is an important test case for our understanding of quantum magnetism. It was constructed to have an exactly solvable 2-spin dimer singlet ground state within a certain range of exchange parameters and frustration. While the exact dimer state and the antiferromagnetic order at both ends of the phase diagram are well known, the ground state and spin correlations in the intermediate frustration range have been widely debated. We report here the first experimental identification of the conjectured plaquette singlet intermediate phase in SrCu2(BO3)2. It is observed by inelastic neutron scattering after pressure tuning to 21.5 kbar. This gapped singlet state leads to a transition to long-range antiferromagnetic order above 40 kbar, consistent with the existence of a deconfined quantum critical point.

  16. Singlet-Fission-Sensitized Hybrid Thin-Films For Next-Generation Photovoltaics

    Science.gov (United States)

    2016-04-12

    SECURITY CLASSIFICATION OF: This grant enabled the acquisition of equipment for the fabrication of organic and nanocrystal based photovoltaic (PV... Photovoltaics . The views, opinions and/or findings contained in this report are those of the author(s) and should not contrued as an official Department of...Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 singlet fission, nanocrystal, triplet, hybrid, photovoltaic REPORT

  17. Mechanisms of photoaddition of xanthotoxin to thymine and DNA

    International Nuclear Information System (INIS)

    Kittler, L.; Hradecna, Z.

    1980-01-01

    It has been shown that singlet oxygen is not involved in the photochemically induced covalent addition reaction of xanthotoxin to thymine or DNA. Although both heavy water and azide ions are known, to increase and decrease, respectively, the lifetime of singlet oxygen drastically, none of those additives was capable of influencing the amount of formed photoproducts. This is thought to mean that singlet oxygen drastically does not play a significant role in the photoaddition of xanthotoxin, independent of whether or not the drug is intercalated prior to the photoreaction. (author)

  18. 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.

  19. Deep blue exciplex organic light-emitting diodes with enhanced efficiency; P-type or E-type triplet conversion to singlet excitons?

    Science.gov (United States)

    Jankus, Vygintas; Chiang, Chien-Jung; Dias, Fernando; Monkman, Andrew P

    2013-03-13

    Simple trilayer, deep blue, fluorescent exciplex organic light-emitting diodes (OLEDs) are reported. These OLEDs emit from an exciplex state formed between the highest occupied molecular orbital (HOMO) of N,N'-bis(1-naphthyl)N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine (NPB) and lowest unoccupied molecular orbital (LUMO) of 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi) and the NPB singlet manifold, yielding 2.7% external quantum efficiency at 450 nm. It is shown that the majority of the delayed emission in electroluminescence arises from P-type triplet fusion at NPB sites not E-type reverse intersystem crossing because of the presence of the NPB triplet state acting as a deep trap. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Four-loop non-singlet splitting functions in the planar limit and beyond

    Energy Technology Data Exchange (ETDEWEB)

    Moch, S. [Hamburg Univ. (Germany). 2. Inst. fuer Theoretische Physik; Ruijl, B. [Nikhef, Amsterdam (Netherlands). Theory Group; Leiden Univ. (Netherlands). Leiden Centre of Data Science; Ueda, T.; Vermaseren, J.A.M. [Nikhef, Amsterdam (Netherlands). Theory Group; Vogt, A. [Liverpool Univ. (United Kingdom). Dept. of Mathematical Sciences

    2017-08-15

    We present the next-to-next-to-next-to-leading order (N{sup 3}LO) contributions to the non-singlet splitting functions for both parton distribution and fragmentation functions in perturbative QCD. The exact expressions are derived for the terms contributing in the limit of a large number of colours. For the remaining contributions, approximations are provided that are sufficient for all collider-physics applications. From their threshold limits we derive analytical and high-accuracy numerical results, respectively, for all contributions to the four-loop cusp anomalous dimension for quarks, including the terms proportional to quartic Casimir operators. We briefly illustrate the numerical size of the four-loop corrections, and the remarkable renormalization-scale stability of the N{sup 3}LO results, for the evolution of the non-singlet parton distribution and the fragmentation functions. Our results appear to provide a first point of contact of four-loop QCD calculations and the so-called wrapping corrections to anomalous dimensions in N=4 super Yang-Mills theory.

  1. Singlet and triplet polaron relaxation in doubly charged self-assembled quantum dots

    International Nuclear Information System (INIS)

    Grange, T; Zibik, E A; Ferreira, R; Bastard, G; Carpenter, B A; Phillips, P J; Stehr, D; Winnerl, S; Helm, M; Steer, M J; Hopkinson, M; Cockburn, J W; Skolnick, M S; Wilson, L R

    2007-01-01

    Polaron relaxation in self-assembled InAs/GaAs quantum dot samples containing 2 electrons per dot is studied using far-infrared, time-resolved pump-probe measurements for transitions between the s-like ground and p-like first excited conduction band states. Spin-flip transitions between singlet and triplet states are observed experimentally in the decay of the absorption bleaching, which shows a clear biexponential dependence. The initial fast decay (∼30 ps) is associated with the singlet polaron decay, while the decay component with the longer time constant (∼5 ns) corresponds to the excited state triplet lifetime. The results are explained by considering the intrinsic Dresselhaus spin-orbit interaction, which induces spin-flip transitions by acoustic phonon emission or phonon anharmonicity. We have calculated the spin-flip decay times, and good agreement is obtained between the experiment and the simulation of the pump-probe signal. Our results demonstrate the importance of spin-mixing effects for intraband energy relaxation in InAs/GaAs quantum dots

  2. Neural-network-designed pulse sequences for robust control of singlet-triplet qubits

    Science.gov (United States)

    Yang, Xu-Chen; Yung, Man-Hong; Wang, Xin

    2018-04-01

    Composite pulses are essential for universal manipulation of singlet-triplet spin qubits. In the absence of noise, they are required to perform arbitrary single-qubit operations due to the special control constraint of a singlet-triplet qubit, while in a noisy environment, more complicated sequences have been developed to dynamically correct the error. Tailoring these sequences typically requires numerically solving a set of nonlinear equations. Here we demonstrate that these pulse sequences can be generated by a well-trained, double-layer neural network. For sequences designed for the noise-free case, the trained neural network is capable of producing almost exactly the same pulses known in the literature. For more complicated noise-correcting sequences, the neural network produces pulses with slightly different line shapes, but the robustness against noises remains comparable. These results indicate that the neural network can be a judicious and powerful alternative to existing techniques in developing pulse sequences for universal fault-tolerant quantum computation.

  3. Emission of positive oxygen ions from ion bombardment of adsorbate-covered metal surfaces

    International Nuclear Information System (INIS)

    Kaurin, M.G.

    1989-01-01

    During ion bombardment of metal surfaces, collision cascades can result in the emission of sputtered secondary ions. Recent experiments, however, have suggested that the emission of positive ions of electronegative adsorbates can result from electronic processes rather than from processes involving elastic collisions. This dissertation presents the results of experiments studying the emission of positive oxygen ions from oxygen- and carbon-monoxide-covered transition metal surfaces during bombardment by 25-250 keV ions of neon, argon, and krypton. The systems studied may be grouped into four categories. For a nickel substrate with adsorbed oxygen, the emission of positive oxygen ions proceeds through collision cascades. For titanium and niobium with adsorbed oxygen, the emission of positive oxygen ions is proportional to the primary ion velocity, consistent with emission from electronic processes; for a given primary ion velocity, the oxygen ion yield is independent of primary ion species. For substrates of molybdenum and tungsten, the oxygen yield is proportional to primary ion velocity, but the yield also depends on the primary ion species for a given primary ion velocity in a manner that is consistent with emission resulting from electronic processes. For these two groups, except for titanium, the yields during neon ion bombardment do not extrapolate (assuming linearity with primary ion velocity) to a nonzero value at zero beam velocity. The magnitude of the oxygen ion yields from these targets is not consistent with that expected if the emission were induced by secondary electrons emitted during the ion bombardment

  4. 单线态分裂的超快光谱学研究∗%Ultrafast sp ectroscopic study for singlet fission

    Institute of Scientific and Technical Information of China (English)

    张博; 张春峰; 李希友; 王睿; 肖敏

    2015-01-01

    有机分子中的单线态分裂过程能将单个光激发的单线态激子转化成两个三线态激子。借助此载流子倍增效应,太阳能电池可以更有效地利用太阳光谱中的高能光子,进而突破单结太阳能电池效率的理论极限。因此,单线态分裂备受关注。本文回顾学术界对单线态分裂物理图像的认识以及争议,结合课题组近年来的一些结果,重点总结此领域中运用瞬态光谱学方法取得的实验进展,讨论有关多激子中间暗态机理的不同观点,并介绍单线态分裂材料的发展以及器件应用。%Singlet fission is a spin-allowed process that creates two triplet excitons from one photo-excited singlet exciton in organic semiconductors. This process of carrier multiplication holds the great potential to break the theoretical efficiency limit in single-junction solar cells by making better use of high-energy photons, while capturing lower-energy photons in the usual style. Photovoltaic devices based on singlet fission have achieved external quantum efficiencies in excess of 100%. In this paper, we first introduce the basic concept about singlet fission and review the history of the field briefly. Then, we report some recent advances in the research of singlet fission progress with the combination of our group’s productions. Tetracene and pentacene are chosen as typical polyacene materials for discuss. We describe how scientists make progresses in understanding the underlying physics in singlet fission process. The experimental methods of transient absorption spectra, time-resolved fluorescence spectra and time-resolved two-photon photoemission spectra render numerous results for analysis. Moreover, a survey about the debate on the direct or indirect mechanism with transient optical study is provided. It has been verified that multiexciton state intermediates in singlet fission process and the factors of energy level alignments, intermolecular

  5. Efficient singlet exciton fission in pentacene prepared from a soluble precursor

    Directory of Open Access Journals (Sweden)

    Maxim Tabachnyk

    2016-11-01

    Full Text Available Carrier multiplication using singlet exciton fission (SF to generate a pair of spin-triplet excitons from a single optical excitation has been highlighted as a promising approach to boost the photocurrent in photovoltaics (PVs thereby allowing PV operation beyond the Shockley-Queisser limit. The applicability of many efficient fission materials, however, is limited due to their poor solubility. For instance, while acene-based organics such as pentacene (Pc show high SF yields (up to200%, the plain acene backbone renders the organic molecule insoluble in common organic solvents. Previous approaches adding solubilizing side groups such as bis(tri-iso-propylsilylethynyl to the Pc core resulted in low vertical carrier mobilities due to reduction of the transfer integrals via steric hindrance, which prevented high efficiencies in PVs. Here we show how to achieve good solubility while retaining the advantages of molecular Pc by using a soluble precursor route. The precursor fully converts into molecular Pc through thermal removal of the solubilizing side groups upon annealing above 150 °C in the solid state. The annealed precursor shows small differences in the crystallinity compared to evaporated thin films of Pc, indicating that the Pc adopts the bulk rather than surface polytype. Furthermore, we identify identical SF properties such as sub-100 fs fission time and equally long triplet lifetimes in both samples.

  6. Theory of singlet-doublet excitations in praseodymium

    International Nuclear Information System (INIS)

    Bak, P.

    1975-10-01

    The magnetic excitation spectrum in a paramagnetic singlet-doublet system is calculated using a diagrammatic high density expansion technique. The lowest order diagrams, which correspond to the random phase approximation (RPA), give a detailed description of the wave vector and temperature dependence of the four exciton modes in praseodymium in terms of a Hamiltonian including isotropic Heisenberg exchange interactions and anisotropic, dipolar-like interactions. The leading contributions to the linewidths of the excitations are obtained by extending the 1/Z expansion of the generalized susceptibility propagators one order beyond the random phase approximation. This damping corresponds to spin wave scattering on single-site fluctuations. The theoretical spectral functions are in detailed agreement with experiment

  7. 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.

  8. Photodynamic mechanisms induced by a combination of hypericin and a chlorin based-photosensitizer in head and neck squamous cell carcinoma cells.

    Science.gov (United States)

    Gyenge, Emina Besic; Lüscher, Daniel; Forny, Patrick; Antoniol, Martina; Geisberger, Georg; Walt, Heinrich; Patzke, Greta; Maake, Caroline

    2013-01-01

    The aim of this study was to elucidate photodynamic therapy (PDT) effects mediated by hypericin and a liposomal meso-tetrahydroxyphenyl chlorin (mTHPC) derivative, with focus on their 1:1 mixture, on head and neck squamous cell carcinoma cell lines. Absorption, excitation and photobleaching were monitored using fluorescence spectrometry, showing the same spectral patterns for the mixture as measured for single photosensitizers. In the mixture mTHPC showed a prolonged photo-stability. Singlet oxygen yield for light-activated mTHPC was Φ(Δ) = 0.66, for hypericin Φ(Δ) = 0.25 and for the mixture Φ(Δ) = ~0.4. A linear increase of singlet oxygen yield for mTHPC and the mixture was found, whereas hypericin achieved saturation after 35 min. Reactive oxygen species fluorescence was only visible after hypericin and mixture-induced PDT. Cell viability was also more affected with these two treatment options under the selected conditions. Examination of death pathways showed that hypericin-mediated cell death was apoptotic, with mTHPC necrotic and the 1:1 mixture showed features of both. Changes in gene expression after PDT indicated strong up-regulation of selected heat-shock proteins. The application of photosensitizer mixtures with the features of reduced dark toxicity and combined apoptotic and necrotic cell death may be beneficial in clinical PDT. This will be the focus of our future investigations. © 2012 Wiley Periodicals, Inc. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

  9. Quantum chemical DFT study of the interaction between molecular oxygen and FeN₄ complexes, and effect of the macrocyclic ligand.

    Science.gov (United States)

    Silva, Adilson Luís Pereira; de Almeida, Luciano Farias; Marques, Aldaléa Lopes Brandes; Costa, Hawbertt Rocha; Tanaka, Auro Atsushi; da Silva, Albérico Borges Ferreira; de Jesus Gomes Varela, Jaldyr

    2014-03-01

    Density functional theory (DFT) was used to examine the interaction between molecular oxygen (O₂) and macrocyclic iron complexes of the type FeN₄ during the formation of FeN₄--O₂ adducts. In order to understand how this interaction is affected by different macrocyclic ligands, O₂ was bonded to iron-tetraaza[14]annulene (FeTAA), iron-tetramethyl-tetraaza[14]annulene (FeTMTAA), iron-hexamethyl-tetraaza[14]annulene (FeHMTAA), iron dibenzotetraaza[14]annulene (FeDBTAA), and two iron-tetramethyl-dibenzotetraaza[14]annulene complexes (FeTMDBTAA1, FeTMDBTAA2). The ground state for FeN₄-O₂ adducts was the open-shell singlet. Analysis of the factors influencing the O₂ bonding process showed that different macrocyclic ligands yielded adducts with differences in O--O and Fe--O₂ bond lengths, total charge over the O₂ fragment, O--O vibrational frequency, and spin density in the O₂ fragment. A smaller energy gap between the α-HOMO of the FeN₄ complexes and the β-LUMO of O₂ increased the interaction between the complex and the O₂ molecule. The order of activity was FeDBTAA < FeTMDBTAA2 < FeTMDBTAA1 < FeTAA < FeTMTAA < FeHMTAA.

  10. Viable dark matter via radiative symmetry breaking in a scalar singlet Higgs portal extension of the standard model.

    Science.gov (United States)

    Steele, T G; Wang, Zhi-Wei; Contreras, D; Mann, R B

    2014-05-02

    We consider the generation of dark matter mass via radiative electroweak symmetry breaking in an extension of the conformal standard model containing a singlet scalar field with a Higgs portal interaction. Generating the mass from a sequential process of radiative electroweak symmetry breaking followed by a conventional Higgs mechanism can account for less than 35% of the cosmological dark matter abundance for dark matter mass M(s)>80 GeV. However, in a dynamical approach where both Higgs and scalar singlet masses are generated via radiative electroweak symmetry breaking, we obtain much higher levels of dark matter abundance. At one-loop level we find abundances of 10%-100% with 106 GeVdark matter mass. The dynamical approach also predicts a small scalar-singlet self-coupling, providing a natural explanation for the astrophysical observations that place upper bounds on dark matter self-interaction. The predictions in all three approaches are within the M(s)>80 GeV detection region of the next generation XENON experiment.

  11. Toward industrial scale synthesis of ultrapure singlet nanoparticles with controllable sizes in a continuous gas-phase process

    Science.gov (United States)

    Feng, Jicheng; Biskos, George; Schmidt-Ott, Andreas

    2015-10-01

    Continuous gas-phase synthesis of nanoparticles is associated with rapid agglomeration, which can be a limiting factor for numerous applications. In this report, we challenge this paradigm by providing experimental evidence to support that gas-phase methods can be used to produce ultrapure non-agglomerated “singlet” nanoparticles having tunable sizes at room temperature. By controlling the temperature in the particle growth zone to guarantee complete coalescence of colliding entities, the size of singlets in principle can be regulated from that of single atoms to any desired value. We assess our results in the context of a simple analytical model to explore the dependence of singlet size on the operating conditions. Agreement of the model with experimental measurements shows that these methods can be effectively used for producing singlets that can be processed further by many alternative approaches. Combined with the capabilities of up-scaling and unlimited mixing that spark ablation enables, this study provides an easy-to-use concept for producing the key building blocks for low-cost industrial-scale nanofabrication of advanced materials.

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

    International Nuclear Information System (INIS)

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

    2009-01-01

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

  13. Is the Chemical Strategy for Imbuing "Polyene" Character in Diketopyrrolopyrrole-Based Chromophores Sufficient for Singlet Fission?

    Science.gov (United States)

    Mukhopadhyay, Tushita; Musser, Andrew J; Puttaraju, Boregowda; Dhar, Joydeep; Friend, Richard H; Patil, Satish

    2017-03-02

    In this work, we have rationally designed and synthesized a novel thiophene-diketopyrrolopyrrole (TDPP)-vinyl-based dimer. We have investigated the optical and electronic properties and have probed the photophysical dynamics using transient absorption to investigate the possibility of singlet exciton fission. These revealed extremely rapid decay to the ground state (TDPP-V-TDPP under direct photoexcitation. This may be a consequence of significant singlet stabilization in the dimer, bringing it below the energy needed to form two triplets. Our studies on this model compound set valuable lessons for design of novel triplet-forming materials and highlight the need for more broadly applicable design principles.

  14. On the atmospheric oxidation of liquid toluene.

    Science.gov (United States)

    Pritchard, Huw O

    2006-10-21

    This communication presents preliminary computational results on the interaction between triplet (3Sigma) and singlet (1Sigma, 1Delta) oxygen molecules with toluene. All three oxygen species form very weak complexes with toluene and all also appear capable of abstracting a benzylic hydrogen atom to form the HO2 radical. Reaction with singlet molecular oxygen does not convincingly explain the formation of benzylhydroperoxide from toluene residues stored over a long time in brown glass bottles, and it is speculated that this may be a surface-catalysed photochemical reaction. The possible involvement of singlet oxygen molecules in the spontaneous ignition of tyre rubber and of soft coal is discussed briefly and the need for new experimental studies is stressed.

  15. Double logarithmic term Ln2(1/x) in the polarized non singlet structure function at small x in valon model

    International Nuclear Information System (INIS)

    Taghavi Shahri Fatemeh; Arash, F.

    2009-01-01

    We study the low x behavior of non-singlet spin structure Function, of the nucleon in the so-called the valon representation. We find the double logarithmic term Ln 2 (1/x) in the polarized non singlet structure function at small x with using the valon model .The Structure of the valon itself develops through the perturbative dressing of a valence quark in QCD, which is independent of the hosting hadron. The results of non-singlet spin structure Function is in excellent agreement with the experimental data from HERMES collaborations for the entire measured range of x. It also provides an acceptable agreement with the older data from SMC, E143 and E155 experiments. We have further compared our results with those from AA, BB, GRSV, and DNS global fits. (authors)

  16. Stability of mass hierarchy in models with a sliding singlet

    International Nuclear Information System (INIS)

    Smirnov, A.Yu.; Tainov, E.A.

    1986-01-01

    In the broad class of models with a heavy sliding singlet and softly broken supersymmetry (e.g. by the effects of N=1 supergravity) it is shown that the doublet-triplet hierarchy obtained at the tree level is not destroyed by quantum correction at any loop order. As an example the simplest SU(5) model with a stable doublet-triplet hierarchy is proposed. The necessary and sufficient conditions of the hierarchy stability are discussed. (orig.)

  17. Ground-Laboratory to In-Space Atomic Oxygen Correlation for the PEACE Polymers

    Science.gov (United States)

    Stambler, Arielle H.; Inoshita, Karen E.; Roberts, Lily M.; Barbagallo, Claire E.; de Groh, Kim K.; Banks, Bruce A.

    2009-01-01

    The Materials International Space Station Experiment 2 (MISSE 2) Polymer Erosion and Contamination Experiment (PEACE) polymers were exposed to the environment of low Earth orbit (LEO) for 3.95 years from 2001 to 2005. There were forty-one different PEACE polymers, which were flown on the exterior of the International Space Station (ISS) in order to determine their atomic oxygen erosion yields. In LEO, atomic oxygen is an environmental durability threat, particularly for long duration mission exposures. Although space flight experiments, such as the MISSE 2 PEACE experiment, are ideal for determining LEO environmental durability of spacecraft materials, ground-laboratory testing is often relied upon for durability evaluation and prediction. Unfortunately, significant differences exist between LEO atomic oxygen exposure and atomic oxygen exposure in ground-laboratory facilities. These differences include variations in species, energies, thermal exposures and radiation exposures, all of which may result in different reactions and erosion rates. In an effort to improve the accuracy of ground-based durability testing, ground-laboratory to in-space atomic oxygen correlation experiments have been conducted. In these tests, the atomic oxygen erosion yields of the PEACE polymers were determined relative to Kapton H using a radio-frequency (RF) plasma asher (operated on air). The asher erosion yields were compared to the MISSE 2 PEACE erosion yields to determine the correlation between erosion rates in the two environments. This paper provides a summary of the MISSE 2 PEACE experiment; it reviews the specific polymers tested as well as the techniques used to determine erosion yield in the asher, and it provides a correlation between the space and ground-laboratory erosion yield values. Using the PEACE polymers' asher to in-space erosion yield ratios will allow more accurate in-space materials performance predictions to be made based on plasma asher durability evaluation.

  18. MISSE PEACE Polymers Atomic Oxygen Erosion Results

    Science.gov (United States)

    deGroh, Kim, K.; Banks, Bruce A.; McCarthy, Catherine E.; Rucker, Rochelle N.; Roberts, Lily M.; Berger, Lauren A.

    2006-01-01

    Forty-one different polymer samples, collectively called the Polymer Erosion and Contamination Experiment (PEACE) Polymers, have been exposed to the low Earth orbit (LEO) environment on the exterior of the International Space Station (ISS) for nearly 4 years as part of Materials International Space Station Experiment 2 (MISSE 2). The objective of the PEACE Polymers experiment was to determine the atomic oxygen erosion yield of a wide variety of polymeric materials after long term exposure to the space environment. The polymers range from those commonly used for spacecraft applications, such as Teflon (DuPont) FEP, to more recently developed polymers, such as high temperature polyimide PMR (polymerization of monomer reactants). Additional polymers were included to explore erosion yield dependence upon chemical composition. The MISSE PEACE Polymers experiment was flown in MISSE Passive Experiment Carrier 2 (PEC 2), tray 1, on the exterior of the ISS Quest Airlock and was exposed to atomic oxygen along with solar and charged particle radiation. MISSE 2 was successfully retrieved during a space walk on July 30, 2005, during Discovery s STS-114 Return to Flight mission. Details on the specific polymers flown, flight sample fabrication, pre-flight and post-flight characterization techniques, and atomic oxygen fluence calculations are discussed along with a summary of the atomic oxygen erosion yield results. The MISSE 2 PEACE Polymers experiment is unique because it has the widest variety of polymers flown in LEO for a long duration and provides extremely valuable erosion yield data for spacecraft design purposes.

  19. Singlet structure function F_1 in double-logarithmic approximation

    Science.gov (United States)

    Ermolaev, B. I.; Troyan, S. I.

    2018-03-01

    The conventional ways to calculate the perturbative component of the DIS singlet structure function F_1 involve approaches based on BFKL which account for the single-logarithmic contributions accompanying the Born factor 1 / x. In contrast, we account for the double-logarithmic (DL) contributions unrelated to 1 / x and because of that they were disregarded as negligibly small. We calculate the singlet F_1 in the double-logarithmic approximation (DLA) and account at the same time for the running α _s effects. We start with a total resummation of both quark and gluon DL contributions and obtain the explicit expression for F_1 in DLA. Then, applying the saddle-point method, we calculate the small- x asymptotics of F_1, which proves to be of the Regge form with the leading singularity ω _0 = 1.066. Its large value compensates for the lack of the factor 1 / x in the DLA contributions. Therefore, this Reggeon can be identified as a new Pomeron, which can be quite important for the description of all QCD processes involving the vacuum (Pomeron) exchanges at very high energies. We prove that the expression for the small- x asymptotics of F_1 scales: it depends on a single variable Q^2/x^2 only instead of x and Q^2 separately. Finally, we show that the small- x asymptotics reliably represent F_1 at x ≤ 10^{-6}.

  20. The antioxidant action of Polypodium leucotomos extract and kojic acid: reactions with reactive oxygen species

    Directory of Open Access Journals (Sweden)

    A.J. Gomes

    2001-11-01

    Full Text Available Two natural products Polypodium leucotomos extract (PL and kojic acid (KA were tested for their ability to scavenge reactive oxygen species (·OH, ·O2-, H2O2, ¹O2 in phosphate buffer. Hydroxyl radicals were generated by the Fenton reaction, and the rate constants of scavenging were 1.6 x 10(9 M-1 s-1 for KA and 1.0 x 10(9 M-1 s-1 for PL, similar to that of ethanol (1.4 x 10(9 M-1 s-1. With superoxide anions generated by the xanthine/hypoxanthine system, KA and PL (0.2-1.0 mg/ml inhibited ·O2-dependent reduction of nitroblue tetrazolium by up to 30 and 31%, respectively. In the detection of ¹O2 by rose bengal irradiation, PL at 1.0 mg/ml quenched singlet oxygen by 43% relative to azide and KA by 36%. The present study demonstrates that PL showed an antioxidant effect, scavenging three of four reactive oxygen species tested here. Unlike KA, PL did not significantly scavenge hydrogen peroxide.

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

    KAUST Repository

    Sun, Zhe; Huang, Kuo-Wei; Wu, Jishan

    2011-01-01

    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.

  2. 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.

  3. Electron Transfer from Triplet State of TIPS-Pentacene Generated by Singlet Fission Processes to CH3NH3PbI3 Perovskite.

    Science.gov (United States)

    Lee, Sangsu; Hwang, Daesub; Jung, Seok Il; Kim, Dongho

    2017-02-16

    To reveal the applicability of singlet fission processes in perovskite solar cell, we investigated electron transfer from TIPS-pentacene to CH 3 NH 3 PbI 3 (MAPbI 3 ) perovskite in film phase. Through the observation of the shorter fluorescence lifetime in TIPS-pentacene/MAPbI 3 perovskite bilayer film (5 ns) compared with pristine MAPbI 3 perovskite film (20 ns), we verified electron-transfer processes between TIPS-pentacene and MAPbI 3 perovskite. Furthermore, the observation of singlet fission processes, a faster decay rate, TIPS-pentacene cations, and the analysis of kinetic profiles of the intensity ratio between 500 and 525 nm in the TA spectra of the TIPS-pentacene/MAPbI 3 perovskite bilayer film indicate that electron transfer occurs from triplet state of TIPS-pentacene generated by singlet fission processes to MAPbI 3 perovskite conduction band. We believe that our results can provide useful information on the design of solar cells sensitized by singlet fission processes and pave the way for new types of perovskite solar cells.

  4. Quadrupole singlet focusing for achromatic parallel-to-parallel devices

    International Nuclear Information System (INIS)

    Brown, K.L.

    1983-01-01

    A first order achromatic magnetic deflection system for use in conjunction with a charged particle accelerator is realized from a stepped gap magnet wherein charged particles propagating through the system are subject to at least two adjacent homogeneous magnetic fields in adjacent regions in traversing one-half of a symmetric trajectory through the system. A quadrupole singlet element Q of adjustable focal length disposed substantially at the entrance plane of such a symmetric system makes possible the coincidence of the waists of the beam in both the vertical (transverse) and (radial) bending planes. (author)

  5. Quantitative measurements of ground state atomic oxygen in atmospheric pressure surface micro-discharge array

    Science.gov (United States)

    Li, D.; Kong, M. G.; Britun, N.; Snyders, R.; Leys, C.; Nikiforov, A.

    2017-06-01

    The generation of atomic oxygen in an array of surface micro-discharge, working in atmospheric pressure He/O2 or Ar/O2 mixtures, is investigated. The absolute atomic oxygen density and its temporal and spatial dynamics are studied by means of two-photon absorption laser-induced fluorescence. A high density of atomic oxygen is detected in the He/O2 mixture with up to 10% O2 content in the feed gas, whereas the atomic oxygen concentration in the Ar/O2 mixture stays below the detection limit of 1013 cm-3. The measured O density near the electrode under the optimal conditions in He/1.75% O2 gas is 4.26  ×  1015 cm-3. The existence of the ground state O (2p 4 3 P) species has been proven in the discharge at a distance up to 12 mm away from the electrodes. Dissociative reactions of the singlet O2 with O3 and deep vacuum ultraviolet radiation, including the radiation of excimer \\text{He}2\\ast , are proposed to be responsible for O (2p 4 3 P) production in the far afterglow. A capability of the surface micro-discharge array delivering atomic oxygen to long distances over a large area is considered very interesting for various biomedical applications.

  6. Joint absorption of lithium and oxygen on the tungsten (100) face

    International Nuclear Information System (INIS)

    Gupalo, M.S.; Smereka, T.P.; Babkin, G.V.; Palyukh, B.M.

    1981-01-01

    The paper deals with studying the effect of oxygen on emission-adsorption properties of metal-film Li-W system. Data on work of phi yield and adsorption heat q of lithium on tungsten face (100), preliminarily coated with different quantity of oxygen, are obtained. The method of contact potential difference was used. Strong decrease of yield work with the increase of oxygen coatings, as well as essential growth of initial adsorption heat are observed. Temperature dependence of phi is not practically observed. The data obtained point out, that oxygen presence on the surface causes increase of dipole momentum of lithium adatoms, which results in bond energy growth and reduction phi minimal value of lithium in the presence of oxygen phi=2 eV, q=2.2 eV is obtained at optimal compositions of oxygen-lithium layers on W (100) [ru

  7. 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

  8. Impact of Dielectric Constant on the Singlet-Triplet Gap in Thermally Activated Delayed Fluorescence (TADF) Materials

    KAUST Repository

    Sun, Haitao

    2017-04-28

    Thermally activated delayed fluorescence (TADF) relies on the presence of a very small energy gap, ΔEST, between the lowest singlet and triplet excited states. ΔEST is thus a key factor in the molecular design of more efficient materials. However, its accurate theoretical estimation remains challenging, especially in the solid state due to the influence of polarization effects. We have quantitatively studied ΔEST as a function of dielectric constant, ε, for four representative organic molecules using the methodology we recently proposed at the Tamm-Dancoff approximation ωB97X level of theory, where the range-separation parameter ω is optimized with the polarizable continuum model. The results are found to be in very good agreement with experimental data. Importantly, the polarization effects can lead to a marked reduction in the ΔEST value, which is favorable for TADF applications. This ΔEST decrease in the solid state is related to the hybrid characters of the lowest singlet and triplet excited states, whose dominant contribution switches to charge-transfer-like with increasing ε. The present work provides a theoretical understanding on the influence of polarization effect on the singlet-triplet gap and confirms our methodology to be a reliable tool for the prediction and development of novel TADF materials.

  9. 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

  10. Carotenoids quench evolution of excited species in epidermis exposed to UV-B (290-320 nm) light

    International Nuclear Information System (INIS)

    Mathews-Roth, M.M.

    1986-01-01

    Reactions involving singlet oxygen and other free radicals have been identified in epidermis containing either exogenous or endogenous photosensitizers, soaked in a singlet oxygen/free radical trap, and then exposed to visible or UV-A (320-400 nm) light. Such reactions can be quenched by the presence of the carotenoid pigments β-carotene and canthaxanthin which accumulate in epidermis after oral administration. It is reported that the carotenoid pigments β-carotene, canthaxanthin and phytoene accumulating in epidermis can also quench to some degree those photochemical reactions involving singlet oxygen and free radicals that occur when epidermis is exposed to the sunburn spectrum of light (UV-B, 290-320 nm). (author)

  11. Photophysical and photochemical properties of Bauhinia megalandra (Caesalpinaceae) extracts as new PDT photosensitizer

    Science.gov (United States)

    Vargas Tovar, Franklin R.; Rivas, C.; Estrada, O.; Marcano O., Aristides A.; Echevarria, Lorenzo; Diaz, Yrene; Alexander, I.; Rodriguez, L.; Padron, L.; Rivera, I. R.

    2004-10-01

    Recently new photosensitizers, chlorophyll "a and b" derivatives, for photodynamic therapy (PDT) have been presented. It already passed complete pre-clinical investigations. This prompted us to carry out an extensive study of photophysical properties of chlorine derivatives, important both for optimization of their clinic applications and for study of mechanisms of chlorine PDT&. The fresh leaves of Bauhinia megalandra (Caesalpinaceae) were extracted with methanol by percolation, and re-extract with a mixture of methanol-water (1:1), the insoluble fraction was then separated by column chromatography [RP18/hexane-ethylacetate (9:1)] to obtain four fractions named 1 to 4. These compounds were identified by NMR data. We found that 3 and 4 efficiently generates singlet oxygen when irradiated with visible light. Detection of the singlet oxygen was fulfilled by its reaction with histidine and detected by bleaching p-nitrosodimethylaniline under 440 nm irradiation. The quantum yields of singlet oxygen determined by us were 0.088 (1), 0.151 (2), 0.219 (3) and 0.301 (4). We measured absorption and fluorescence spectra of compounds 1 to 4 (Mg-chlorophyll-a, Pheophytin, Mg-chlorophyll-b and chlorophyll-b respectively) in different media and in aqueous solutions of human serum albumin. The association constant of the compounds 1, 2, 3 and 4 in the presence of HSA were estimated. The binding and quenching studies suggest that only 1 and 3 may serve as a useful fluorescence probe for structure/function studies of different chlorophyll binding proteins. No photoinduced binding was observed after irradiation by all the studied compounds in presence of human serum albumin.

  12. 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

  13. cis-Stilbene and (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)benzene as mechanistic probes in the Mn(III)(salen)-catalyzed epoxidation: influence of the oxygen source and the counterion on the diastereoselectivity of the competitive concerted and radical-type oxygen transfer.

    Science.gov (United States)

    Adam, Waldemar; Roschmann, Konrad J; Saha-Möller, Chantu R; Seebach, Dieter

    2002-05-08

    cis-Stilbene (1) has been epoxidized by a set of diverse oxygen donors [OxD], catalyzed by the Mn(III)(salen)X complexes 3 (X = Cl, PF(6)), to afford a mixture of cis- and trans-epoxides 2. The cis/trans ratios range from 29:71 (extensive isomerization) to 92:8, which depends both on the oxygen source [OxD] and on the counterion X of the catalyst. When (1 alpha,2 beta,3 alpha)-(2-ethenyl-3-methoxycyclopropyl)-benzene (4) is used as substrate, a mechanistic probe which differentiates between radical and cationic intermediates, no cationic ring-opening products are found in this epoxidation reaction; thus, isomerized epoxide product arises from intermediary radicals. The dependence of the diastereoselectivity on the oxygen source is rationalized in terms of a bifurcation step in the catalytic cycle, in which concerted Lewis-acid-activated oxygen transfer competes with stepwise epoxidation by the established Mn(V)(oxo) species. The experimental counterion effect is attributed to the computationally assessed ligand-dependent reaction profiles and stereoselectivities of the singlet, triplet, and quintet spin states available to the manganese species.

  14. 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.

  15. Dark-matter sterile neutrinos in models with a gauge singlet in the Higgs sector

    International Nuclear Information System (INIS)

    Petraki, Kalliopi; Kusenko, Alexander

    2008-01-01

    Sterile neutrino with mass of several keV can be the cosmological dark matter, can explain the observed velocities of pulsars, and can play an important role in the formation of the first stars. We describe the production of sterile neutrinos in a model with an extended Higgs sector, in which the Majorana mass term is generated by the vacuum expectation value of a gauge-singlet Higgs boson. In this model the relic abundance of sterile neutrinos does not necessarily depend on their mixing angles, the free-streaming length can be much smaller than in the case of warm dark matter produced by neutrino oscillations, and, therefore, some of the previously quoted bounds do not apply. The presence of the gauge singlet in the Higgs sector has important implications for the electroweak phase transition, baryogenesis, and the upcoming experiments at the Large Hadron Collider and a Linear Collider.

  16. Does interchain stacking morphology contribute to the singlet-triplet interconversion dynamics in polymer heterojunctions?

    Energy Technology Data Exchange (ETDEWEB)

    Bittner, Eric R. [Department of Chemistry and Texas Center for Superconductivity, University of Houston, Houston, TX 77204 (United States)], E-mail: bittner@uh.edu; Burghardt, Irene [Departement de Chimie, Ecole Normale Superieure, 24 rue Lhomond, F-75231 Paris cedex 05 (France); Friend, Richard H. [Cavendish Laboratory, Madingley Road, Cambridge CB3 0HE (United Kingdom)

    2009-02-23

    Time-dependent density functional theory (TD-DFT) is used to examine the effect of stacking in a model semiconducting polymer hetrojunction system consisting of two co-facially stacked oligomers. We find that the excited electronic states are highly sensitive to the alignment of the monomer units of the two chains. In the system we examined, the exchange energy is nearly identical to both the and band off-set at the heterojunction and to the exciton binding energy. Our results indicate that the triplet excitonic states are nearly degenerate with the singlet exciplex states opening the possibility for the interconversion of singlet and triplet electronic states at the heterojunction interface via spin-orbit coupling localized on the heteroatoms. Using Russell-Saunders theory, we estimate this interconversion rate to be approximately 700-800 ps, roughly a 5-10-fold increase compared to isolated organic polymer chains.

  17. Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission.

    Science.gov (United States)

    Sakuma, Takao; Sakai, Hayato; Araki, Yasuyuki; Mori, Tadashi; Wada, Takehiko; Tkachenko, Nikolai V; Hasobe, Taku

    2016-03-24

    Intramolecular singlet fission (ISF) is a promising photophysical process to construct more efficient light energy conversion systems as one excited singlet state converts into two excited triplet states. Herein we synthesized and evaluated bent-shaped pentacene dimers as a prototype of ISF to reveal intrinsic characters of triplet states (e.g., lifetimes of triplet excited states). In this study, meta-phenylene-bridged TIPS-pentacene dimer (PcD-3Ph) and 2,2'-bipheynyl bridged TIPS-pentacene dimer (PcD-Biph) were newly synthesized as bent-shaped dimers. In the steady-state spectroscopy, absorption and emission bands of these dimers were fully characterized, suggesting the appropriate degree of electronic coupling between pentacene moieties in these dimers. In addition, the electrochemical measurements were also performed to check the electronic interaction between two pentacene moieties. Whereas the successive two oxidation peaks owing to the delocalization were observed in a directly linked-pentacene dimer (PcD) by a single bond, the cyclic voltammograms in PcD-Biph and PcD-3Ph implied the weaker interaction compared to that of p-phenylene-bridged TIPS-pentacene dimer (PcD-4Ph) and PcD. The femtosecond and nanosecond transient absorption spectra clearly revealed the slower ISF process in bent-shaped pentacene dimers (PcD-Biph and PcD-3Ph), more notably, the slower relaxation of the excited triplet states in PcD-Biph and PcD-3Ph. Namely, the quantum yields of triplet states (ΦT) by ISF approximately remain constant (ca. 180-200%) in all dimer systems, whereas the lifetimes of the triplet excited states became much longer (up to 360 ns) in PcD-Biph as compared to PcD-4Ph (15 ns). Additionally, the lifetimes of the corresponding triplet states in PcD-Biph and PcD-3Ph were sufficiently affected by solvent viscosity. In particular, the lifetimes of PcD-Biph triplet state in THF/paraffin (1.0 μs) increased up to approximately three times as compared to that in THF

  18. Low Temperature Soda-Oxygen Pulping of Bagasse.

    Science.gov (United States)

    Yue, Fengxia; Chen, Ke-Li; Lu, Fachuang

    2016-01-13

    Wood shortages, environmental pollution and high energy consumption remain major obstacles hindering the development of today's pulp and paper industry. Energy-saving and environmental friendly pulping processes are still needed, especially for non-woody materials. In this study, soda-oxygen pulping of bagasse was investigated and a successful soda-oxygen pulping process for bagasse at 100 °C was established. The pulping parameters of choice were under active alkali charge of 23%, maximum cooking temperature 100 °C, time hold at maximum temperature 180 min, initial pressure of oxygen 0.6 MPa, MgSO4 charge 0.5%, and de-pithed bagasse consistency 12%. Properties of the resultant pulp were screened yield 60.9%, Kappa number 14, viscosity 766 dm³/kg, and brightness 63.7% ISO. Similar pulps were also obtained at 110 °C or 105 °C with a cooking time of 90 min. Compared with pulps obtained at higher temperatures (115-125 °C), this pulp had higher screened yield, brightness, and acceptable viscosity, while the delignification degree was moderate. These results indicated that soda-oxygen pulping at 100 °C, the lowest cooking temperature reported so far for soda-oxygen pulping, is a suitable process for making chemical pulp from bagasse. Pulping at lower temperature and using oxygen make it an environmental friendly and energy-saving pulping process.

  19. Low Temperature Soda-Oxygen Pulping of Bagasse

    Directory of Open Access Journals (Sweden)

    Fengxia Yue

    2016-01-01

    Full Text Available Wood shortages, environmental pollution and high energy consumption remain major obstacles hindering the development of today’s pulp and paper industry. Energy-saving and environmental friendly pulping processes are still needed, especially for non-woody materials. In this study, soda-oxygen pulping of bagasse was investigated and a successful soda-oxygen pulping process for bagasse at 100 °C was established. The pulping parameters of choice were under active alkali charge of 23%, maximum cooking temperature 100 °C, time hold at maximum temperature 180 min, initial pressure of oxygen 0.6 MPa, MgSO4 charge 0.5%, and de-pithed bagasse consistency 12%. Properties of the resultant pulp were screened yield 60.9%, Kappa number 14, viscosity 766 dm3/kg, and brightness 63.7% ISO. Similar pulps were also obtained at 110 °C or 105 °C with a cooking time of 90 min. Compared with pulps obtained at higher temperatures (115–125 °C, this pulp had higher screened yield, brightness, and acceptable viscosity, while the delignification degree was moderate. These results indicated that soda-oxygen pulping at 100 °C, the lowest cooking temperature reported so far for soda-oxygen pulping, is a suitable process for making chemical pulp from bagasse. Pulping at lower temperature and using oxygen make it an environmental friendly and energy-saving pulping process.

  20. Properties of pseudoscalar flavor singlet mesons from lattice QCD

    International Nuclear Information System (INIS)

    Ottnad, Konstantin

    2014-01-01

    The central topic of this work are masses and mixing parameters of the η-η' system, which are investigated within the framework of Wilson twisted mass lattice QCD, using gauge configurations provided by the European Twisted Mass Collaboration. We present the first calculation with N f =2+1+1 dynamical quark flavors performed at three different values of the lattice spacing and multiple values of the light quark mass, corresponding to charged pion masses ranging from ∝230 MeV to ∝500 MeV. Moreover, we use selected ensembles which differ only by the value of the strange quark mass while all other parameters are kept fixed in order to obtain information on the strange quark mass dependence of our observables. This allows us to carry out chiral and continuum extrapolations with well-controlled systematics for the mass of the η meson. Using the standard method, the statistical error for the η' turns out significantly larger due to the large contributions of quark disconnected diagrams and autocorrelation effects. However, employing an improved analysis method based on an excited state subtraction in the connected pieces of the correlation function matrix, it becomes feasible to obtain a result for the η' mass with controlled systematics as well. The values for both masses M η =551(8) stat (6) sys MeV and M η' =1006(54) stat (38) sys (+64) ex MeV turn out to be in excellent agreement with experiment. Considering matrix elements in the quark-flavor basis, one expects the mixing in the η-η' system to be described reasonably well by a single mixing angle φ and two decay constants f l , f s . The required accuracy of the matrix elements is again guaranteed by the aforementioned, improved analysis method, yielding a value of φ=46.0(0.9) stat (2.7) sys circle for the mixing angle extrapolated to the physical point. In addition we obtain results for the ratios f l /f PS =0.859(07) stat (64) sys and f s /f K =1.166(11) stat (31) sys . We find that our data is

  1. Probing the singlet character of the two-hole states in cuprate superconductors

    NARCIS (Netherlands)

    Ghiringhelli, G; Brookes, NB; Tjeng, LH; Mizokawa, T; Tjernberg, O; Menovsky, AA; Steeneken, P.G.

    Using spin-resolved resonant photoemission we have probed the singlet vs. triplet character of the two-hole state in the layered cuprates Bi2Sr2CaCu2O8+delta La2-xSrxCuO4 and Sr2CuO2Cl2. The combination of the photon circular polarization with the photoelectron spin detection gives access to the

  2. Iridium complexes for the application of photodynamic therapy

    Directory of Open Access Journals (Sweden)

    SHI Min

    2015-10-01

    Full Text Available Photodynamic therapy can destruct tumor cells by singlet oxygen which is generated via a photodynamic reaction of the photosensitizer under a specfic excitation wavelength.Due to the heavy atom effect of metal iridium,iridiumcomplexes are excited by suitable light and then reach their excited triple state through intersystem crossing.The excited iridium complexes transfer energy to oxygen molecules to produce singlet oxygen for photodynamic therapy.

  3. Device-independent parallel self-testing of two singlets

    Science.gov (United States)

    Wu, Xingyao; Bancal, Jean-Daniel; McKague, Matthew; Scarani, Valerio

    2016-06-01

    Device-independent self-testing offers the possibility of certifying the quantum state and measurements, up to local isometries, using only the statistics observed by querying uncharacterized local devices. In this paper we study parallel self-testing of two maximally entangled pairs of qubits; in particular, the local tensor product structure is not assumed but derived. We prove two criteria that achieve the desired result: a double use of the Clauser-Horne-Shimony-Holt inequality and the 3 ×3 magic square game. This demonstrate that the magic square game can only be perfectly won by measuring a two-singlet state. The tolerance to noise is well within reach of state-of-the-art experiments.

  4. Photosensitizing Nanoparticles and The Modulation of Reactive Oxygen Species generation

    Directory of Open Access Journals (Sweden)

    Dayane Batista Tada

    2015-05-01

    Full Text Available The association of PhotoSensitizer (PS molecules with nanoparticles (NPs forming photosensitizing NPs, has emerged as a therapeutic strategy to improve PS tumor targeting, to protect PS from deactivation reactions and to enhance both PS solubility and circulation time. Since association with NPs usually alters PS photophysical and photochemical properties, photosensitizing NPs are an important tool to modulate reactive oxygen species (ROS generation. Depending on the design of the photosensitizing NP, i.e., type of PS, the NP material and the method applied for the construction of the photosensitizing NP, the deactivation routes of the excited state can be controlled, allowing the generation of either singlet oxygen or other ROS. Controlling the type of generated ROS is desirable not only in biomedical applications, as in Photodynamic Therapy where the type of ROS affects therapeutic efficiency, but also in other technological relevant fields like energy conversion, where the electron and energy transfer processes are necessary to increase the efficiency of photoconversion cells. The current review highlights some of the recent developments in the design of Photosensitizing NPs aimed at modulating the primary photochemical events after light absorption.

  5. Experimental assessment of bacterial storage yield

    DEFF Research Database (Denmark)

    Karahan-Gül, Ö.; Artan, N.; Orhon, D.

    2002-01-01

    to the amount of oxygen associated with substrate storage. Model simulation was used to evaluate the procedure for different initial experimental conditions. The procedure was tested on acetate. The same storage yield value of 0.76 gCOD/gCOD was calculated for two experiments, starting with different F/M ratios...

  6. Biocompatible ZnS:Mn quantum dots for reactive oxygen generation and detection in aqueous media

    International Nuclear Information System (INIS)

    Diaz-Diestra, Daysi; Beltran-Huarac, Juan; Bracho-Rincon, Dina P.; González-Feliciano, José A.; González, Carlos I.; Weiner, Brad R.; Morell, Gerardo

    2015-01-01

    We report here the versatility of Mn-doped ZnS quantum dots (ZnS:Mn QDs) synthesized in aqueous medium for generating reactive oxygen species and for detecting cells. Our experiments provide evidence leading to the elimination of Cd-based cores in CdSe/ZnS systems by substitution of Mn-doped ZnS. Advanced electron microscopy, X-ray diffraction, and optical spectroscopy were applied to elucidate the formation, morphology, and dispersion of the products. We study for the first time the ability of ZnS:Mn QDs to act as immobilizing agents for Tyrosinase (Tyr) enzyme. It was found that ZnS:Mn QDs show no deactivation of Tyr enzyme, which efficiently catalyzed the hydrogen peroxide (H 2 O 2 ) oxidation and its eventual reduction (−0.063 V vs. Ag/AgCl) on the biosensor surface. The biosensor showed a linear response in the range of 12 μmol/L–0.1 mmol/L at low operation potential. Our observations are explained in terms of a catalase-cycled kinetic mechanism based on the binding of H 2 O 2 to the axial position of one of the active copper sites of the oxy-Tyr during the catalase cycle to produce deoxy-Tyr. A singlet oxygen quantum yield of 0.62 in buffer and 0.54 in water was found when ZnS:Mn QDs were employed as a photosensitizer in the presence of a chemical scavenger and a standard dye. These results are consistent with a chemical trapping energy transfer mechanism. Our results also indicate that ZnS:Mn QDs are well tolerated by HeLa Cells reaching cell viabilities as high as 88 % at 300 µg/mL of QDs for 24 h of incubation. The ability of ZnS:Mn QDs as luminescent nanoprobes for bioimaging is also discussed.Graphical Abstract

  7. Biocompatible ZnS:Mn quantum dots for reactive oxygen generation and detection in aqueous media

    Science.gov (United States)

    Diaz-Diestra, Daysi; Beltran-Huarac, Juan; Bracho-Rincon, Dina P.; González-Feliciano, José A.; González, Carlos I.; Weiner, Brad R.; Morell, Gerardo

    2015-12-01

    We report here the versatility of Mn-doped ZnS quantum dots (ZnS:Mn QDs) synthesized in aqueous medium for generating reactive oxygen species and for detecting cells. Our experiments provide evidence leading to the elimination of Cd-based cores in CdSe/ZnS systems by substitution of Mn-doped ZnS. Advanced electron microscopy, X-ray diffraction, and optical spectroscopy were applied to elucidate the formation, morphology, and dispersion of the products. We study for the first time the ability of ZnS:Mn QDs to act as immobilizing agents for Tyrosinase (Tyr) enzyme. It was found that ZnS:Mn QDs show no deactivation of Tyr enzyme, which efficiently catalyzed the hydrogen peroxide (H2O2) oxidation and its eventual reduction (-0.063 V vs. Ag/AgCl) on the biosensor surface. The biosensor showed a linear response in the range of 12 μmol/L-0.1 mmol/L at low operation potential. Our observations are explained in terms of a catalase-cycled kinetic mechanism based on the binding of H2O2 to the axial position of one of the active copper sites of the oxy-Tyr during the catalase cycle to produce deoxy-Tyr. A singlet oxygen quantum yield of 0.62 in buffer and 0.54 in water was found when ZnS:Mn QDs were employed as a photosensitizer in the presence of a chemical scavenger and a standard dye. These results are consistent with a chemical trapping energy transfer mechanism. Our results also indicate that ZnS:Mn QDs are well tolerated by HeLa Cells reaching cell viabilities as high as 88 % at 300 µg/mL of QDs for 24 h of incubation. The ability of ZnS:Mn QDs as luminescent nanoprobes for bioimaging is also discussed.

  8. Sputtering of solid nitrogen and oxygen by keV hydrogen ions

    DEFF Research Database (Denmark)

    Ellegaard, O.; Schou, Jørgen; Stenum, B.

    1994-01-01

    Electronic sputtering of solid nitrogen and oxygen by keV hydrogen ions has been studied at two low-temperature setups. The yield of the sputtered particles has been determined in the energy regime 4-10 keV for H+, H-2+ and H-3+ ions. The yield for oxygen is more than a factor of two larger than...... that for nitrogen. The energy distributions of the sputtered N2 and O2 molecules were measured for hydrogen ions in this energy regime as well. The yields from both solids turn out to depend on the sum of the stopping power of all atoms in the ion. The yield increases as a quadratic function of the stopping power...

  9. Topological quantum phase transitions in the spin–singlet superconductor with Rashba and Dresselhaus (110) spin–orbit couplings

    Energy Technology Data Exchange (ETDEWEB)

    You, Jia-Bin, E-mail: jiabinyou@gmail.com [Centre for Quantum Technologies, National University of Singapore, 117543 (Singapore); Chan, A.H. [Department of Physics, National University of Singapore, 117542 (Singapore); Oh, C.H., E-mail: phyohch@nus.edu.sg [Centre for Quantum Technologies, National University of Singapore, 117543 (Singapore); Department of Physics, National University of Singapore, 117542 (Singapore); Vedral, Vlatko [Centre for Quantum Technologies, National University of Singapore, 117543 (Singapore); Department of Physics, National University of Singapore, 117542 (Singapore); Department of Physics, University of Oxford, Clarendon Laboratory, Oxford, OX1 3PU (United Kingdom)

    2014-10-15

    We examine the topological properties of a spin–singlet superconductor with Rashba and Dresselhaus (110) spin–orbit couplings. We demonstrate that there are several topological invariants in the Bogoliubov–de Gennes (BdG) Hamiltonian by symmetry analysis. In particular, the Pfaffian invariant P for the particle–hole symmetry can be used to demonstrate all the possible phase diagrams of the BdG Hamiltonian. We find that the edge spectrum is either Dirac cone or flat band which supports the emergence of the Majorana fermion in this system. For the Majorana flat bands, an edge index, namely the Pfaffian invariant P(k{sub y}) or the winding number W(k{sub y}), is needed to make them topologically stable. These edge indices can also be used in determining the location of the Majorana flat bands. - Highlights: • Majorana fermion can emerge in the spin–orbit coupled singlet superconductor. • Pfaffian invariant and 1D winding number can be used to identify the nontrivial topological phase where Majorana flat band exists. • All the possible phase diagrams in the spin–orbit coupled singlet superconductor are demonstrated. • Majorana flat band only exists in the y direction in our model. • Majorana flat band has a significant experimental signature in the tunneling conductance measurement.

  10. Simultaneous sampling of tissue oxygenation and oxygen consumption in skeletal muscle.

    Science.gov (United States)

    Nugent, William H; Song, Bjorn K; Pittman, Roland N; Golub, Aleksander S

    2016-05-01

    Under physiologic conditions, microvascular oxygen delivery appears to be well matched to oxygen consumption in respiring tissues. We present a technique to measure interstitial oxygen tension (PISFO2) and oxygen consumption (VO2) under steady-state conditions, as well as during the transitions from rest to activity and back. Phosphorescence Quenching Microscopy (PQM) was employed with pneumatic compression cycling to achieve 1 to 10 Hz sampling rates of interstitial PO2 and simultaneous recurrent sampling of VO2 (3/min) in the exteriorized rat spinotrapezius muscle. The compression pressure was optimized to 120-130 mmHg without adverse effect on the tissue preparation. A cycle of 5s compression followed by 15s recovery yielded a resting VO2 of 0.98 ± 0.03 ml O2/100 cm(3)min while preserving microvascular oxygen delivery. The measurement system was then used to assess VO2 dependence on PISFO2 at rest and further tested under conditions of isometric muscle contraction to demonstrate a robust ability to monitor the on-kinetics of tissue respiration and the compensatory changes in PISFO2 during contraction and recovery. The temporal and spatial resolution of this approach is well suited to studies seeking to characterize microvascular oxygen supply and demand in thin tissues. Copyright © 2015 Elsevier Inc. All rights reserved.

  11. The role of reactive oxygen species in the degradation of lignin derived dissolved organic matter

    Science.gov (United States)

    Waggoner, Derek C.; Wozniak, Andrew S.; Cory, Rose M.; Hatcher, Patrick G.

    2017-07-01

    Evidence suggests that reactive oxygen species (ROS) are important in transforming the chemical composition of the large pool of terrestrially-derived dissolved organic matter (DOM) exported from land to water annually. However, due to the challenges inherent in isolating the effects of individual ROS on DOM composition, the role of ROS in the photochemical alteration of DOM remains poorly characterized. In this work, terrestrial DOM was independently exposed to singlet oxygen (1O2), and superoxide (O2-rad under controlled laboratory conditions). Using ultra-high resolution mass spectrometry to track molecular level alterations of DOM by ROS, these findings suggest exposure to 1O2 (generated using Rose Bengal and visible light) removed formulas with an O/C > 0.3, and primarily resulted in DOM comprised of formulas with higher oxygen content, while O2-rad exposure (from KO2 in DMSO) removed formulas with O/C 1.5). Comparison of DOM altered by ROS in this study to riverine and coastal DOM showed that (20-80%) overlap in formulas, providing evidence for the role of ROS in shaping the composition of DOM exported from rivers to oceans.

  12. Entanglement sharing via qudit channels: Nonmaximally entangled states may be necessary for one-shot optimal singlet fraction and negativity

    Science.gov (United States)

    Pal, Rajarshi; Bandyopadhyay, Somshubhro

    2018-03-01

    We consider the problem of establishing entangled states of optimal singlet fraction and negativity between two remote parties for every use of a noisy quantum channel and trace-preserving local operations and classical communication (LOCC) under the assumption that the parties do not share prior correlations. We show that for a family of quantum channels in every finite dimension d ≥3 , one-shot optimal singlet fraction and entanglement negativity are attained only with appropriate nonmaximally entangled states. A consequence of our results is that the ordering of entangled states in all finite dimensions may not be preserved under trace-preserving LOCC.

  13. Formation and reactivity of free radicals in 5-hydroxymethyl-2-furaldehyde--the effect on isoprenaline photostability.

    Science.gov (United States)

    Brustugun, Jørgen; Tønnesen, Hanne H; Edge, Ruth; Navaratnam, Suppiah

    2005-05-13

    Solutions of glucose are used as diluents for drugs in various drug infusions. When sterilized by heat small amounts of the substance 5-hydroxymethyl-2-furaldehyde (5-HMF) is produced from glucose. At a hospital ward such infusions may be exposed to irradiation; including UV-light. The photoreactivity of the furaldehyde is investigated. It is shown to photodestabilize the catecholamine isoprenaline. It is shown to be a producer, but also a consumer, of singlet oxygen. The excited triplet, cation and anion radical have been produced by pulse radiolysis and flash photolysis and their absorbance characteristics have been determined. The triplet absorption spectrum showed absorption bands at 320 and 430 nm with molar absorption coefficients of 4700 and 2600 M-1 cm-1, respectively. The anion radical showed absorption bands at 330 and 420 nm with molar absorption coefficients of 2000 and 300 M-1 cm-1, respectively. The cation radical had an absorption band at 320 nm with a molar absorption coefficient of 5000 M-1 cm-1. The quantum yield for the production of singlet oxygen, sensitized by the 5-HMF triplet, was determined to be 0.6, whilst the quantum yield for the triplet formation was 1.0. Aqueous solutions of 5-HMF were found to photoionize to yield the hydrated electron and the cation radical of 5-HMF in a biphotonic process. The influences of pH, buffer and glucose on the formation of transients were evaluated. The reactions between 5-HMF and the solvated electron, the hydroxyl radical and the superoxide were also studied.

  14. Singlet Higgs phenomenology and the electroweak phase transition

    International Nuclear Information System (INIS)

    Profumo, Stefano; Ramsey-Musolf, Michael J.; Shaughnessy, Gabe

    2007-01-01

    We study the phenomenology of gauge singlet extensions of the Standard Model scalar sector and their implications for the electroweak phase transition. We determine the conditions on the scalar potential parameters that lead to a strong first order phase transition as needed to produce the observed baryon asymmetry of the universe. We analyze the constraints on the potential parameters derived from Higgs boson searches at LEP and electroweak precision observables. For models that satisfy these constraints and that produce a strong first order phase transition, we discuss the prospective signatures in future Higgs studies at the Large Hadron Collider and a Linear Collider. We argue that such studies will provide powerful probes of phase transition dynamics in models with an extended scalar sector

  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. 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.

  17. Yeast alter micro-oxygenation of wine: oxygen consumption and aldehyde production.

    Science.gov (United States)

    Han, Guomin; Webb, Michael R; Richter, Chandra; Parsons, Jessica; Waterhouse, Andrew L

    2017-08-01

    Micro-oxygenation (MOx) is a common winemaking treatment used to improve red wine color development and diminish vegetal aroma, amongst other effects. It is commonly applied to wine immediately after yeast fermentation (phase 1) or later, during aging (phase 2). Although most winemakers avoid MOx during malolactic (ML) fermentation, it is often not possible to avoid because ML bacteria are often present during phase 1 MOx treatment. We investigated the effect of common yeast and bacteria on the outcome of micro-oxygenation. Compared to sterile filtered wine, Saccharomyces cerevisiae inoculation significantly increased oxygen consumption, keeping dissolved oxygen in wine below 30 µg L -1 during micro-oxygenation, whereas Oenococcus oeni inoculation was not associated with a significant impact on the concentration of dissolved oxygen. The unfiltered baseline wine also had both present, although with much higher populations of bacteria and consumed oxygen. The yeast-treated wine yielded much higher levels of acetaldehyde, rising from 4.3 to 29 mg L -1 during micro-oxygenation, whereas no significant difference was found between the bacteria-treated wine and the filtered control. The unfiltered wine exhibited rapid oxygen consumption but no additional acetaldehyde, as well as reduced pyruvate. Analysis of the acetaldehyde-glycerol acetal levels showed a good correlation with acetaldehyde concentrations. The production of acetaldehyde is a key outcome of MOx and it is dramatically increased in the presence of yeast, although it is possibly counteracted by the metabolism of O. oeni bacteria. Additional controlled experiments are necessary to clarify the interaction of yeast and bacteria during MOx treatments. Analysis of the glycerol acetals may be useful as a proxy for acetaldehyde levels. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

  18. Spectroscopy and photophysics of flavin related compounds: Riboflavin and iso-(6,7)-riboflavin

    International Nuclear Information System (INIS)

    Sikorska, Ewa; Khmelinskii, Igor; Komasa, Anna; Koput, Jacek; Ferreira, Luis F.V.; Herance, Jose R.; Bourdelande, Jose L.; Williams, Sian L.; Worrall, David R.; Insinska-Rak, MaIgorzata; Sikorski, Marek

    2005-01-01

    The photochemistry and photophysics of isoalloxazines (10-substituted 2,3,4,10-tetrahydro-benzo[g]pteridine-2,4-diones), and especially flavins (7,8-dimethyl substituted isoalloxazines), are of considerable interest due to the biological relevance of these compounds. In this paper we report data concerning the photophysics of riboflavin and iso-(6,7)-riboflavin (10-(2,3,4,5-tetrahydroxypentyl)-6,7-dimethylbenzo[g]pteridine-2,4(3H,10H) -dione), and correlate the spectroscopic observations with theoretical calculations performed using time-dependent density functional theory. On the basis of these calculations the lowest excited singlet and triplet states are both assigned (π,π*) symmetry, and this result is used to explain the relatively low singlet oxygen quantum yields in comparison with alloxazines. Time-resolved emission studies have indicated 6,7-dimethylalloxazine a photodegradation product of iso-(6,7)-riboflavin

  19. (Gold core)/(titania shell) nanostructures for plasmon-enhanced photon harvesting and generation of reactive oxygen species

    KAUST Repository

    Fang, Caihong; Jia, Henglei; Chang, Shuai; Ruan, Qifeng; Wang, Peng; Chen, Tao; Wang, Jianfang

    2014-01-01

    Integration of gold and titania in a nanoscale core/shell architecture can offer large active metal/semiconductor interfacial areas and avoid aggregation and reshaping of the metal nanocrystal core. Such hybrid nanostructures are very useful for studying plasmon-enhanced/enabled processes and have great potential in light-harvesting applications. Herein we report on a facile route to (gold nanocrystal core)/(titania shell) nanostructures with their plasmon band synthetically variable from ∼700 nm to over 1000 nm. The coating method has also been applied to other mono- and bi-metallic Pd, Pt, Au nanocrystals. The gold/titania nanostructures have been employed as the scattering layer in dye-sensitized solar cells, with the resultant cells exhibiting a 13.3% increase in the power conversion efficiency and a 75% decrease in the scattering-layer thickness. Moreover, under resonant excitation, the gold/titania nanostructures can efficiently utilize low-energy photons to generate reactive oxygen species, including singlet oxygen and hydroxyl radicals.

  20. A Singlet Extension of the Minimal Supersymmetric Standard Model: Towards a More Natural Solution to the Little Hierarchy Problem

    Energy Technology Data Exchange (ETDEWEB)

    de la Puente, Alejandro [Univ. of Notre Dame, IN (United States)

    2012-05-01

    In this work, I present a generalization of the Next-to-Minimal Supersymmetric Standard Model (NMSSM), with an explicit μ-term and a supersymmetric mass for the singlet superfield, as a route to alleviating the little hierarchy problem of the Minimal Supersymmetric Standard Model (MSSM). I analyze two limiting cases of the model, characterized by the size of the supersymmetric mass for the singlet superfield. The small and large limits of this mass parameter are studied, and I find that I can generate masses for the lightest neutral Higgs boson up to 140 GeV with top squarks below the TeV scale, all couplings perturbative up to the gauge unification scale, and with no need to fine tune parameters in the scalar potential. This model, which I call the S-MSSM is also embedded in a gauge-mediated supersymmetry breaking scheme. I find that even with a minimal embedding of the S-MSSM into a gauge mediated scheme, the mass for the lightest Higgs boson can easily be above 114 GeV, while keeping the top squarks below the TeV scale. Furthermore, I also study the forward-backward asymmetry in the t¯t system within the framework of the S-MSSM. For this purpose, non-renormalizable couplings between the first and third generation of quarks to scalars are introduced. The two limiting cases of the S-MSSM, characterized by the size of the supersymmetric mass for the singlet superfield is analyzed, and I find that in the region of small singlet supersymmetric mass a large asymmetry can be obtained while being consistent with constraints arising from flavor physics, quark masses and top quark decays.