Science.gov

Sample records for pulse radiolysis method

  1. Development of double-decker pulse radiolysis.

    PubMed

    Kan, K; Kondoh, T; Yang, J; Ogata, A; Norizawa, K; Yoshida, Y

    2012-07-01

    Double-decker pulse radiolysis (DDPR), which utilizes double-decker electron beams, was investigated to develop a new pulse radiolysis with a high time resolution. The double-decker electron beams were generated by injecting two UV pulses into a photocathode radio-frequency gun. In the pulse radiolysis, one electron beam was used as a pump beam, and the other was converted to a probe pulse. Finally, as its first application, the DDPR was successfully used for observing solvated electrons in water, with a 10%-90% rise time of 8.6 ps.

  2. Folding dynamics of cytochrome c using pulse radiolysis.

    PubMed

    Choi, Jungkweon; Fujitsuka, Mamoru; Tojo, Sachiko; Majima, Tetsuro

    2012-08-15

    Pulse radiolysis is a powerful method to realize real-time observation of various redox processes, which induces various structural and functional changes occurring in biological systems. However, its application has been mainly limited to studies of the redox reactions of rather smaller biological systems such as DNA because of an undesired reaction due to various free radicals generated by pulse radiolysis. For application of pulse radiolysis to generate plenty of redox reactions of biological systems, selective redox reactions induced by electron pulses have to be developed. In this study, we report that in the presence of the high concentration of the denaturant, guanidine HCl (GdHCl), the selective reduction of the oxidized cytochrome c (Cyt c) takes place in time scales of a few microseconds by the electron transfer from the guanidine radical that is formed by the fast reaction of e(aq)(-) with GdHCl, consequently leading to folding kinetics of Cyt c. By providing insight into the folding dynamics of Cyt c, we show that the pulse radiolysis technique can be used to track the folding dynamics of various biomolecules in the presence of a denaturant including GdHCl.

  3. Pulse radiolysis of epicatechin in aqueous solution

    NASA Astrophysics Data System (ADS)

    Li, Fengmei; Fang, Xingwang

    1998-06-01

    Pulse radiolysis of epicatechin in aqueous solution has been done to investigate the reactions of epicatechin derived phenoxy radical (EpO) at neutral pH. EpO was generated by N 3 reacting toward EpOH, the rate constant was measured to be 3 × 10 8 dm 3 mol -1 s -1. The biomolecular termination of EpO is rather slow ((2 k < × 10 6 dm 3 mol -1 s -1) and results in products exhibiting strong visible absorption around 450 nm. No reactions have been observed for EpO with O 2 and O 2 in the time scale of pulse radiolysis (0.01 s), suggesting the bimolecular rate constant are less than 10 4 and 5 × 10 6 dm 3 mol -1 s -1, respectively.

  4. The Novel Science of Pulse Radiolysis with Nanosecond Infrared Detection

    NASA Astrophysics Data System (ADS)

    Farrington, Jaime A.; Cook, Andrew R.; Fujita, Etsuko; Preses, Jack M.; Wishart, James F.; Grills, David C.

    2012-02-01

    Pulse radiolysis is a powerful technique to characterize important transient species in fields such as solar energy conversion, catalytic hydrogen production, radiation chemistry and other areas of basic research in the chemical, material and biological sciences. It utilizes short electron pulses to create an array of transient species by adding single positive or negative charges to molecules. In combination with different spectroscopic detection schemes, pulse radiolysis provides a unique understanding of the properties of such species and the roles they play in important reaction mechanisms. Time-resolved infrared (TRIR) spectroscopy in the mid-IR region would improve the identification of transient species and offer the highly specific molecular and structural characterization that is currently lacking. However, incorporating TRIR spectroscopy with pulse radiolysis has proven to be difficult due to technical complications. At the Laser Electron Accelerator Facility at Brookhaven National Laboratory, a unique mid-IR TRIR pulse radiolysis setup has been constructed utilizing a new electron beam line dedicated to IR studies and a suite of tunable high power quantum cascade mid IR lasers. Preliminary results with various systems of interest will be presented.

  5. Pulse radiolysis studies on charge carriers in conjugated polymers

    NASA Astrophysics Data System (ADS)

    Burrows, H. D.; Miguel, M. da G.; Monkman, A. P.; Horsburgh, L. E.; Hamblett, I.; Navaratnam, S.

    2000-02-01

    The charged states of the conjugated polymers poly(2-methoxy,5-(2'-ethylhexyloxy)-p- phenylenevinylene) (MEH-PPV) and poly(2,5-pyridinediyl) (PPY) have been studied by pulse radiolysis. Following pulse radiolysis of argon-saturated solutions of MEH-PPV in chloroform, a new absorption is seen to grow in over a few hundred microseconds. This has a principal absorption at 1.43 eV and a weaker, low energy band (⩽0.80 eV), and is assigned to the positive one-electron charge state (positive polaron) of MEH-PPV. The slow absorption decay is unaffected by oxygen. Negative charge states (negative polarons), with absorptions around 1.4 eV, are produced upon pulse radiolysis of MEH-PPV in argon-saturated solutions in tetrahydrofuran (THF) or benzonitrile. A small solvatochromic shift is observed. In contrast to the behavior of the positive polaron, the MEH-PPV negative charge carriers decay fairly rapidly, and are readily quenched by molecular oxygen. Previous results on chemically produced positive and negative charge states of conjugated polymers and oligomers are discussed on the basis of these assignments, and comparison is made with theoretical calculations. Using benzophenone as a charge scavenger, pulse radiolysis of formic acid is shown to generate one-electron reducing species. Various derivatives of PPY, including a regioregular polymer (rPPY) and a hexyl substituted compound (HPPY) have been studied by pulse radiolysis in formic acid solution. With rPPY, new absorptions are observed at 2.59 and 1.40 eV, and are assigned to the one-electron reduced species. These are strongly quenched by molecular oxygen. With HPPY, the lower energy transition is broadened to give a maximum below 1.21 eV and a shoulder at 1.65 eV. The differences between rPPY and HPPY are interpreted on the basis of differences in the rigidity of the polymer. The relevance of these assignments to the identification of charged species in photoinduced absorption measurements is indicated.

  6. One-electron oxidations of ferrocenes: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Faraggi, Moshe; Weinraub, Dany; Broitman, Federico; DeFelippis, Michael R.; Klapper, Michael H.

    Using the pulse radiolysis technique we have studied the oxidation by various inorganic radicals of four water soluble ferrocene derivatives, hydroxyethyl, dimethylaminomethyl, monocarboxylic acid and dicarboxylic acid. We report the second order rate constants for these reactions, the stabilities and spectral properties of the ferrocinium products, and the electrochemically determined ferrocinium/ferrocene redox potentials. We also present preliminary estimates of tyrosine and tryptophan radical redox potentials obtained with the dicarboxylic acid ferrocene derivative as reference, and we discuss the relationship between redox potential differences and the reactivities of the ferrocenes with the inorganic radicals.

  7. Pulse radiolysis of epoxy-based matrix materials

    NASA Technical Reports Server (NTRS)

    Coulter, D. R.; Gupta, A.; Tsay, F. D.; Moacanin, J.; Liang, R.

    1983-01-01

    Electron beam pulse radiolysis (600 KeV, 3 nsec) experiments have been carried out on epoxy-based matrix materials. Time and wavelength resolved emission and transient absorption techniques as well as ESR studies have been utilized to identify and monitor short lived reactive intermediates resulting from energetic electron impact. An energy deactivation model based on the results of this work has been developed. Recombination of primary charged species is found to be fast, resulting in the formation of longer lived excited electronic states and radicals which control the subsequent energy deactivation.

  8. Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility

    SciTech Connect

    Grills, David C.; Farrington, Jaime A.; Layne, Bobby H.; Preses, Jack M.; Bernstein, Herbert J.; Wishart, James F.

    2015-04-27

    When coupled with transient absorption spectroscopy, pulse radiolysis, which utilizes high-energy electron pulses from an accelerator, is a powerful tool for investigating the kinetics and thermodynamics of a wide range of radiation-induced redox and electron transfer processes. The majority of these investigations detect transient species in the UV, visible, or near-IR spectral regions. Unfortunately, the often-broad and featureless absorption bands in these regions can make the definitive identification of intermediates difficult. Time-resolved vibrational spectroscopy would offer much improved structural characterization, but has received only limited application in pulse radiolysis. In this paper, we describe in detail the development of a unique nanosecond time-resolved infrared (TRIR) detection capability for condensed-phase pulse radiolysis on a new beam line at the LEAF facility of Brookhaven National Laboratory. The system makes use of a suite of high-power, continuous wave external-cavity quantum cascade lasers as the IR probe source, with coverage from 2330-1051 cm⁻¹. The response time of the TRIR detection setup is ~40 ns, with a typical sensitivity of ~100 µOD after 4-8 signal averages using a dual-beam probe/reference normalization detection scheme. As a result, this new detection method has enabled mechanistic investigations of a range of radiation-induced chemical processes, some of which are highlighted here.

  9. Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility

    SciTech Connect

    Grills, David C. Farrington, Jaime A.; Layne, Bobby H.; Preses, Jack M.; Wishart, James F.; Bernstein, Herbert J.

    2015-04-15

    When coupled with transient absorption spectroscopy, pulse radiolysis, which utilizes high-energy electron pulses from an accelerator, is a powerful tool for investigating the kinetics and thermodynamics of a wide range of radiation-induced redox and electron transfer processes. The majority of these investigations detect transient species in the UV, visible, or near-IR spectral regions. Unfortunately, the often-broad and featureless absorption bands in these regions can make the definitive identification of intermediates difficult. Time-resolved vibrational spectroscopy would offer much improved structural characterization, but has received only limited application in pulse radiolysis. In this paper, we describe in detail the development of a unique nanosecond time-resolved infrared (TRIR) detection capability for condensed-phase pulse radiolysis on a new beam line at the LEAF facility of Brookhaven National Laboratory. The system makes use of a suite of high-power, continuous wave external-cavity quantum cascade lasers as the IR probe source, with coverage from 2330 to 1051 cm{sup −1}. The response time of the TRIR detection setup is ∼40 ns, with a typical sensitivity of ∼100 μOD after 4-8 signal averages using a dual-beam probe/reference normalization detection scheme. This new detection method has enabled mechanistic investigations of a range of radiation-induced chemical processes, some of which are highlighted here.

  10. Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility.

    PubMed

    Grills, David C; Farrington, Jaime A; Layne, Bobby H; Preses, Jack M; Bernstein, Herbert J; Wishart, James F

    2015-04-01

    When coupled with transient absorption spectroscopy, pulse radiolysis, which utilizes high-energy electron pulses from an accelerator, is a powerful tool for investigating the kinetics and thermodynamics of a wide range of radiation-induced redox and electron transfer processes. The majority of these investigations detect transient species in the UV, visible, or near-IR spectral regions. Unfortunately, the often-broad and featureless absorption bands in these regions can make the definitive identification of intermediates difficult. Time-resolved vibrational spectroscopy would offer much improved structural characterization, but has received only limited application in pulse radiolysis. In this paper, we describe in detail the development of a unique nanosecond time-resolved infrared (TRIR) detection capability for condensed-phase pulse radiolysis on a new beam line at the LEAF facility of Brookhaven National Laboratory. The system makes use of a suite of high-power, continuous wave external-cavity quantum cascade lasers as the IR probe source, with coverage from 2330 to 1051 cm(-1). The response time of the TRIR detection setup is ∼40 ns, with a typical sensitivity of ∼100 μOD after 4-8 signal averages using a dual-beam probe/reference normalization detection scheme. This new detection method has enabled mechanistic investigations of a range of radiation-induced chemical processes, some of which are highlighted here.

  11. Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility

    DOE PAGES

    Grills, David C.; Farrington, Jaime A.; Layne, Bobby H.; ...

    2015-04-27

    When coupled with transient absorption spectroscopy, pulse radiolysis, which utilizes high-energy electron pulses from an accelerator, is a powerful tool for investigating the kinetics and thermodynamics of a wide range of radiation-induced redox and electron transfer processes. The majority of these investigations detect transient species in the UV, visible, or near-IR spectral regions. Unfortunately, the often-broad and featureless absorption bands in these regions can make the definitive identification of intermediates difficult. Time-resolved vibrational spectroscopy would offer much improved structural characterization, but has received only limited application in pulse radiolysis. In this paper, we describe in detail the development of amore » unique nanosecond time-resolved infrared (TRIR) detection capability for condensed-phase pulse radiolysis on a new beam line at the LEAF facility of Brookhaven National Laboratory. The system makes use of a suite of high-power, continuous wave external-cavity quantum cascade lasers as the IR probe source, with coverage from 2330-1051 cm⁻¹. The response time of the TRIR detection setup is ~40 ns, with a typical sensitivity of ~100 µOD after 4-8 signal averages using a dual-beam probe/reference normalization detection scheme. As a result, this new detection method has enabled mechanistic investigations of a range of radiation-induced chemical processes, some of which are highlighted here.« less

  12. Flash photolysis and pulse radiolysis studies on elastin hydrolysates.

    PubMed

    Sionkowska, Alina

    2013-08-05

    The formation of reactive species and free radicals in water soluble elastin hydrolysates have been investigated by pulse radiolysis and flash photolysis. Elastin hydrolysates were obtained by hydrolysis of elastin extracted from aorta. An investigation of the photochemical properties of elastin hydrolysates in water was carried out using nanosecond laser irradiation. The transient spectra of elastin hydrolysates solution excited at 266 nm showed two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The reactions of hydrated electrons and ˙OH radicals with elastin have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of elastin with e(aq)(-) small maximum absorption in UV and visible light was observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with elastin two bands were observed. The first one at 320 nm and the second one at 410 nm. Reaction of OH radicals with elastin hydrolysates lead to formation of Tyr phenoxyl radicals with absorption at 410 nm. The influence of the addition of sodium azide NaN3 on the formation of the transients was evaluated. Copyright © 2013 Elsevier B.V. All rights reserved.

  13. Application of Pulse Radiolysis to Mechanistic Investigations of Catalysis Relevant to Artificial Photosynthesis

    DOE PAGES

    Fujita, Etsuko; Grills, David C.; Polyansky, Dmitry E.

    2017-09-12

    Taking inspiration from natural photosystems, the goal of artificial photosynthesis is to harness solar energy to convert abundant materials, such as CO2 and H2O, into solar fuels. Catalysts are required to ensure that the necessary redox half-reactions proceed in the most energy-efficient manner. It is thus critical to gain a detailed mechanistic understanding of these catalytic reactions in order to develop new and improved catalysts. Many of the key catalytic intermediates are short-lived transient species, requiring time-resolved spectroscopic techniques for their observation. The two main methods for rapidly generating such species on the sub-microsecond timescale are laser flash photolysis andmore » pulse radiolysis. These methods complement one another, and both can provide important spectroscopic and kinetic information. However, pulse radiolysis proves to be superior in systems with significant spectroscopic overlap between photosensitizer and other species present during the reaction. In this paper, we review the pulse radiolysis technique and how it has been applied to mechanistic investigations of half-reactions relevant to artificial photosynthesis.« less

  14. Application of Pulse Radiolysis to Mechanistic Investigations of Catalysis Relevant to Artificial Photosynthesis.

    PubMed

    Fujita, Etsuko; Grills, David C; Polyansky, Dmitry E

    2017-09-12

    Taking inspiration from natural photosystems, the goal of artificial photosynthesis is to harness solar energy to convert abundant materials, such as CO2 and H2O, into solar fuels. Catalysts are required to ensure that the necessary redox half-reactions proceed in the most energy-efficient manner. It is therefore critical to gain a detailed mechanistic understanding of these catalytic reactions in order to develop new and improved catalysts. Many of the key catalytic intermediates are short-lived transient species, requiring time-resolved spectroscopic techniques for their observation. The two main methods for rapidly generating such species on the sub-microsecond timescale are laser flash photolysis and pulse radiolysis. These methods complement one another, and both can provide important spectroscopic and kinetic information. However, pulse radiolysis proves to be superior in systems with significant spectroscopic overlap between photosensitizer and other species present during the reaction. Here, we review the pulse radiolysis technique and how it has been applied to mechanistic investigations of half-reactions relevant to artificial photosynthesis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Pulse radiolysis of aqueous solutions of sodium tetraphenylborate

    NASA Astrophysics Data System (ADS)

    Crawford, Charles L.; Gholami, Mohammad R.; Bhave, Ravindra N.; Hanrahan, Robert J.

    1994-09-01

    In previous work on the 60Co γ-radiolysis of aqueous tetraphenylborate (TPB -) solutions carried out in this laboratory, it was found that several organic products, including benzene, phenol and biphenyl, are produced with substantial yield. However, the reaction mechanism was not established. In the present study, reactions initiated by OḢ radicals, N 3 radicals and e -aq in aqueous TPB - solutions were studied by pulse radiolysis using a 600 keV Febetron electron accelerator. The lack of reactivity between TPB - and e -aq was demonstrated by directly monitoring the transient optical absorbance of e -aq. Concerning the reaction with O Ḣ, two schemes were considered: (1) electron transfer from B(C 6H 5) -4 to O Ḣ; or (2) O Ḣ addition to B(C 6H 5) -4. Comparison of observed transient absorption spectra with expectations based on two different schemes suggests that O Ḣ addition is the dominant reaction pathway under conditions of N 2O saturation, with an experimentally determined second-order rate constant of 6.2×10 9M -1s -1. A mechanism based on an initial first-order self-decomposition of the O Ḣ adduct, (C 6H 5) 3BC 6H 5OH -· with a measured rate constant of 4×10 4s -1 is proposed. Kinetic modeling on the proposed mechanistic scheme gives good agreement with our experimental results.

  16. Oxidation intermediates of α-glucosyl rutin by pulse radiolysis

    NASA Astrophysics Data System (ADS)

    Nakata, Kunihiko; Morita, Naofumi; Horii, Hideo; Chubachi, Mitsuo

    1997-11-01

    Transient intermediates generated in the reaction of α-glucosyl rutin (G-rutin) with the OH radical or the azide radical were investigated by pulse radiolysis. The OH radical reacted with G-rutin to produce the OH-adduct radical, followed by deprotonation in neutral and acidic solutions. In alkaline solutions, the OH-adduct di-anion radical formed from the di-anions of G-rutin were dehydrated to the phenoxyl radical. On the other hand, G-rutin was oxidized to one-electron oxidized cation radical by the azide radical. The pK a values of the OH radical adduct were found to be 6.83 ± 0.10 and 8.87 ± 0.13. While, the pK a values of the phenoxyl radical of G-rutin were found to be 7.52 ± 0.11 and 9.95 ± 0.13.

  17. Pulse radiolysis studies in supercritical CO{sub 2}

    SciTech Connect

    Jonah, C. D.; Dimitrijevic, N. M.; Bartels, D. M.; Takahashi, K.

    2000-03-09

    The pulse radiolysis technique has been applied to study reactions of ions in supercritical solutions. Evidence for the formation of C{sub 2}O{sub 4}{sup +} has been found in supercritical CO{sub 2}. The rate of the electron transfer reaction from dimethyl aniline to the C{sub 2}O{sub 4}{sup +} was measured over the density range of 0.17--0.7 g/cm{sup 3}. The reaction rate was measured to be close to diffusion-controlled at the lowest density; at higher densities, the rate was considerably below the apparent diffusion-controlled rate. Similar behavior was found for the reaction of the anion (presumably C{sub 2}O{sub 4}{sup {minus}}) with benzoquinone. The reaction of O{sub 2} with C{sub 2}O{sub 4}{sup +} was considerably slower than the expected diffusion-controlled rate.

  18. [Production of superoxide radicals with pulse radiolysis of water with high linear energy transfer].

    PubMed

    Baldacchino, G; Trupin-Wasselin, V; Bouffard, S; Balanzat, E; Gardès-Albert, M; Abedinzadeh, Z; Jore, D; Deycard, S; Hickel, B

    2001-02-01

    The radiolysis of water with heavy ions of high linear energy transfer (LET) (-dE/dx) is characterized, in deaerated medium, by the production of superoxide anions, the radiolytic yields of which increase with the LET. Radiobiological interest in such radical species comes from the oxidative stress which may be generated by their dismutation in O2 and H2O2 in anoxic medium (radiotherapy with heavy ions). A brief review of the measurements of superoxide free radicals in aqueous solution by indirect or direct methods is presented. Moreover, some experimental results obtained by pulse radiolysis with Ar18+ ions (TEL = 290 keV x microm(-1)), are described. The interpretation of the kinetics takes into account the superoxide absorbance and that of hydrogen peroxide, which is present at the millisecond time scale.

  19. Pulse radiolysis and spectrophotometric studies on the binding of organic cations with heparin

    NASA Astrophysics Data System (ADS)

    Jakubowska, Małgorzata; Adamus, Jan; Gębicki, Jerzy; Marcinek, Andrzej; Sikora, Adam

    2014-06-01

    Here we present the spectroscopic and pulse radiolysis studies of the interactions of heparin and some organic cations:methylene blue (MB), 1-methylnicotinamide (MNA+), and its dimer 1,3-bis(1-methylnicotinamide)propane (bis(MNA+)).

  20. Picosecond Pulse Radiolysis of Highly Concentrated Carbonate Solutions.

    PubMed

    Ghalei, Mohammad; Ma, Jun; Schmidhammer, Uli; Vandenborre, Johan; Fattahi, Massoud; Mostafavi, Mehran

    2016-03-10

    Highly concentrated potassium carbonate aqueous solutions are studied by picosecond pulse radiolysis with the purpose of exploring the formation processes of carbonate radical CO3(•-). The transient absorption band of solvated electron produced by ionizing is markedly shifted from 715 to 600 nm when the solute concentration of K2CO3 is 5 mol L(-1). This spectral shift is even more important than that observed for the solvated electron in 10 mol L(-1) KOH solutions. The broad absorption band of solvated electron in K2CO3 solutions overlaps with that of carbonate radical CO3(•-) formed at ultrashort time. Nitrate ion is used to scavenge the solvated electron and to observe the contribution of carbonate radical CO3(•-). The analysis of the amplitude and the kinetics of carbonate radical formation in highly concentrated solutions shows that CO3(•-) is formed within the electron pulse (7 ps) by two parallel mechanisms: a direct effect on the solute and the oxidation of the solute by water radical hole H2O(•+). These two mechanisms are followed by an additional one, by reaction between the solute and OH(•) radical especially in lower concentration. The radiolytic yield of each process is discussed.

  1. Pulse radiolysis of catalase in solution—II. Reactions of primary products from water radiolysis with catalase

    NASA Astrophysics Data System (ADS)

    Gȩbicka, Lidia; Gȩbicki, Jerzy L.

    The mechanism of the reaction of catalase with e -aq, H and OH has been studied by pulse radiolysis at room temperature. Some evidences have been found that e -eq/H react with porphyrin ring of catalase to form π-radical without reduction of heme iron within investigated time span of 1 s after the pulse. OH radicals react mainly with the protein moiety of the enzyme but the formation and decay of compound I, an intermediate of the catalytic reaction of catalase can be observed as well.

  2. Rapid "step capture" of holes in chloroform during pulse radiolysis.

    PubMed

    Cook, Andrew R; Bird, Matthew J; Asaoka, Sadayuki; Miller, John R

    2013-08-22

    The fundamental process of hole capture in solution was investigated following pulse radiolysis with polyfluorene and 4-cyano-4″-pentyl-p-terphenyl scavengers. Contrary to expectation, a large fraction of holes were captured in experimental time-resolution limited ∼20 ps steps, by a process much faster than diffusion of the initially formed solvent molecular cation. At the highest concentrations, 1.92 mM for a 52 unit long polyfluorene and 800 mM for 4-cyano-4″-pentyl-p-terphenyl, 66% and 99%, respectively, of the initially formed holes were captured by 20 ps, with radiation chemical yield G = 1.2 × 10(-7) and 1.7 × 10(-7) mol J(-1). The data can be explained by capture of presolvated holes, analogous to presolvated electrons, possibly possessing extended wave functions, high mobilities, or excess kinetic energy for the first few picoseconds after their creation. Such a process is not generally known in solution; however, the observed step capture as a function of solute concentration is shown to be well explained by this model. In addition to understanding the capture process in solution, the very large step yields formed in 20 ps will provide the ability to resolve subsequent hole transfer on the polymers with >2 orders of magnitude better time resolution than expected.

  3. Structure and dynamics of paramagnetic transients by pulsed EPR and NMR detection of nuclear resonance. [Pulse radiolysis of methanol in D/sub 2/O

    SciTech Connect

    Trifunac, A.D.

    1981-01-01

    Structure and dynamics of transient radicals in pulse radiolysis can be studied by time resolved EPR and NMR techniques. EPR study of kinetics and relaxation is illustrated. The NMR detection of nuclear resonance in transient radicals is a new method which allows the study of hyperfine coupling, population dynamics, radical kinetics, and reaction mechanism. 9 figures.

  4. Pulse radiolysis of butyl acrylate in aqueous solution

    NASA Astrophysics Data System (ADS)

    Kujawa, P.; Mohid, N.; Zaman, K.; Manshol, W.; Ulanski, P.; Rosiak, J. M.

    1998-10-01

    The pulse radiolysis of n-butyl acrylate (nBA) in aqueous solution was studied. The rate constant of the reaction of nBA with hydroxyl radicals was calculated as 1.5×10 10 dm 3 mol -1 s -1. The absorption spectrum of the OH ·-nBA adduct appeared to have a broad maximum at 300 nm. This spectrum was attributed to the α-carbon centred radicals. It decayed with the first-order rate constant k=1.5×10 4 s -1 (pH 10.8). The rate constant of the nBA reaction with hydrated electrons was determined as k=1.6×10 10 dm 3 mol -1 s -1. The spectrum of H ·-nBA adduct was similar to that recorded for OH · adduct. It decayed with first-order kinetics at k=1.0×10 4 s -1. Spectra of the electron adduct were characterised by the band with a maximum at 285 nm (pH 10.0) or at 280 nm (pH 4.0) with ɛ=10 500 dm 3 mol -1 cm -1. In acidic solution, radical anion formed upon addition of hydrated electrons to the nBA molecule, undergoes fast, reversible protonation. The decay of the reversibly protonated electron adduct was a second-order process at k=2.5×10 9 dm 3 mol -1 s -1. This reaction took place at the carbonyl oxygen. Slow, irreversible protonation of the electron adduct at high pH takes place at the β-carbon atom at k=2.9×10 4 s -1.

  5. Pulse radiolysis in model studies toward radiation processing

    NASA Astrophysics Data System (ADS)

    Von Sonntag, C.; Bothe, E.; Ulanski, P.; Deeble, D. J.

    1995-02-01

    Using the pulse radiolysis technique, the OH-radical-induced reactions of poly(vinyl alcohol) PVAL, poly(acrylic acid) PAA, poly(methacrylic acid) PMA, and hyaluronic acid have been investigated in dilute aqueous solution. The reactions of the free-radical intermediates were followed by UV-spectroscopy and low-angle laser light-scattering; the scission of the charged polymers was also monitored by conductometry. For more detailed product studies, model systems such as 2,4-dihydroxypentane (for PVAL) and 2,4-dimethyl glutaric acid (for PAA) was also investigated. With PVA, OH-radicals react predominantly by abstraction of an H-atom in α-position to the hydroxyl group (70%). The observed bimolecular decay rate constant of the PVAL-radicals decreases with time. This has been interpreted as being due to an initially fast decay of proximate radicals and a decrease of the probability of such encounters with time. Intramolecular crosslinking (loop formation) predominates at high doses per pulse. In the presence of O 2, peroxyl radicals are formed which in the case of the α-hydroxyperoxyl radicals can eliminate HO 2-radicals in competition with bimolecular decay processes which lead to a fragmentation of the polymer. In PAA, radicals both in α-position (characterized by an absorption near 300 nm) and in β-position to the carboxylate groups are formed in an approximately 1:2 ratio. The lifetime of the radicals increases with increasing electrolytic dissociation of the polymer. The β-radicals undergo a slow (intra- as well as intermolecular) H-abstraction yielding α-radicals, in competition to crosslinking and scission reactions. In PMA only β-radicals are formed. Their fragmentation has been followed by conductometry. In hyaluronic acid, considerable fragmeentation is observed even in the absence of oxygen which, in fact, has some protective effect against this process. Thus free-radical attack on this important biopolymer makes it especially vulnerable with respect

  6. Radiolytic reactions of nitro blue tetrazolium under oxidative and reductive conditions: a pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Kovacs, A.; Wojnarovits, L.; Baranyai, M.; Moussa, A.; Othman, I.; McLaughlin, W. L.

    1999-08-01

    The radiolytic reactions of the ditetrazolium salt nitro blue tetrazolium chloride (NBTCl 2) were studied by pulse radiolysis technique in aqueous solution under reducing and oxidising conditions with the aim of potential dosimetry application. Under reducing conditions the fast formation of the tetrazolinyl radical is observed that is followed by the appearance of monoformazan (MF +), i.e. one of the tetrazolium rings is reduced to formazan. The formation of the water-insoluble diformazan, i.e. the result of the second reduction step was not observed in pulse radiolysis. Formazan formation was not found under oxidative conditions.

  7. Oxidation reactions of thymol: a pulse radiolysis and theoretical study.

    PubMed

    Venu, S; Naik, D B; Sarkar, S K; Aravind, Usha K; Nijamudheen, A; Aravindakumar, C T

    2013-01-17

    The reactions of (•)OH and O(•-), with thymol, a monoterpene phenol and an antioxidant, were studied by pulse radiolysis technique and DFT calculations at B3LYP/6-31+G(d,p) level of theory. Thymol was found to efficiently scavenge OH radicals (k = 8.1 × 10(9) dm(3) mol(-1) s(-1)) to produce reducing adduct radicals, with an absorption maximum at 330 nm and oxidizing phenoxyl radicals, with absorption maxima at 390 and 410 nm. A major part of these adduct radicals was found to undergo water elimination, leading to phenoxyl radicals, and the process was catalyzed by OH(-) (or Na(2)HPO(4)). The rate of reaction of O(•-) with thymol was found to be comparatively low (k = 1.1 × 10(9) dm(3) mol(-1) s(-1)), producing H abstracted species of thymol as well as phenoxyl radicals. Further, these phenoxyl radicals of thymol were found to be repaired by ascorbate (k = 2.1 × 10(8) dm(3) mol(-1) s(-1)). To support the interpretation of the experimental results, DFT calculations were carried out. The transients (both adducts and H abstracted species) have been optimized in gas phase at B3LYP/6-31+G(d,p) level of calculation. The relative energy values and thermodynamic stability suggests that the ortho adduct (C6_OH adduct) to be most stable in the reaction of thymol with OH radicals, which favors the water elimination. However, theoretical calculations showed that C4 atom in thymol (para position) can also be the reaction center as it is the main contributor of HOMO. The absorption maxima (λ(max)) calculated from time-dependent density functional theory (TDDFT) for these transient species were close to those obtained experimentally. Finally, the redox potential value of thymol(•)/thymol couple (0.98 V vs NHE) obtained by cyclic voltammetry is less than those of physiologically important oxidants, which reveals the antioxidant capacity of thymol, by scavenging these oxidants. The repair of the phenoxyl radicals of thymol with ascorbate together with the redox potential

  8. Time-resolved spectroscopy of solid poly/1-vinyl naphthalene/ following electron beam pulse radiolysis - Pulse radiolytic studies on polymers

    NASA Technical Reports Server (NTRS)

    Coulter, D. R.; Liang, R. H.; Di Stefano, S.; Moacanin, J.; Gupta, A.

    1982-01-01

    Transient emission studies following pulse radiolysis of solid poly(1-vinyl naphthalene) show existence of excited monomers and two excimers. Quenching experiments indicate that excimers are not formed directly by recombination of ions but probably by trapping of migrating monomeric excitation in preformed traps whose density is approximately one in 1000.

  9. Radiation-induced pink nickel oligomeric clusters in water. Pulse radiolysis study.

    PubMed

    Hioul, Mohamed Larbi; Lin, Mingzhang; Belloni, Jacqueline; Keghouche, Nassira; Marignier, Jean-Louis

    2014-10-09

    γ-rays and pulse radiolysis of aqueous solutions of Ni(2+) ions in the presence of polyacrylate (PA(-)) and 2-propanol leads to the formation of metastable species absorbing at 540 nm that are ascribed to "pink" oligomeric clusters of a few nickel atoms only. The molar absorption coefficient is evaluated as ε540 nm = 3300 ± 300 L mol(-1) cm(-1) per Ni(0) atom. The successive steps from the reduction of Ni(2+) into Ni(+) ions to the formation of the pink clusters at 540 nm under conditions of complexation by PA(-) are investigated by pulse radiolysis. The yield of the formation of pink clusters increases markedly with the irradiation dose rate, demonstrating the occurrence of the disproportionation of the [Ni(+), PA(-)] complex after a single electron pulse. The reduction and nucleation mechanisms, including rate constants, in competition with the back oxidation by protons, particularly at low dose rate, are discussed.

  10. Pulse radiolysis studies of berkelium(III): preparation and identification of berkelium(II) in aqueous perchlorate media. [Pulsed Electrons

    SciTech Connect

    Sullivan, J.C.; Schmidt, K.H.; Morss, L.R.; Pippin, C.G.; Williams, C. )

    1988-02-24

    The first direct evidence for the formation of Bk(II) in aqueous solutions as a result of pulse radiolysis is reported herein. The barrier that the necessity of a high pH has presented for this reaction was circumvented by using bicarbonate to adjust the pH, by maintaining rigorously oxygen-free conditions, and by using ethanol to suppress radiolysis products. The absorption ascribed to Bk(II) occurs at 310nm, and the molar absorptivity at this wavelength is consistent with theoretical considerations advanced by Carnall and Crosswhite. 10 references, 2 figures.

  11. Picosecond Pulse Radiolysis of Highly Concentrated Phosphoric Acid Solutions: Mechanism of Phosphate Radical Formation.

    PubMed

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2015-06-18

    Eight solutions containing phosphoric acid with concentrations ranging from 2 mol L(-1) to neat acid have been studied by picosecond pulse radiolysis. The absorbance of the secondary radical H2PO4(•) formed within 7 ps of the electron pulse is observed using pulse-probe method in the visible. Kinetic analysis shows that the radicals of phosphoric acid are formed via two mechanisms: direct electron detachment and oxidation by the radical cation of water, H2O(•+). On the basis of molar extinction coefficient value of 1850 L mol(-1) cm(-1), at 15 ps the radiolytic yield of H2PO4(•) formation by direct energy absorption is 3.7 ± 0.1 × 10(-7) mol J(-1) in neat phosphoric acid. In highly concentrated phosphoric acid solutions, the total yield of phosphate radical at 15 ps exhibits an additional contribution that can be explained by electron transfer from phosphoric acid to H2O(•+). The efficiency of the electron transfer to this strongly oxidizing species in phosphoric acid solutions is lower compared with the one in sulfuric acid solutions. Two explanations are given to account for a relatively low efficiency of H2O(•+) scavenging in concentrated phosphoric acid solutions.

  12. Hydroxyl radical-induced degradation of fenuron in pulse and gamma radiolysis: kinetics and product analysis.

    PubMed

    Kovács, Krisztina; Mile, Viktoria; Csay, Tamás; Takács, Erzsébet; Wojnárovits, László

    2014-11-01

    Radiolytic reactions of phenylureas were studied in detail with fenuron model compound in dilute aqueous solutions using pulse radiolysis for detection of the intermediates, gamma radiolysis with UV-Vis and HPLC-MS techniques for analysis of the final products. The kinetics of oxidation was followed by COD, TOC and toxicity measurements. During radiolysis of aerated solutions hydroxyl radical ((•)OH), eaq (-), H(•) and O2 (•-)/HO2 (•) reactive intermediates are produced, the degradation of solute takes place practically entirely through (•)OH reactions. Therefore, the product distribution is similar to the distributions reported in other advanced oxidation processes with (•)OH as main reactant. (•)OH mainly reacts with the aromatic ring, forming cyclohexadienyl radical as an intermediate. This radical in pulse radiolysis has a wide absorption band in the 310-390 nm wavelength range with a maximum at 350 nm. Cyclohexadienyl radical reacts with dissolved O2 with a rate coefficient of ∼ 4 × 10(8) mol(-1) dm(3) s(-1) forming peroxy radical. The latter may eliminate HO2 (•) giving phenols or undergoes fragmentation. The one-electron oxidant (•)OH on average induces more than two-electron oxidations. The toxicity first increases with absorbed dose, then decreases. This increase is partly due to phenols formed during the first degradation period.

  13. Pulsed electron beam water radiolysis for submicrosecond hydroxyl radical protein footprinting.

    PubMed

    Watson, Caroline; Janik, Ireneusz; Zhuang, Tiandi; Charvátová, Olga; Woods, Robert J; Sharp, Joshua S

    2009-04-01

    Hydroxyl radical footprinting is a valuable technique for studying protein structure, but care must be taken to ensure that the protein does not unfold during the labeling process due to oxidative damage. Footprinting methods based on submicrosecond laser photolysis of peroxide that complete the labeling process faster than the protein can unfold have been recently described; however, the mere presence of large amounts of hydrogen peroxide can also cause uncontrolled oxidation and minor conformational changes. We have developed a novel method for submicrosecond hydroxyl radical protein footprinting using a pulsed electron beam from a 2 MeV Van de Graaff electron accelerator to generate a high concentration of hydroxyl radicals by radiolysis of water. The amount of oxidation can be controlled by buffer composition, pulsewidth, dose, and dissolved nitrous oxide gas in the sample. Our results with ubiquitin and beta-lactoglobulin A demonstrate that one submicrosecond electron beam pulse produces extensive protein surface modifications. Highly reactive residues that are buried within the protein structure are not oxidized, indicating that the protein retains its folded structure during the labeling process. Time-resolved spectroscopy indicates that the major part of protein oxidation is complete in a time scale shorter than that of large scale protein motions.

  14. Pulsed Electron Beam Water Radiolysis for Sub-Microsecond Hydroxyl Radical Protein Footprinting

    PubMed Central

    Watson, Caroline; Janik, Ireneusz; Zhuang, Tiandi; Charvátová, Olga; Woods, Robert J.; Sharp, Joshua S.

    2009-01-01

    Hydroxyl radical footprinting is a valuable technique for studying protein structure, but care must be taken to ensure that the protein does not unfold during the labeling process due to oxidative damage. Footprinting methods based on sub-microsecond laser photolysis of peroxide that complete the labeling process faster than the protein can unfold have been recently described; however, the mere presence of large amounts of hydrogen peroxide can also cause uncontrolled oxidation and minor conformational changes. We have developed a novel method for sub-microsecond hydroxyl radical protein footprinting using a pulsed electron beam from a 2 MeV Van de Graaff electron accelerator to generate a high concentration of hydroxyl radicals by radiolysis of water. The amount of oxidation can be controlled by buffer composition, pulsewidth, dose, and dissolved nitrous oxide gas in the sample. Our results with ubiquitin and β-lactoglobulin A demonstrate that one sub-microsecond electron beam pulse produces extensive protein surface modifications. Highly reactive residues that are buried within the protein structure are not oxidized, indicating that the protein retains its folded structure during the labeling process. Time-resolved spectroscopy indicates that the major part of protein oxidation is complete in a timescale shorter than that of large scale protein motions. PMID:19265387

  15. A pulse radiolysis study of the dynamics of ascorbic acid free radicals within a liposomal environment.

    PubMed

    Kobayashi, Kazuo; Seike, Yumiko; Saeki, Akinori; Kozawa, Takahiro; Takeuchi, Fusako; Tsubaki, Motonari

    2014-10-06

    The dynamics of free-radical species in a model cellular system are examined by measuring the formation and decay of ascorbate radicals within a liposome with pulse radiolysis techniques. Upon pulse radiolysis of an N2O-saturated aqueous solution containing ascorbate-loaded liposome vesicles, ascorbate radicals are formed by the reaction of OH(·) radicals with ascorbate in unilamellar vesicles exclusively, irrespective of the presence of vesicle lipids. The radicals are found to decay rapidly compared with the decay kinetics in an aqueous solution. The distinct radical reaction kinetics in the vesicles and in bulk solution are characterized, and the kinetic data are analyzed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Electron pulse radiolysis determination of hydroxyl radical rate constants with Suwannee River fulvic acid and other dissolved organic matter isolates.

    PubMed

    Westerhoff, Paul; Mezyk, Stephen P; Cooper, William J; Minakata, Daisuke

    2007-07-01

    Pulse radiolysis experiments were conducted on dissolved organic matter (DOM) samples isolated as hydrophobic and hydrophilic acids and neutrals from different sources (i.e., stream, lake, wastewater treatment plant). Absolute bimolecular reaction rate constants for the reaction of hydroxyl radicals (*OH) with DOM (k*(OH), DOM) were determined. k*(OH, DOM) values are expressed as moles of carbon. Based on direct measurement of transient DOM radicals (DOM*) and competition kinetic techniques, both using pulse radiolysis, the k*(OH, DOM) value for a standard fulvic acid from the Suwannee River purchased from the International Humic Substances Society was (1.60 +/- 0.24) x 10(8) M(-1) s(-1). Both pulse radiolysis methods yielded comparable k*(OH, DOM) values. The k*(OH, DOM) values for the seven DOM isolates from different sources ranged from 1.39 x 10(8) M(-1) s(-1) to 4.53 x 10(8) M(-1) s(-1), and averaged 2.23 x 108 M(-1) s(-1) (equivalent to 1.9 x 10(4) (mgC/L)(-1) s(-1)). These values represent the first direct measurements of k*(OH, DOM,) and they compare well with literature values obtained via competition kinetic techniques during ozone or ultraviolet irradiation experiments. More polar, lower-molecular-weight DOM isolates from wastewater have higher k*(OH, DOM) values. In addition, the formation (microsecond time scale) and decay (millisecond time scale) of DOM* transients were observed for the first time. DOM* from hydrophobic acids exhibited broader absorbance spectra than transphilic acids, while wastewater DOM isolates had narrower DOM* spectra more skewed toward shorter wavelengths than did DOM* spectra for hydrophobic acids.

  17. Studies on the transient species formed in the pulse radiolysis of benzotriazole

    NASA Astrophysics Data System (ADS)

    Naik, D. B.; Moorthy, P. N.

    1995-09-01

    Rate constants for the reaction of benzotriazole (BTZ) with the primary species of water radiolysis (e.g. eaq-, OH, H and O -) have been determined at different pHs using the pulse radiolysis technique. Absorption spectra of the transient intermediates formed have been recorded in the region 220-650 nm. Semireduced radicals formed by eaq- reaction with benzotriazole are found to be strongly reducing in nature and they transfer electrons to various acceptors such as thionine, methylene blue, paraquat with diffusion controlled rate constants. Only SO 4- radicals were found to oxidize benzotriazole. Reactivity of BTZ towards eaq- and specific oxidants has been compared with that of indole. Evidence for characterization of both semireduced and semioxidized benzotriazole as three electron bonded species are given.

  18. Arsenic(IV). A Pulse-radiolysis study

    SciTech Connect

    Klaening, U.K. ); Bielski, B.H.J. ); Sehested, K. )

    1989-07-12

    Four As(IV) species assumed to be As(OH){sub 4} and HAsO{sub 3}{sup {minus}} and the corresponding bases As(OH){sub 3}O{sup {minus}} and AsO{sub 3}{sup 2{minus}} (pK{sub a} = 7.38 and 7.81, respectively) were observed by the radiolysis technique in aqueous arsenious acid, arsenite, and arsenate solutions. As(OH){sub 4} and As(OH){sub 3}O{sup {minus}} were observed in acid and weakly alkaline solution by the reaction of arsenious acid or arsenite with OH. HAsO{sub 3}{sup {minus}} and/or AsO{sub 3}{sup 2{minus}} are formed by the reaction of e{sup {minus}}{sub aq} with H{sub 2}AsO{sub 4}{sup {minus}} and HAsO{sub 4}{sup 2{minus}}; AsO{sub 3}{sup 2{minus}} is formed by the reaction of arsenite with O{sup {minus}} in strongly alkaline solution and by the reaction of arsenite with the carbonate radical anion CO{sub 3}{sup {minus}}. As(OH){sub 4} and As(OH){sub 3}O{sup {minus}} convert into HAsO{sub 3}{sup {minus}} and AsO{sub 3}{sup 2{minus}} by general-base-catalyzed reactions. In acid solution an equilibrium between As(OH){sub 4} and HAsO{sub 3}{sup {minus}} is observed. The kinetics of dehydration of As(OH){sub 4} suggest a slow dehydration step catalyzed by H{sup +} followed by protolysis. The thermodynamic parameters are reported. By comparison with activation parameters of other dehydration-hydration processes, these values are taken to suggest a cyclic transition state containing an extra water molecule. While As(OH){sub 4} and As(OH){sub 3}O{sup {minus}} react with O{sub 2} to yield directly HO{sub 2} and O{sub 2}{sup {minus}}, HAsO{sub 3}{sup {minus}} and AsO{sub 3}{sup 2{minus}} react with O{sub 2} with formation of a relatively stable complex that subsequently decomposes to HO{sub 2} or O{sub 2}{sup {minus}} in reactions catalyzed by H{sup +} and OH{sup {minus}}. The various As(IV) species disappear in second-order reactions. 42 refs., 8 figs., 2 tabs.

  19. Pulse radiolysis study of the reactions of catechins with nitrogen dioxide

    NASA Astrophysics Data System (ADS)

    Gebicki, Jerzy L.; Meisner, Piotr; Stawowska, Katarzyna; Gebicka, Lidia

    2012-12-01

    Nitrogen dioxide (•NO2), one of the oxidizing radicals formed in vivo is suspected to play a role in various pathophysiological processes. The reactions of •NO2 with dietary catechins, the group of flavonoids present in high amounts in green tea and red wine, have been investigated by pulse radiolysis method. The kinetics of the reaction of •NO2 with gallic acid have been also studied for comparison. The spectra of transient intermediates are presented. The rate constants of the reaction of •NO2 with catechin, epigallocatechin, epigallocatechin gallate and gallic acid determined by the competition method with 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulfonate) at pH 7.0 and room temperature have been found to be 0.9, 1.0, 2.3 and 0.5×108 M-1 s-1, respectively. The values for catechins are among the highest reported for the reactions of •NO2 with non-radical compounds.

  20. Reduction of earth alkaline metal salts in THF solution studied by picosecond pulse radiolysis.

    PubMed

    Ma, Jun; Archirel, Pierre; Schmidhammer, Uli; Teuler, Jean-Marie; Pernot, Pascal; Mostafavi, Mehran

    2013-12-27

    Picosecond pulse radiolysis of tetrahydrofuran (THF) solutions containing earth alkaline metal salt, M(II)(ClO4)2, at different concentrations are performed using two different supercontinua as probe pulse, one covering the visible and another the near-infrared (NIR) down to the visible. Two types of line scan detectors are used to record the absorption spectra in the range from 400 to 1500 nm. Because of the strong overlap between the spectra of the absorbing species in the present wavelength range, global matrices were built for each M(II) system, by delay-wise binding the matrix for pure THF with the available matrices for this cation. The number of absorbers was assessed by Singular Value Decomposition of the global matrix, and a MCR-ALS analysis with the corresponding number of species was performed. The analysis of the results show clearly that solvated electron reacts with the earth alkaline metal molecule and the product has an optical absorption band very different than that of solvated electron in pure THF. So, contrarily to the case of solution containing free Na(+), in the presence of Mg(II), Ca(II) and Sr(II) the observed absorption band is not only blueshifted, but its shape is also drastically changed. In fact with Na(+) solvated electron forms a tight-contact pair but with earth alkaline metal cation solvated electron is scavenged by the undissociated molecule M(II)(ClO4)2. In order to determine the structure of the absorbing species observed after the electron pulse, Monte Carlo/DFT simulations were performed in the case of Mg(II), based on a classical Monte Carlo code and DFT/PCM calculation of the solute. The UV-visible spectrum of the solute is calculated with the help of the TDDFT method. The calculated spectrum is close to the experimental one. It is due to two species, a contact pair and an anion.

  1. Reaction between ortho-semiquinones and oxygen: pulse radiolysis, electron spin resonance, and oxygen uptake studies.

    PubMed

    Kalyanaraman, B; Korytowski, W; Pilas, B; Sarna, T; Land, E J; Truscott, T G

    1988-10-01

    The cytotoxicity to tumor cells or cardiotoxic side effects of certain para-quinone antitumor drugs have been attributed to the corresponding semiquinones and derived superoxide and hydroxyl radicals. It has also been suggested that ortho-semiquinones, including those that arise during melanogenesis, produced via either the one-electron oxidation of catechol(amine)s or the one-electron reduction of the corresponding quinones, react with molecular oxygen to give superoxide and hydrogen peroxide. Furthermore it has been shown that catechol(amine)s which form noncyclizable quinones are more cytotoxic toward melanogenic cells than those forming cyclizable quinones. In order to provide further kinetic information on the interaction of oxygen with ortho-semiquinones, using pulse radiolysis we directly measured the rates of reaction of various ortho-semiquinones with molecular oxygen. The semiquinones of the corresponding catechol(amine)s were also produced by the horseradish peroxidase/hydrogen peroxide system, and detected by electron spin resonance spectroscopy using the spin stabilization method. Oxygen consumption was monitored using a standard Clark oxygen electrode. Our data indicate that while ortho-semiquinones from catechol(amine)s and catechol estrogens do not react with molecular oxygen at a rate equal to or greater than k less than or equal to 10(5) M-1 s-1, semiquinones from hydroxy-substituted catechol(amine)s react with dioxygen with rates in the range k = 10(6)-10(7) M-1 s-1.

  2. Pulse Radiolysis Using Very-high-energy Ions for Optimizing Cancer Therapy.

    PubMed

    Getoff, Nikola

    2016-01-01

    Cancer therapy by means of high-energy ions is very efficient. As a consequence of the linear-energy-transfer effect only a negligible part of the produced free radicals can escape combination processes to form molecular products and to cause undesired side processes. Positrons (e⁺) and γ-rays, generated by the nuclear interaction of high-energy ions in the medium, serve in monitoring the radiation dose absorbed by the tumor. However, due to the dipole nature of water molecules a small proportion of thermalized positrons (e⁺th) can become solvated (e⁺aq). Hence, they are stabilized, live longer and can initiate side reactions. In addition, positronium (Ps), besides solvated electrons (e⁺aq), can be generated and involved in the reaction mechanisms. For a better understanding of the reaction mechanisms involved and to improve cancer therapy, a time-resolved pulse radiolysis instrument using high-energy particles is discussed here. The proposed method is examined and recommended by CERN experts. It is planned to be realized at the MedAustron Radiation Therapy and Research Centre in Wiener Neustadt, Austria. Copyright © 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

  3. Reactivity of OH radicals with chlorobenzoic acids—A pulse radiolysis and steady-state radiolysis study

    NASA Astrophysics Data System (ADS)

    Zona, Robert; Solar, Sonja; Getoff, Nikola; Sehested, Knud; Holcman, Jerzy

    2010-05-01

    The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k( rad OH+substrates)=(4.5-6.2)×10 9 dm 3 mol -1 s -1, have been studied by pulse radiolysis in N 2O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320-340 nm. Their decay was according to a second-order reaction, 2 k=(1-9)×10 8 dm 3 mol -1 s -1. In the presence of N 2O/O 2 the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O 2)=(2-4)×10 7 dm 3 mol -1 s -1, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N 2O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only ˜60% of rad OH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.

  4. Nanosecond pulse radiolysis study of metal aggregation in polymeric membranes

    SciTech Connect

    Platzer, O.; Amblard, J.; Marignier, J.L.; Belloni, J.

    1992-03-05

    After an electron pulse, the transient optical absorption spectrum and the decay rate in a perfluorosulfonated ion-exchange membrane such as Nafion swollen by a 2-propanol/water mixture are found to be similar to those of the solvated electron in the same free solvent. The radiolytic yield is G(e{sub s}{sup {minus}}) = 2. In membranes swollen by a solution of silver ions, chosen as a model system for the study of metal aggregation in a microheterogeneous environment, the end-of-pulse spectrum is that of Ag{sub 2}{sup +} (G = 3.7). The following step is a fast dimerization of Ag{sub 2}{sup +} giving Ag{sub 4}{sup 2+}, occurring inside one single hydrophilic cavity, with a rate slightly higher than in the free solvent. On the contrary, the further coalescence rate drops suddenly to a value 10{sup 4} times lower than in a free solution, due to the slower diffusion of the transient species of silver aggregation through the hydrophilic channels. This process competes on the 10{sup {minus}1}{sub {minus}s} range with a corrosion of the smallest aggregate by H{sub 3}O{sup +} contained in the same cavity. Thus the polymeric medium allowed the authors to observe directly the corrosion of a noble metal aggregate by the acidic cations. In a repetitive pulse regime, it can be observed that the aggregates generated in the primary pulses act as growth centers and induce the coalescence of the new atoms further produced, thus protecting them from corrosion. 36 refs., 10 figs., 1 tab.

  5. The reduction process of phytic acid silver ion system: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Joshi, Ravi; Mukherjee, Tulsi

    2007-05-01

    Reduction of silver ion in a silver-phytic acid (1:1 ratio) system has been studied using pulse radiolysis technique. Time-resolved transformation of the intermediates, Ag +→Ag 0→Ag 2+→Ag 32+, has been clearly observed in the reduction of silver-phytic acid (1:1) system. The effect of phytic acid on the formation and decay of initial silver clusters has been also studied. The surface plasmon absorption band of stable silver nanoparticle (410 nm) and dynamic light scattering technique has been used to characterize the nanoparticles and measure the average size ( Rav=100 nm).

  6. A pulse--radiolysis approach to fast reductive cleavage of a disulfide bond to uncage enzyme activity.

    PubMed

    Milanesi, Lilia; Tomas, Salvador; Hunter, Christopher A; Weinstein, Julia A; Edge, Ruth; Navaratnam, Suppiah; Waltho, Jonathan P; Best, Jonathan

    2008-11-01

    The essential thiol of the enzyme papain has been caged by linking to an aromatic thiol. The resulting caged protein is inactive but enzymatic activity is fully restored upon chemical cleavage of the protective disulfide bond. We have exploited the chemistry of this disulfide bond to uncage papain by pulse radiolysis. We have shown that up to 10% of the enzyme activity can be restored by reductive pulse radiolysis. This approach has been tested on a small-molecule model system, and experiments on this model compound show that pulse radiolysis of the mixed cysteine-aromatic disulfide results in selective reduction of the disulfide bond to generate a thiol in 10-20% yield, consistent with the radiolytically restored activity of the caged papain quantified by the biochemical assay.

  7. Application of External-Cavity Quantum Cascade Infrared Lasers to Nanosecond Time-Resolved Infrared Spectroscopy of Condensed-Phase Samples Following Pulse Radiolysis

    SciTech Connect

    Grills, D.C.; Cook, A.R.; Fujita, E.; George, M.W.; Miller, J.R.; Preses, J.M.; Wishart, J.F.

    2010-06-01

    Pulse radiolysis, utilizing short pulses of high-energy electrons from accelerators, is a powerful method for rapidly generating reduced or oxidized species and other free radicals in solution. Combined with fast time-resolved spectroscopic detection (typically in the ultraviolet/visible/near-infrared), it is invaluable for monitoring the reactivity of species subjected to radiolysis on timescales ranging from picoseconds to seconds. However, it is often difficult to identify the transient intermediates definitively due to a lack of structural information in the spectral bands. Time-resolved vibrational spectroscopy offers the structural specificity necessary for mechanistic investigations but has received only limited application in pulse radiolysis experiments. For example, time-resolved infrared (TRIR) spectroscopy has only been applied to a handful of gas-phase studies, limited mainly by several technical challenges. We have exploited recent developments in commercial external-cavity quantum cascade laser (EC-QCL) technology to construct a nanosecond TRIR apparatus that has allowed, for the first time, TRIR spectra to be recorded following pulse radiolysis of condensed-phase samples. Near single-shot sensitivity of DeltaOD <1 x 10(-3) has been achieved, with a response time of <20 ns. Using two continuous-wave EC-QCLs, the current apparatus covers a probe region from 1890-2084 cm(-1), and TRIR spectra are acquired on a point-by-point basis by recording transient absorption decay traces at specific IR wavelengths and combining these to generate spectral time slices. The utility of the apparatus has been demonstrated by monitoring the formation and decay of the one-electron reduced form of the CO(2) reduction catalyst, [Re(I)(bpy)(CO)(3)(CH(3)CN)](+), in acetonitrile with nanosecond time resolution following pulse radiolysis. Characteristic red-shifting of the nu(CO) IR bands confirmed that one-electron reduction of the complex took place. The availability of

  8. Application of external-cavity quantum cascade infrared lasers to nanosecond time-resolved infrared spectroscopy of condensed-phase samples following pulse radiolysis.

    PubMed

    Grills, David C; Cook, Andrew R; Fujita, Etsuko; George, Michael W; Preses, Jack M; Wishart, James F

    2010-06-01

    Pulse radiolysis, utilizing short pulses of high-energy electrons from accelerators, is a powerful method for rapidly generating reduced or oxidized species and other free radicals in solution. Combined with fast time-resolved spectroscopic detection (typically in the ultraviolet/visible/near-infrared), it is invaluable for monitoring the reactivity of species subjected to radiolysis on timescales ranging from picoseconds to seconds. However, it is often difficult to identify the transient intermediates definitively due to a lack of structural information in the spectral bands. Time-resolved vibrational spectroscopy offers the structural specificity necessary for mechanistic investigations but has received only limited application in pulse radiolysis experiments. For example, time-resolved infrared (TRIR) spectroscopy has only been applied to a handful of gas-phase studies, limited mainly by several technical challenges. We have exploited recent developments in commercial external-cavity quantum cascade laser (EC-QCL) technology to construct a nanosecond TRIR apparatus that has allowed, for the first time, TRIR spectra to be recorded following pulse radiolysis of condensed-phase samples. Near single-shot sensitivity of DeltaOD <1 x 10(-3) has been achieved, with a response time of <20 ns. Using two continuous-wave EC-QCLs, the current apparatus covers a probe region from 1890-2084 cm(-1), and TRIR spectra are acquired on a point-by-point basis by recording transient absorption decay traces at specific IR wavelengths and combining these to generate spectral time slices. The utility of the apparatus has been demonstrated by monitoring the formation and decay of the one-electron reduced form of the CO(2) reduction catalyst, [Re(I)(bpy)(CO)(3)(CH(3)CN)](+), in acetonitrile with nanosecond time resolution following pulse radiolysis. Characteristic red-shifting of the nu(CO) IR bands confirmed that one-electron reduction of the complex took place. The availability of

  9. Pulse radiolysis system of OPU-LINAC in RIAST, Osaka Prefecture University

    NASA Astrophysics Data System (ADS)

    Kojima, Takao; Taniguchi, Ryoichi; Furuta, Masakazu; Okuda, Shuichi; Hara, Masayuki; Fujita, Shin'ichi

    2004-09-01

    Micro- to milli-second pulse radiolysis apparatus using short electron pulse form 18 MeV linear accelerator (Linac) is in-service at the Research institute for advanced science and technology (RIAST), Osaka Prefecture University. This apparatus is an effective tool, not only for investigation of primary process on radiation chemistry, but also for research of electron transfer mechanism playing an important role in chemistry and bioscience. This apparatus is composed of an 18 MeV electron linear accelerator (electron pulse duration: about 4 μs) and a transient light absorption measurement system. We introduce the outline of this system, transient absorption spectrum of thiocyanate aqueous solution as an example of measured data and future plan.

  10. Pulse radiolysis of nucleic acids and their base constituents: Bibliographies on radiation chemistry. XI

    NASA Astrophysics Data System (ADS)

    von Sonntag, Clemens; Ross, Alberta B.

    In the elucidation of the primary processes involved in the free-radical-induced damage to DNA and its subunits, pulse radiolysis proves to be one of the most powerful tools. The first studies data back to 1964. The updating review (C. v. Sonntag, Radiat. Phys. Chem. 1987, 30, 313) which precedes this compilation has placed the emphasis on the more recent developments. It has been felt that a bibliography including the earlier literature on this subject might be helpful for further reading. For this compilation the data stored by the Radiation Chemistry Data Center bibliographic database (1) through 1986 were processed using the SELECT keywords: purines, pyrimidines, nucleotides, nucleosides, nucleic acids and pulse radiolysis. The number of citations found was reduced by about one-third by eliminating privately published symposia papers, theses and papers not strictly relevant to this topic, e.g. on flavins, NADH, one-electron reduction of nitrouracil or the redox potential of isobarbituric acid. On the other hand, a few more papers known to us but not revealed by the keywords were added. The bibliography is arranged in approximately chronological order, references grouped by year of publication. Reviews are collected at the end of the bibliography in a separate section.

  11. Spur reactions observed by picosecond pulse radiolysis in highly concentrated bromide aqueous solutions.

    PubMed

    El Omar, Abdel Karim; Schmidhammer, Uli; Balcerzyk, Anna; LaVerne, Jay; Mostafavi, Mehran

    2013-03-21

    The formation of the well-known product Br3(-), observed in the steady-state radiolysis of highly concentrated Br(-) aqueous solutions, has now been directly observed at ultrashort times corresponding to the relaxation of the spur. The transient absorption induced by picosecond pulse radiolysis of 6 M Br(-) aqueous solution was probed simultaneously at 260 nm with the third harmonic laser wave and from 350 to 750 nm with a supercontinuum generated by the fundamental laser wave. This approach allows several transient radiolytic species to be followed in parallel, particularly the solvated electron, BrOH(-•), Br2(-•), and Br3(-). The kinetics measured within 4 ns at 260 and 370 nm clearly exhibit that the decay of Br2(•-) is correlated with the formation of Br3(-). In highly concentrated Br(-) solutions, the OH(•) radical is fully replaced by Br2(•-), and the spur kinetics of OH(•) radical in pure water is comparable with that of Br2(-•). Model calculations indicate that the main OH(•) radical combination product H2O2 in pure water has formation kinetics similar to that of Br3(-) in 6 M Br(-) solutions. Moreover, they point out that oxidation of Br(-) occurs within the electron pulse both by direct energy absorption and by scavenging of the water radical cation, H2O(•+).

  12. Picosecond pulse radiolysis of direct and indirect radiolytic effects in highly concentrated halide aqueous solutions.

    PubMed

    Balcerzyk, Anna; Schmidhammer, Uli; El Omar, Abdel Karim; Jeunesse, Pierre; Larbre, Jean-Philippe; Mostafavi, Mehran

    2011-08-25

    Recently we measured the amount of the single product, Br(3)(-), of steady-state radiolysis of highly concentrated Br(-) aqueous solutions, and we showed the effect of the direct ionization of Br(-) on the yield of Br(3)(-). Here, we report the first picosecond pulse-probe radiolysis measurements of ionization of highly concentrated Br(-) and Cl(-) aqueous solutions to describe the oxidation mechanism of the halide anions. The transient absorption spectra are reported from 350 to 750 nm on the picosecond range for halide solutions at different concentrations. In the highly concentrated halide solutions, we observed that, due to the presence of Na(+), the absorption band of the solvated electron is shifted to shorter wavelengths, but its decay, taking place during the spur reactions, is not affected within the first 4 ns. The kinetic measurements in the UV reveal the direct ionization of halide ions. The analysis of pulse-probe measurements show that after the electron pulse, the main reactions in solutions containing 1 M of Cl(-) and 2 M of Br(-) are the formation of ClOH(-•) and BrOH(-•), respectively. In contrast, in highly concentrated halide solutions, containing 5 M of Cl(-) and 6 M of Br(-), mainly Cl(2)(-•) and Br(2)(-•) are formed within the electron pulse without formation of ClOH(-•) and BrOH(-•). The results suggest that, not only Br(-) and Cl(-) are directly ionized into Br(•) and Cl(•) by the electron pulse, the halide atoms can also be rapidly generated through the reactions initiated by excitation and ionization of water, such as the prompt oxidation by the hole, H(2)O(+•), generated in the coordination sphere of the anion. © 2011 American Chemical Society

  13. Pulse radiolysis of fast reactions in molecular systems. Progress report, November 1979-September 1980

    SciTech Connect

    Dorfman, L.M.

    1980-01-01

    The rates of elementary chemical reactions in irradiated solutions are being studied by observation of reactive intermediates using the pulse radiolysis technique. Optical absorption spectra of these transient species, which determine the course of the chemistry, are being obtained. The types of reactive species currently of interest are organic molecule ions (both cations and anions) and radical ions, and transition metal carbonyl radicals in solution. Since reaction is initiated by a pulse of high energy electrons, our investigations inherently relate to radiation chemical systems. The information obtained is, however, also of interest in various areas of organic reaction kinetics in which ionic species are known to play a central role. The rectivity of the transition metal carbonyl radicals is of interest in the area of homogeneous catalysis. Current activities involve: spectra and reactivities of transition metal carbonyl radicals of the type M(CO)/sub 5/; reactivity of organic ionic species (including carbocations and carbanions) in irradiated solutions.

  14. Pulsed radiolysis of model aromatic polymers and epoxy based matrix materials

    NASA Technical Reports Server (NTRS)

    Gupta, A.; Moacanin, J.; Liang, R.; Coulter, D.

    1982-01-01

    Models of primary processes leading to deactivation of energy deposited by a pulse of high energy electrons were derived for epoxy matrix materials and polyl-vinyl naphthalene. The basic conclusion is that recombination of initially formed charged states is complete within 1 nanosecond, and subsequent degradation chemistry is controlled by the reactivity of these excited states. Excited states in both systems form complexes with ground state molecules. These excimers or exciplexes have their characteristics emissive and absorptive properties and may decay to form separated pairs of ground state molecules, cross over to the triplet manifold or emit fluorescence. ESR studies and chemical analyses subsequent to pulse radiolysis were performed in order to estimate bond cleavage probabilities and net reaction rates. The energy deactivation models which were proposed to interpret these data have led to the development of radiation stabilization criteria for these systems.

  15. Hydroxyl Radical Rate Constants: Comparing UV/H2O2 and Pulse Radiolysis for Environmental Pollutants

    EPA Science Inventory

    The objective of this study was to measure OH radical rates using both UV/H2O2 and pulse radiolysis techniques for 13 US EPA Contaminant Candidate List compounds (2,6- and 2,4-DNT, EPTC, prometon, linuron, diuron, dyfonate, diazinon, RDX, molinate, nitrobenz...

  16. Carbon- and nitrogen-centered radicals produced from L-lysine by radiation-induced oxidation: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Ito, Takeo; Morimoto, Shota; Fujita, Shin-ichi; Kobayashi, Kazuo; Tagawa, Seiichi; Nishimoto, Sei-ichi

    2008-09-01

    Radical species generated from the reactions of a basic amino acid, L-lysine (Lys), with hydroxyl radicals ( rad OH) and sulfate radical anion ( SO4-rad ) have been detected by the method of pulse radiolysis. On the basis of electron transfer reactivities toward tetranitromethane (TNM), it was demonstrated that reducing carbon-centered radicals are generated as a result of hydrogen abstraction from CH 2 of Lys with a G-value of 1.9 × 10 -7 mol J -1. On the other hand, direct oxidation of L-Lys by SO4-rad formed a transient species with different spectroscopic properties, most likely, the ɛ-N-centered Lys radical.

  17. Direct Evidence for Transient Pair Formation between a Solvated Electron and H3O(+) Observed by Picosecond Pulse Radiolysis.

    PubMed

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2014-07-03

    The reaction between the solvated electron and hydronium cation H3O(+) in water constitutes a fundamental reaction in chemistry. Due to significant rearrangement of solvent molecules around both the electron and H3O(+), the reaction rate of this process is not controlled by diffusion. The presence of a reaction barrier suggests the formation of an intermediate that has so far not been observed. Here, the time-resolved visible absorption spectra in three concentrated acid solutions, perchloric, sulfuric, and phosphoric, at various concentrations are recorded by the picosecond pulse radiolysis method. In contrast to previous reports, a strong blue shift of the absorption band of the solvated electron in acidic solutions compared to neat water is clearly observed, consistent with formation of a pair between the solvated electron and hydronium cation.

  18. Pulse radiolysis of supercritical water II. Reaction of nitrobenzene with hydrated electrons and hydroxyl radicals.

    SciTech Connect

    Marin, T. W.; Cline, J. A.; Bartels, D. M.; Jonah, C. D.; Takahashi, K.; Chemistry; Hakkaido Univ.

    2003-12-26

    The rate constants for the reactions of nitrobenzene with the hydroxyl radical (OH{sup {sm_bullet}}) and hydrated electron ((e{sup -}){sub aq}) in water have been measured from room temperature to 400 {sup o}C using electron pulse radiolysis and transient absorption spectroscopy. The diffusion-limited reaction of nitrobenzene with (e{sup 0}){sub aq} exhibits temperature-insensitive activation energy up to 300 {sup o}C, indicating that the activation energy for electron diffusion remains high over this range. The (e{sup -}){sub aq} reactivity is explained as a long-range electron transfer, and the results are interpreted in terms of extended Marcus theory and Smoluchowski relationships. At 380 {sup o}C, the rate constant has a density dependence similar to that previously reported for other (e{sup -}){sub aq} scavenging reactions. The reaction rate of nitrobenzene with OH{sup {sm_bullet}} is very insensitive to temperature from room temperature up to 300 {sup o}C, in agreement with previous studies. Above 300 {sup o}C, the rate constant increases as the critical temperature is approached and exceeded. Time-resolved electronic absorption spectra of the nitrobenzene radiolysis transients reveal complex kinetics involving multiple absorbing species.

  19. Reactions of OH-radicals with procarbazine. A pulse radiolysis and computer simulation study.

    PubMed

    Delipetar-Grudl, A; Solar, S; Getoff, N

    2006-01-01

    Pulse radiolysis was applied to study the reactivity of *OH radicals with procarbazine (PC), a cytostatic agent widely used in radiation- and chemotherapy. An overall rate constant of k(*OH+PC) = 3.7 x 10(9) l.mol(-1).s(-1) was determined. The thereby formed transients had a strong absorption at 350 nm, epsilon350 = 4.46 x 10(3) l.mol(-1).cm(-1), and a weak absorption band around 530 nm. Computer simulation studies to elucidate the most probable sites of *OH attack on the PC molecule showed that *OH radical addition to the aromatic ring had the highest probability. These transients decayed by a first order reaction, k = 1.75 x 10(3) s(-1), whereby species having a maximum absorption at 300 nm and broad shoulder at 340-380 nm were formed. Similar absorptions were observed after gamma radiolysis of PC. A reaction mechanism is suggested. For the reaction of H-atoms with PC, a rate constant k(*H+PC) = 6.4 x 10(8) l.mol(-1).s(-1) was determined.

  20. Emission mechanism of doubly ortho-linked quinoxaline/diphenylfluorene or cis-stilbene/fluorene hybrid compounds based on the transient absorption and emission measurements during pulse radiolysis.

    PubMed

    Wei, Yi; Samori, Shingo; Tojo, Sachiko; Fujitsuka, Mamoru; Lin, Jin-Sheng; Chen, Chien-Tien; Majima, Tetsuro

    2009-05-20

    A series of bipolar OLED materials were subjected to pulsed radiolysis experiments to determine their transient absorption and lifetime profiles of the independently in situ generated radical cations and anions in solutions. Moreover, their emission behaviors from the charge recombination of their radical ions were also determined by the pulse radiolysis method. It was found the absorption bands in doubly ortho-linked quinoxaline/diphenylfluorene hybrids 1a-e are red-shifted progressively with increasing electron-donating nature at the C5 and C8 positions of the quinoxaline template. The incipient radical anions in 1a-e are mainly localized on the quinoxaline heterocyclic moiety, whereas the incipient radical cations are mainly distributed onto the attached electron-donating groups at the C5 and C8 positions of the quinoxaline template. For other doubly ortho-linked cis-stilbene derivatives 3d, 3f, and 4f, the radical anions are mainly localized on the cis-stilbene central moiety and the radical cation is mainly distributed onto both para substituents of the cis-stilbene templates. It was also shown that there is a correlation between their optoelectronic emission efficiencies and the radiolysis induced emission intensities. In addition, the charge transporting behaviors within an OLED device were found to show the relationship with transient absorption half-lives (tau(1/2)) of the radical ions. Charge recombination mechanisms in both the OLED and pulsed radiolysis experiments were proposed to rationalize these observations, allowing us to establish some guidelines for an ultimate molecular design of ideal bipolar optoelectronic materials with a judicious choice of local charge appendages in the optoelectronic templates.

  1. Dynamic spectral shifts of molecular anions in organic glasses. [Pulse radiolysis

    SciTech Connect

    Huddleston, R.K.; Miller, J.R.

    1982-06-24

    Time-dependent spectra of the radical anions of pyromellitic dianhydride and p-dinitrobenzene have been observed after formation by pulse radiolysis in frozen 2-methyltetrahydrofuran and triacetin glasses. At temperatures near the glass transition, the spectra shift toward the blue over the entire observed time range 100 ns to 100 s), while at temperatures well below the glass transition, the spectral shifts can be stopped or greatly slowed. The magnitudes of the shifts are not large (typically approx. = to 10 nm), but because they are larger than the vibrational line widths, dramatic kinetics may be observed: the absorbance grows or decays by more than a factor of five at some wavelengths. The observations are consistent with a solvent molecule reorientation mechanism for spectral shifts of molecular ions in low-temperature organic glasses. 6 figures.

  2. Design of an optical cell for pulse radiolysis of supercritical water

    NASA Astrophysics Data System (ADS)

    Takahashi, Kenji; Cline, Jason A.; Bartels, David M.; Jonah, Charles D.

    2000-09-01

    The design of a flow cell that is applicable to pulse radiolysis/transient absorption experiments on supercritical water is described. The cell is designed to minimize dead volume and prevent the accumulation of radiolytic products. It is also necessary to minimize emission and absorption of sapphire windows from high energy electron beam irradiation. To obtain an optical throughput of f/4, the inner diameter is 6 mm, and distance between windows is 25 mm. The effective optical path length is 20 mm for irradiation from the side through a thin Hastelloy wall. Belleville spring washers were used to keep a constant force on the 3 mm sapphire windows, which were sealed to the Hastelloy body with copper gaskets. An application of this cell to measurements of solvated electrons in supercritical water is demonstrated.

  3. Antioxidative properties of hydroxycinnamic acid derivatives and a phenylpropanoid glycoside. A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Lin, Weizhen; Navaratnam, Suppiah; Yao, Side; Lin, Nianyun

    1998-10-01

    Spectral and redox properties of the phenoxyl radicals from hydroxycinnamic acid derivatives and one selected component of phenylpropanoid glycosides, verbascoside, were studied using pulse radiolysis techniques. On the basis of the pH dependence of phenoxyl radical absorptions, the p Ka values for deprotonation of sinapic acid radical and ferulic acid radical are 4.9 and 5.2. The rate constants of one electron oxidation of those antioxidants by azide radical and bromide radical ion were determined at pH 7. The redox potentials of those antioxidants were determined as 0.59-0.71 V vs NHE at pH 7 with reference standard 4-methoxyphenol and resorcinol.

  4. Application of pulse radiolysis to the study of proteins: chymotrypsin and trypsin.

    PubMed Central

    Faraggi, M; Klapper, M H; Dorfman, L M

    1978-01-01

    The one-electron reduction of chymotrypsin, trypsin, and their zymogens have been studied by pulse radiolysis. The optical spectra of the transient products from the two active enzymes display a pH-dependent band at 360 nm, associated with the histidine-electron adduct. The yield of the histidyl radical as a function of pH is consistent with a pK(a) less than 4.5, which suggests that the radical is located at the enzyme active site. The histidines of the proenzymes chymotrypsinogen and trypsinogen are unreactive towards the hydrated electron. We conclude that formation of the histidine-electron adduct at the serine protease active site is sensitive to the physical alterations which accompany protease activation. PMID:708836

  5. Competition reactions of H2O•+ radical in concentrated Cl- aqueous solutions: picosecond pulse radiolysis study.

    PubMed

    El Omar, Abdel Karim; Schmidhammer, Uli; Rousseau, Bernard; LaVerne, Jay; Mostafavi, Mehran

    2012-11-29

    Picosecond pulse-probe radiolysis measurements of highly concentrated Cl(-) aqueous solutions are used to probe the oxidation mechanism of the Cl(-). The transient absorption spectra are measured from 340 to 710 nm in the picosecond range for the ultrafast electron pulse radiolysis of halide solutions at different concentrations up to 8 M. The amount of Cl(2)(•-) formation within the electron pulse increases notably with increasing Cl(-) concentration. Kinetic measurements reveal that the direct ionization of Cl(-) cannot solely explain the significant amount of fast Cl(2)(•-) formation within the electron pulse. The results suggest that Cl(-) reacts with the precursor of the OH(•) radical, i.e., H(2)O(•+) radical, to form Cl(•) atom within the electron pulse and the Cl(•) atom reacts subsequently with Cl(-) to form Cl(2)(•-) on very short time scales. The proton transfer reaction between H(2)O(•+) and the water molecule competes with the electron transfer reaction between Cl(-) and H(2)O(•+). Molecular dynamics simulations show that number of water molecules in close proximity decreases with increasing concentration of the salt (NaCl), confirming that for highly concentrated solutions the proton transfer reaction between H(2)O(•+) and a water molecule becomes less efficient. Diffusion-kinetic simulations of spur reactions including the direct ionization of Cl(-) and hole scavenging by Cl(-) show that up to 30% of the H(2)O(•+) produced by the irradiation could be scavenged for solutions containing 5.5 M Cl(-). This process decreases the yield of OH(•) radical in solution on the picosecond time scale. The experimental results for the same concentration of Cl(-) at a given absorbed dose show that the radiation energy absorbed by counterions is transferred to Cl(-) or water molecules and the effect of the countercation such as Li(+), K(+), Na(+), and Mg(2+) on the oxidation yield of Cl(-) is negligible.

  6. Pulse radiolysis study of ion-species effects on the solvated electron in alkylammonium ionic liquids

    NASA Astrophysics Data System (ADS)

    Kondoh, Takafumi; Asano, Akira; Yang, Jinfeng; Norizawa, Kimihiro; Takahashi, Kenji; Taguchi, Mitsumasa; Nagaishi, Ryuji; Katoh, Ryuzi; Yoshida, Yoichi

    2009-12-01

    The spectra and kinetic behavior of solvated electrons (e sol-) in alkyl ammonium ionic liquids (ILs), i.e. N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMMA-BF 4), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13-TFSI), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13-TFSI), and N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P14-TFSI) were investigated by the pulse radiolysis method. The e sol- in each of the ammonium ILs has an absorption peak at 1100 nm, with molar absorption coefficients of 1.5-2.3×10 4 dm 3 mol -1 cm -1. The e sol- decayed by first order with a rate constant of 1.4-6.4×10 6 s -1. The reaction rate constant of the solvated electron with pyrene (Py) was 1.5-3.5×10 8 dm 3 mol -1 s -1 in the various ILs. These values were about one order of magnitude higher than the diffusion-controlled limits calculated from measured viscosities. The radiolytic yields ( G-value) of the e sol- were 0.8-1.7×10 -7 mol J -1. The formation rate constant of e sol- in DEMMA-TFSI was 3.9×10 10 s -1. The dry electron (e dry-) in DEMMA-TFSI reacts with Py with a rate constant of 7.9×10 11 dm 3 mol -1 s -1, three orders of magnitude higher than that of the e sol- reactions. The G-value of the e sol- in the picosecond time region is 1.2×10 -7 mol J -1. The capture of e dry- by scavengers was found to be very fast in ILs.

  7. Pulse radiolysis of alkanes: A time-resolved electron paramagnetic resonance study

    SciTech Connect

    Shkrob, I.A.; Trifunac, A.D.

    1994-02-14

    Time-resolved spin-echo-detected electron paramagnetic resonance (EPR) was applied to examine short-lived alkyl radicals formed in pulse radiolysis of liquid alkanes. It was found that the ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation is temperature-independent and is ca. 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the fast ion molecule reactions involving radical cations are a significant route of radical generation. The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals are emissively polarized in spur reactions. this initial polarization rapidly increases with shortening of the aliphatic chain. Another finding is that a long-chain structure of these radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. Effects of phenolic and alkene additives in radiolysis of n-alkanes are examined. It is demonstrated that phenoxy radicals are produced in dissociative capture of electrons and alkane holes. Another route is a reaction of phenols with free hydrogen atoms. A rapid transfer of singlet correlation from the geminate radical ion pairs is responsible for unusual polarization patterns in the phenoxy and cyclohexadienyl radicals. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. 56 refs.

  8. Oxidation reactions of 2-thiouracil: a theoretical and pulse radiolysis study.

    PubMed

    Prasanthkumar, K P; Suresh, C H; Aravindakumar, C T

    2012-11-08

    The reaction of hydroxyl radical ((•)OH) with the nucleic acid base analogue 2-thiouracil (1) has been studied by pulse radiolysis experiments and DFT. The generic intermediate radicals feasible for the (•)OH reactions with 1, namely, one electron oxidation product (1(•+)), (•)OH-adducts (3(•), 4(•), and 5(•)), and H-abstracted radicals (6(•) and 7(•)), were characterized by interpreting their electronic and structural properties along with calculated energetics and UV-vis spectra. Pulse radiolysis experiments showed that the transient formed in the reaction of (•)OH with 1 in water at pH 6.5 has λ(max) at 430 nm. A bimolecular rate constant, k(2) of 9.6 × 10(9) M(-1) s(-1), is determined for this reaction via competition kinetics with 2-propanol. The experiments suggested that the transient species could be a dimer radical cation 2(•+), formed by the reaction of 1 with the radical cation 1(•+). For this reaction, an equilibrium constant of 4.7 × 10(3) M(-1) was determined. The transient formed in the reaction of 1 with pulse radiolytically produced Br(2)(•-) at pH 6.5 as well as Cl(2)(•-) at pH 1 has also produced λ(max) at 430 nm and suggested the formation of 2(•+). The calculated UV-vis spectra of the transient species (1(•+), 3(•), 4(•), 5(•), 6(•), and 7(•)) showed no resemblance to the experimental spectra, while that of 2(•+) (λ(max) = 420 nm) agreed well with the experimental value and thus confirmed the formation of 2(•+). The 420 nm peak was due to σ → σ* electronic excitation centered on a 2-center-3-electron (2c-3e) sulfur-sulfur bond [-S∴S-]. 2(•+) is the first reported example of a dimer radical cation in a pyrimidine heterocyclic system. Further, 5-C and 6-C substituted (substituents are -F, -Cl, -NH(2), -N(CH(3))(2), -OCH(3), -CF(3), -CH(3), -CH(2)CH(3), n-propyl, phenyl, and benzyl) and 5,6-disubstituted 2-thiouracil systems have been characterized by DFT and found that the reaction (1 + 1

  9. A laser flash photolysis and pulse radiolysis study of primary photochemical processes of flumequine.

    PubMed

    Bazin, M; Bosca, F; Marin, M L; Miranda, M A; Patterson, L K; Santus, R

    2000-10-01

    The 355 nm laser flash photolysis of argon-saturated pH 8 phosphate buffer solutions of the fluoroquinolone antibiotic flumequine produces a transient triplet state with a maximum absorbance at 575 nm where the molar absorptivity is 14,000 M(-1) cm(-1). The quantum yield of triplet formation is 0.9. The transient triplet state is quenched by various Type-1 photodynamic substrates such as tryptophan (TrpH), tyrosine, N-acetylcysteine and 2-deoxyguanosine leading to the formation of the semireduced flumequine species. This semireduced form has been readily identified by pulse radiolysis of argon-saturated pH 8 buffered aqueous solutions by reaction of the hydrated electrons and the CO2*- radicals with flumequine. The absorption maximum of the transient semireduced species is found at 570 nm with a molar absorptivity of 2,500 M(-1) cm(-1). In argon-saturated buffered solutions, the semireduced flumequine species formed by the reaction of the flumequine triplet with TrpH stoichiometrically reduces ferricytochrome C (Cyt Fe3+) under steady state irradiation with ultraviolet-A light. In the presence of oxygen, O2*- is formed but the photoreduction of Cyt Fe3+ by O2*- competes with an oxidizing pathway which involves photo-oxidation products of TrpH.

  10. Pulse radiolysis of silybin: One-electron oxidation of the flavonoid at neutral pH

    NASA Astrophysics Data System (ADS)

    György, I.; Antus, S.; Földiák, G.

    One-electron oxidation of silybin, a flavonoid drug used in human therapy of liver, was investigated by pulse radiolysis at neutral pH. Phenoxyl radicals formed from the substrate by oxidising N .3 radicals were identified by comparing the transient optical absorption spectra with those obtained from model compounds. The orto-methoxy-phenolic structure (ring B) is the exclusive target for one-electron oxidation of silybin. The 5.7-dihydroxy-chromanone moiety (ring A) withstands free-radical attack at neutral pH due to the chelatic H-bond (p Ka = 10.2) existing between the 5-OH and 4-oxo groups. Hydroxyl radicals react with silybin at diffusion controlled rate ( k = 1.8 x 10 10 dm 3 mol -1 s -1). The reactivity of silybin towards free radicals at neutral pH is conform with the assumption that the physiological activity of the flavonoid is due to its chain-breaking antioxidant behaviour.

  11. One-electron transfer reactions of the couple NAD. /NADH. [Pulse radiolysis

    SciTech Connect

    Grodkowski, J.; Neta, P.; Carlson, B.W.; Miller, L.

    1983-08-04

    One-electron transfer reactions involving nicotinamide-adenine dinucleotide in its oxidized and reducd forms (NAD./NADH) were studied by pulse radiolysis in aqueous solutions. One-electron oxidation of NADH by various phenoxyl radicals and phenothiazine cation radicals was found to take place with rate constants in the range of 10/sup 5/ to 10/sup 8/ M/sup -1/ s/sup -1/, depending on the redox potential of the oxidizing species. In all cases, NAD. is formed quantitatively with no indication for the existence of the protonated form (NADH/sup +/.). The spectrum of NAD., as well as the rates of oxidation of NADH by phenoxyl and by (chlorpromazine)/sup +/. were independent of pH between pH 4.5 and 13.5. Reaction of deuterated NADH indicated only a small kinetic isotope effect. All these findings point to an electron transfer mechanism. On the other hand, attempts to observe the reverse electron transfer, i.e., one-electron reduction of NAD. to NADH by radicals such as semiquinones, showed that k was less than 10/sup 4/ to 10/sup 5/ M/sup -1/ s/sup -1/, so that it was unobservable. Consequently, it was not possible to achieve equilibrium conditions which would have permitted the direct measurement of the redox potential for NAD./NADH. One-electron reduction of NAD. appears to be an unlikely process. 1 table.

  12. A direct demonstration of the catalytic action of monodehydroascorbate reductase by pulse radiolysis.

    PubMed

    Kobayashi, K; Tagawa, S; Sano, S; Asada, K

    1995-11-17

    To elucidate the catalytic mechanism of monodehydroascorbate (MDA) reductase from cucumber, its interaction with MDA radical was investigated by the use of pulse radiolysis. When approximately equimolar MDA radical to the fully reduced MDA reductase was generated, the fully reduced enzyme reacted first with MDA radical to form the red semiquinone, and the semiquinone further reacted with MDA radical to form the oxidized enzyme. At a low ratio (< 20) of MDA radical to enzyme concentration, the fully reduced enzyme reacted quantitatively with MDA radical to form the semiquinone with a second-order rate constant of 2.6 x 10(8) M-1 s-1 at pH 7.4. At excess MDA radical to enzyme concentration, a similar rate constant was obtained from the decay of MDA radical. These results suggest that the reaction of the semiquinone with MDA radical occurs at the same rate or rate-limiting step of the oxidation of the fully reduced enzyme by MDA radical. The rate constants decreased with an increase in NaCl concentration, suggesting that the localization of cationic groups of amino acid residue near the active site may provide electrostatic guidance to the anionic substrate of MDA radical.

  13. Pulse radiolysis studies of mangiferin: A C- glycosyl xanthone isolated from Mangifera indica

    NASA Astrophysics Data System (ADS)

    Mishra, B.; Priyadarsini, K. Indira; Sudheerkumar, M.; Unnikrishhnan, M. K.; Mohan, H.

    2006-01-01

    Pulse radiolysis technique has been employed to study the reaction of different oxidizing and reducing radicals with mangiferin. The reaction of rad OH radical showed the formation of transient species absorbing in 380-390 and 470-480 nm region. The reaction with specific one-electron oxidants (N 3rad , CCl 3O 2rad ) also showed the formation of similar transient absorption bands and is assigned to phenoxyl radicals. The p Ka values of the transient species have been determined to be 6.3 and 11.9. One-electron oxidation potential of mangiferin at pH 9 has been found to be 0.62 V vs. NHE. The reaction of e aq- showed the formation of transient species with λmax at 340 nm, which is assigned to the ketyl anion radical formed on addition of e aq- at carbonyl site. Reactions of one-electron oxidised mangiferin radicals with ascorbic acid have also been studied.

  14. Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.

    PubMed

    Sionkowska, Alina

    2006-07-03

    An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).

  15. Pulse radiolysis studies on the hypoxia-selective toxicity of a colbalt-mustard complex.

    PubMed Central

    Anderson, R. F.; Denny, W. A.; Ware, D. C.; Wilson, W. R.

    1996-01-01

    The kinetic basis for the in vitro hypoxia-selective cytotoxicity (HSC) of the Co(III)-nitrogen mustard complex SN 24771 (NSC 675352) has been investigated using pulse radiolysis. The rate constants for the one-electron reduction of SN 24771 by model reductants exhibited a marked dependence on the one-electron reduction potential of the reductant, with values up to several orders of magnitude slower than for the nitroimidazole drug misonidazole. Following one-electron reduction to form the Co(II) complex (species I) consecutive conversion to further transient species (II and III) occurs with first order rate constants of 120 +/- 10 s-1 and 10 +/- 2 s-1 and are associated with release of ligands. Neither of these subsequent processes are inhibited by the addition of O2 up to a concentration of 0.5 mmol l-1 suggesting that the HSC action of SN 24771 most likely arises from a mechanism other than simple redox cycling between the Co(III) and Co(II) forms by O2. If the measured low rate constants of one-electron reduction by model reductants of SN 24771 (as compared to the reduction of nitroaromatics), is mirrored by biological reductants, then it is proposed that HSC may occur through competition between SN 24771 and O2 for these reductants. PMID:8763845

  16. One-electron reduction of 17-(dimethylaminoethylamino)-17-demethoxygeldanamycin: a pulse radiolysis study.

    PubMed

    Goldstein, Sara

    2011-08-18

    Geldanamycin, a benzoquinone ansamycin antibiotic, is a natural product inhibitor of Hsp90 with potent and broad anticancer properties but with unacceptable levels of hepatotoxicity. Consequently, numerous structural analogs, which differ only in their 17-substituent, have been synthesized including the water-soluble and less toxic 17-(dimethylaminoethylamino)-17-demethoxygeldanamycin (17-DMAG, Alvespimycin). It has been suggested that the different hepatotoxicity reflects the redox active properties of the quinone moiety. The present pulse radiolysis study was aimed at studying the one-electron reduction of 17-DMAG. The UV-visible spectrum of the semiquinone radical, its pK(a), and the second-order rate constants for the reactions of 17-DMAG with CO(2)(•-) and (CH(3))(2)C(•)OH have been obtained. The reduction potential of 17-DMAG has been determined to be -194 ± 6 mV (vs NHE) using oxygen, 1,4-naphthoquinone, and menadione as electron acceptors. This reduction potential is lower than that of O(2) demonstrating that thermodynamically the semiquinone radical can reduce O(2) to superoxide, particularly since the concentration of O(2) is expected to exceed that of the drug in cells and tissues. © 2011 American Chemical Society

  17. Oxidation of tryptamine and 5-hydroxytryptamine: a pulse radiolysis and quantum chemical study.

    PubMed

    Gaikwad, P; Priyadarsini, K I; Naumov, S; Rao, B S M

    2009-07-23

    The reactions of oxidizing radicals (*)OH, N(3)(*), Br(2)(*-), and NO(2)(*) with tryptamine (Tpe) and 5-hydroxytryptamine (HTpe) were studied by pulse radiolysis and analyzed by quantum chemical calculations. Barring NO(2)(*) radical, the rate constants for their reaction with Tpe and HTpe were found to be diffusion controlled and the rates in the NO(2)(*) radical reaction with HTpe are lower by 2 orders of magnitude with k approximately 1 x 10(7) dm(3) mol(-1) s(-1). The transient spectra formed on oxidation of Tpe and HTpe exhibited peaks at 330 and 530 nm (indolyl radical) and 420 nm (indoloxyl radical), respectively, and the latter is in reasonable agreement with the calculated value (407 nm). Both radicals decay through direct recombination, but only the indoloxyl radical was observed to react with the parent molecule to give a (HTpe-Ind)(*) radical adduct for [HTpe] > or = 50 x 10(-6) mol dm(-3). The calculated optimized geometries in water revealed the formation of two distinct types of radical adducts, one through the H-O bond and the other by C-C linkage. The H-O bonded radical adduct was found to be exothermic with a reaction enthalpy of -4 kcal mol(-1) and bond length 0.1819 nm and the C-C bonded radical adducts are endothermic and rate determining but are finally driven by exothermic processes involving intermolecular H transfer followed by intramolecular reorganization through H shift resulting in stable C4-C4' and C2-C4' dimers with reaction enthalpies of -39 and -44 kcal mol(-1), respectively, and this process was found to be thermodynamically as efficient as direct recombination of indoloxyl radicals. The formation of the two dimer products was also seen in steady-state radiolysis. The lack of adduct formation in the case of indolyl radical with Tpe is due to the positive free energy change (DeltaG = 10 kcal mol(-1)). The energetics for the (*)OH addition have shown dependence on the site of activation with (HTpe-OH)(*) adducts at C2 and C4 and the

  18. Pulse radiolysis of alkyl iodides and oxygen in the gas phase

    SciTech Connect

    Ramirez, J.E.

    1981-01-01

    Using a pulse radiolysis facility for the study of fast chemical kinetics in the gas phase established at the University of Florida Radiation Chemistry Laboratories, parameters relevant to a linear electron beam initiated atomic iodine laser, which would lase on the transition 5/sup 2/P/sub 1/2/ (I*) ..-->.. 5/sup 2/P/sub 3/2/ (I), have been investigated. Kinetic data for the parent compound quenching of I* were obtained by variation of the parent compound pressure at constant buffer gas pressure and observing I* decay rates versus time. Deactivation rate constants for the perfluoroalkyl iodides were found to be much lower than for alkyl iodides (in cm/sup 3//molec s): CH/sub 3/I, 2.0 +- 0.1 x 10/sup -13/; C/sub 2/H/sub 5/I, 5.0 +- 0.3 x 10/sup -13/; CF/sub 3/I, 8.8 +- 1.5 x 10/sup -16/; C/sub 2/F/sub 5/I, 9.7 +- 1.0 x 10/sup -15/; i-C/sub 3/F/sub 7/I, 1.7 +- 0.1 x 10/sup -15/; C/sub 4/F/sub 9/I, 1.8 +- 0.1 x 10/sup -14/. The extent of population inversion was investigated by measuring initial excited state and ground state atomic iodine concentrations and calculating the branching ratio, (I*)/sub 0//(I*)/sub 0//(I)/sub 0/: CH/sub 3/I, 2.7; CF/sub 3/I, 3.8; C/sub 2/F/sub 5/I, 2.7; i-C/sub 3/F/sub 7/I, 3.2; C/sub 4/FgI, 1.8. Perflouromethyl iodide showed the largest population inversion from electron beam irradiation. Using formation of O/sub 3/ from O/sub 2/ as the dosimeter (G = 13.8 molecules/100 eV for ozone), energy deposited per electron pulse in 750 torr O/sub 2/ was 7.3 x 10/sup 1/a* eV/g. Spectrophotometric detection of ozone utilized the 253.7 nm Hg line. The rate of formation of ground vibrational state ozone in the pulse radiolysis of oxygen was followed using the 253.7 nm Hg line. The rate of formation was found to be early second-order with a rate constant of 4.1 +- 0.4 x 10/sup -15/ cm/sup 3//molec s. It is formed from direct combination of oxygen atoms and oxygen molecules and from collisional quenching of vibrationally excited ozone and/or an

  19. Acid proliferation to improve the sensitivity of EUV resists: a pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Enomoto, Kazuyuki; Arimitsu, Koji; Yoshizawa, Atsutaro; Yamamoto, Hiroki; Oshima, Akihiro; Kozawa, Takahiro; Tagawa, Seiichi

    2011-04-01

    The yields of acid have been measured in the electron-beam irradiation of triphenylsulfonium triflate (TPS-Tf) and pinanediol monosulfonates, which consist of tosylate (PiTs), 4-fluorobenzenesulfonate (Pi1F), or 4-trifluoromethylbenzenesulfonate (Pi3F), as an acid amplifier blended in 4-hydroxystyrene matrixes. The acid yields efficiency decreases when PiTs is present, while its efficiency increases in the presence of Pi3F. Reactions of the electrons with TPS-Tf and pinanediol monosulfonates have been studied using pulse radiolysis in liquid tetrahydrofuran (THF) to evaluate the kinetic contributions to acid production. The THF-solvated electrons react with PiTs, Pi1F, and Pi3F to produce the corresponding radical anions; the rate constants are estimated to be 4.1, 5.1, and 9.2 × 1010 M-1 s-1, respectively. Electron transfer from PiTs•-, Pi1F•-, and Pi3F•- radical anions to TPS-Tf occurs with the rate constants of 5.7×1010, 1.2×1011, and 6.3 × 1010 M-1 s-1, respectively. The long-lived Pi3F•- efficiently undergoes the electron transfer to TPS-Tf to form the TPS-Tf•-, which subsequently decompose to generate TfOH. On the other hand, the decay channels of PiTs•- and Pi1F•-, which possess a relatively short lifetime, are presumably dependent on its reactions with solvated protons (charge recombination) rather than the electron transfer to TPS-Tf. The novel acid production pathway via the electron transfer from pinanediol monosulfonate radical anions to TPS-Tf is presented.

  20. Photoreduction of azaoxoisoaporphines by amines: laser flash and steady-state photolysis and pulse radiolysis studies.

    PubMed

    de la Fuente, Julio R; Aliaga, Christian; Cañete, Alvaro; Kciuk, Gabriel; Szreder, Tomasz; Bobrowski, Krzysztof

    2013-01-01

    Photoreduction of 7H-benzo[e]perimidin-7-one (3-AOIA, A1) and its 2-methyl derivative (2-Me-3-AOIA, A2) by non-H-donating amines (1,4-diazabicyclo[2.2.2]octane [DABCO]; 2,2,6,6-tetramethylpiperidine [TMP]), and a hydrogen-donating amine (triethylamine [TEA]), has been studied in deaerated neat acetonitrile solutions using laser flash photolysis (LFP) and steady-state photolysis. The triplet excited states of A1 and A2 were characterized by a strong absorption band with λmax = 440 nm and lifetimes of 20 and 27 μs respectively. In the presence of tertiary amines, both triplet excited states were quenched with rate constants close to the diffusional limit (kq ranged between 10(9) and 10(10) M(-1) s(-1)). The transient absorption spectra observed after quenching with DABCO and TMP were characterized by maxima located at 460 nm and broad shoulders in the range of 500-600 nm. These transient species are attributed to solvent-separated radical ion pairs and/or to isolated radical anions. In the presence of TEA, these transients undergo proton transfer, leading to the neutral hydrogenated radicals, protonated over the N1- and O-atoms. Transient absorption spectra of these transients were characterized by maxima located at 400 and 520 nm and 430 nm respectively. Additional support for these spectral assignments was provided by pulse radiolysis (PR) experiments in acetonitrile and 2-propanol solutions. © 2013 The American Society of Photobiology.

  1. Pulse radiolysis studies of 3,5-dimethyl pyrazole derivatives of selenoethers.

    PubMed

    Barik, Atanu; Singh, Beena G; Sharma, Asmita; Jain, Vimal K; Priyadarsini, K Indira

    2014-11-06

    One electron redox reaction of two asymmetric 3,5-dimethyl pyrazole derivatives of selenoethers attached to ethanoic acid (DPSeEA) and propionic acid (DPSePA) were studied by pulse radiolysis technique using transient absorption detection. The reaction of the hydroxyl ((•)OH) radical with DPSeEA or DPSePA at pH 7 produced transients absorbing at 500 nm and at 300 nm, respectively. The absorbance at 500 nm increased with increasing parent concentration indicating formation of dimer radical cations. From the absorbance changes, the equilibrium constants for the formation of dimer radical cation of DPSeEA and DPSePA were estimated as 2020 and 1608 M(-1), respectively. The rate constants at pH 7 for the reaction of the (•)OH radical with DPSeEA and DPSePA were determined to be 9.6 × 10(9) and 1.4 × 10(10) M(-1) s(-1), respectively. The dimer radical cation of DPSeEA and DPSePA decayed by first order kinetics with a rate constant of 2.8 × 10(4) and 5.5 × 10(3) s(-1), respectively. The yield of radical cations of DPSeEA and DPSePA were estimated from the secondary electron transfer reaction, which corresponds to 38% and 48% of (•)OH radical yield, respectively. Some fraction of monomer radical cation undergoes decarboxylation reaction, and the yield of decarboxylation was 25% and 20% for DPSeEA and DPSePA, respectively. These results have implication in understanding their antioxidant activity. The reaction of trichloromethyl peroxyl radical, glutathione, and ascorbic acid further support their antioxidant behavior.

  2. Picosecond pulse radiolysis study of dynamics of solvation of electron and fluorenone anion in primary alcohols.

    PubMed

    Palit, Dipak K; Torche, Fayçal; Marignier, Jean-Louis

    2014-01-09

    We have studied the dynamics of solvation of electron injected directly into primary alcohols as well as that of fluorenone anion using pulse radiolysis technique with the time resolution of about 15 ps. Unlike in the previous reports, we observe nonexponential dynamics of both electron and anion solvation. While the ultrafast component, τ1 (<15 ps) representing the inertial time scale of the dynamics is faster than the time resolution of the spectrometer, the slower component, τ2, has been assigned to the translational motion leading to structural changes of the hydrogen bonding network of the solvent in the inner solvation cell or alcohol cluster. τ2 agrees well with the electron solvation times reported by the earlier authors. τ3 is associated with the restructuring of the hydrogen bond network structure of the solvent in the region outside the solvation cell. Nonexponential solvation dynamics of the fluorenone anion has been described well by a two-component process. The most important observation in this work is that the lifetime of the shorter component, τ1, determined in four alcoholic solvents, is much longer than the electron solvation time in the corresponding solvents determined in this work or anion solvation time reported earlier. The lifetime of this component is nearly comparable with the average dipolar solvation time but shorter than the longitudinal relaxation time of the solvent. In the case of anion, τ1 has been assigned to the restructuring of the first solvation shell by breakage of solvent hydrogen bonds of the fluorenone molecule and formation of hydrogen bonds with the anion. In this case, too, the longer component, τ2, with the lifetime of a few nanoseconds, has been assigned to reorganization of hydrogen bonds in the solvent hydrogen bond network structure.

  3. Mechanism of oxidative conversion of Amplex® Red to resorufin: Pulse radiolysis and enzymatic studies.

    PubMed

    Dębski, Dawid; Smulik, Renata; Zielonka, Jacek; Michałowski, Bartosz; Jakubowska, Małgorzata; Dębowska, Karolina; Adamus, Jan; Marcinek, Andrzej; Kalyanaraman, Balaraman; Sikora, Adam

    2016-06-01

    Amplex® Red (10-acetyl-3,7-dihydroxyphenoxazine) is a fluorogenic probe widely used to detect and quantify hydrogen peroxide in biological systems. Detection of hydrogen peroxide is based on peroxidase-catalyzed oxidation of Amplex® Red to resorufin. In this study we investigated the mechanism of one-electron oxidation of Amplex® Red and we present the spectroscopic characterization of transient species formed upon the oxidation. Oxidation process has been studied by a pulse radiolysis technique with one-electron oxidants (N3(•), CO3(•-),(•)NO2 and GS(•)). The rate constants for the Amplex® Red oxidation by N3(•) ((2)k=2.1·10(9)M(-1)s(-1), at pH=7.2) and CO3(•-) ((2)k=7.6·10(8)M(-1)s(-1), at pH=10.3) were determined. Two intermediates formed during the conversion of Amplex® Red into resorufin have been characterized. Based on the results obtained, the mechanism of transformation of Amplex® Red into resorufin, involving disproportionation of the Amplex® Red-derived radical species, has been proposed. The results indicate that peroxynitrite-derived radicals, but not peroxynitrite itself, are capable to oxidize Amplex® Red to resorufin. We also demonstrate that horseradish peroxidase can catalyze oxidation of Amplex® Red not only by hydrogen peroxide, but also by peroxynitrite, which needs to be considered when employing the probe for hydrogen peroxide detection. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. Detection of Structural Changes upon One-Electron Oxidation and Reduction of Stilbene Derivatives by Time-Resolved Resonance Raman Spectroscopy during Pulse Radiolysis and Theoretical Calculations.

    PubMed

    Fujitsuka, Mamoru; Cho, Dae Won; Choi, Jungkweon; Tojo, Sachiko; Majima, Tetsuro

    2015-07-02

    Stilbene (St) derivatives have been investigated for many years because of their interesting photochemical reactions such as cis-trans isomerization in the excited states and charged states and their relation to poly(p-phenylenevinylene)s. To clarify their charged state properties, structural information is indispensable. In the present study, radical cations and radical anions of St derivatives were investigated by radiation chemical methods. Absorption spectra of radical ion states were obtained by transient absorption measurements during pulse radiolysis; theoretical calculations that included the solvent effect afforded reasonable assignments. The variation in the peak position was explained by using HOMO and LUMO energy levels. Structural changes upon one-electron oxidation and reduction were detected by time-resolved resonance Raman measurements during pulse radiolysis. Significant downshifts were observed with the CC stretching mode of the ethylenic groups, indicative of the decrease in the bonding order. It was confirmed that the downshifts observed with reduction were larger than those with oxidation. On the other hand, the downshift caused by oxidation depends significantly on the electron-donating or electron-withdrawing nature of the substituents.

  5. Picosecond pulse radiolysis study on the distance dependent reaction of the solvated electron with organic molecules in ethylene glycol.

    PubMed

    El Omar, Abdel Karim; Schmidhammer, Uli; Pernot, Pascal; Murata, Shigeo; Mostafavi, Mehran

    2012-12-13

    The decay of solvated electron e(s)(-) is observed by nanosecond and picosecond pulsed radiolysis, in diluted and highly concentrated solutions of dichloromethane, CH(2)Cl(2), trichloromethane, CHCl(3), tribromomethane, CHBr(3), acetone, CH(3)COCH(3), and nitromethane, CH(3)NO(2), prepared in ethylene glycol. First, second-order rate constants for the reactions between e(-)(s) and the organic scavengers have been determined. The ratio between the highest rate constant that was found for CH(3)NO(2) and the lowest one that was found for acetone is 3. This difference in reactivity cannot be explained by the change of viscosity or the size of the molecules. Then, from the analysis of decay kinetics obtained using ultrafast pulse-probe method, the distance dependent first-order rate constant of electron transfer for each scavenger has been determined. The amplitude of the transient effect observed on the picosecond time scale differs strongly between these solvated electron scavengers. For an identical scavenger concentration, the transient effect lasts ≈650 ps for CH(3)NO(2) compared to ~200 ps for acetone. For acetone, the distance dependent first-order rate constant of electron transfer is decreasing very rapidly with increasing distance, whereas for nitromethane and tribromomethane the rate constant is decreasing gradually with the distance and its value remains non-negligible even at ~10 Å. This rate constant is controlled mostly by the free energy of the reaction. For nitromethane and tribromomethane, the driving force is great, and the reaction can occur even at long distance, whereas for acetone the driving force is small and the reaction occurs almost at the contact distance. For nitromethane and acetone, the one-electron reduction reaction needs less internal reorganization energy than for alkyl halide compounds for which the reaction occurs in concert with bond breaking and geometric adjustment.

  6. Charge transfer from 2-aminopurine radical cation and radical anion to nucleobases: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Manoj, P.; Mohan, H.; Mittal, J. P.; Manoj, V. M.; Aravindakumar, C. T.

    2007-01-01

    Pulse radiolysis study has been carried out to investigate the properties of the radical cation of 2-aminopurine (2AP) and the probable charge transfer from the radical cation and radical anion of 2AP to natural nucleobases in aqueous medium. The radical cation of 2AP was produced by the reaction of sulfate radical anion ( SO4rad -). The time resolved absorption spectra obtained by the reaction of SO4rad - with 2AP at neutral pH have two distinct maxima at 380 and 470 nm and is assigned to the formation of a neutral radical of the form 2AP-N 2(-H) rad ( k2 = 4.7 × 10 9 dm 3 mol -1 s -1 at pH 7). This neutral radical is formed from the deprotonation reaction of a very short-lived radical cation of 2AP. The transient absorption spectra recorded at pH 10.2 have two distinct maxima at 400 and 480 nm and is assigned to the formation of a nitrogen centered radical (2AP-N(9) rad ). As the hole transport from 2AP to guanine is a highly probable process, the reaction of SO4rad - is carried out in the presence of guanosine, adenosine and inosine. The spectrum obtained in the presence of guanosine was significantly different from that in the absence and it showed prominent absorption maxima at 380 and 470 nm, and a weak broad maximum centered around 625 nm which match well with the reported spectrum of a neutral guanine radical (G(-H) rad ). The electron transfer reaction from the radical anion of 2AP to thymine (T), cytidine (Cyd) and uridine (Urd) was also investigated at neutral pH. Among the three pyrimidines, only the transient spectrum in the presence of T gave a significant difference from the spectral features of the electron adduct of 2AP, which showed a prominent absorption maximum at 340 nm and this spectrum is similar to the electron adduct spectrum of T. The preferential reduction of thymine by 2AP rad - and the oxidation of guanosine by 2AP rad + clearly follow the oxidation/reduction potentials of the purines and pyrimidines.

  7. Radiation-Induced Chemical Reactions in Hydrogel of Hydroxypropyl Cellulose (HPC): A Pulse Radiolysis Study.

    PubMed

    Yamashita, Shinichi; Ma, Jun; Marignier, Jean-Louis; Hiroki, Akihiro; Taguchi, Mitsumasa; Mostafavi, Mehran; Katsumura, Yosuke

    2016-12-01

    We performed studies on pulse radiolysis of highly transparent and shape-stable hydrogels of hydroxypropyl cellulose (HPC) that were prepared using a radiation-crosslinking technique. Several fundamental aspects of radiation-induced chemical reactions in the hydrogels were investigated. With radiation doses less than 1 kGy, degradation of the HPC matrix was not observed. The rate constants of the HPC composing the matrix, with two water decomposition radicals [hydroxyl radical ((•)OH) and hydrated electron ([Formula: see text])] in the gels, were determined to be 4.5 × 10(9) and 1.8 × 10(7) M(-1) s(-1), respectively. Direct ionization of HPC in the matrix slightly increased the initial yield of [Formula: see text], but the additionally produced amount of [Formula: see text] disappeared immediately within 200 ps, indicating fast recombination of [Formula: see text] with hole radicals on HPC or on surrounding hydration water molecules. Reactions of [Formula: see text] with nitrous oxide (N2O) and nitromethane (CH3NO2) were also examined. Decay of [Formula: see text] due to scavenging by N2O and CH3NO2 were both slower in hydrogels than in aqueous solutions, showing slower diffusions of the reactants in the gel matrix. The degree of decrease in the decay rate was more effective for N2O than for CH3NO2, revealing lower solubility of N2O in gel than in water. It is known that in viscous solvents, such as ethylene glycol, CH3NO2 exhibits a transient effect, which is a fast reaction over the contact distance of reactants and occurs without diffusions of reactants. However, such an effect was not observed in the hydrogel used in the current study. In addition, the initial yield of [Formula: see text], which is affected by the amount of the scavenged precursor of [Formula: see text], in hydrogel containing N2O was slightly higher than that in water containing N2O, and the same tendency was found for CH3NO2.

  8. Effects of oxidation on copper-binding properties of Aβ1-16 peptide: a pulse radiolysis study.

    PubMed

    Ramteke, S N; Ginotra, Y P; Walke, G R; Joshi, B N; Kumbhar, A S; Rapole, S; Kulkarni, P P

    2013-12-01

    The reaction of hydroxyl radicals ((•)OH) with Aβ1-16 peptide was carried out using pulse radiolysis to understand the effect of oxidation of peptide on its copper-binding properties. This reaction produced oxidized, dimeric and trimeric Aβ1-16 peptide species. The formation of these products was established with the help of fluorescence spectroscopy and mass spectrometry. The mass spectral data indicate that the major site of oxidation is at His6, while the site for dimerization is at Tyr10. Diethyl pyrocarbonate-treated Aβ1-16 peptide did not produce any trimeric species upon oxidation with (•)OH. The quantitative chemical modification studies indicated that one of the three histidine residues is covalently modified during pulse radiolysis. The copper-binding studies of the oxidized peptide revealed that it has similar copper-binding properties as the unoxidized peptide. Further, the cytotoxicity studies point out that both oxidized and unoxidized Aβ1-16 peptide are equally efficient in producing free radicals in presence of copper and ascorbate that resulted in comparable cell death.

  9. Picosecond pulse radiolysis of highly concentrated sulfuric acid solutions: evidence for the oxidation reactivity of radical cation H2O(•+).

    PubMed

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2014-06-12

    Aqueous solution of sulfuric acid is used as a suitable system to investigate the reactivity of the short-lived radical cation H2O(•+) which is generated by radiation in water. Ten aqueous solutions containing sulfuric acid with concentration from 1 to 18 mol L(-1) are studied by picosecond pulse radiolysis. The absorbance of the secondary radical SO4(•-) (or HSO4(•)) formed within the 10 ps electron pulse is measured by a pulse-probe method in the visible range. The analysis of the kinetics show that the radicals of sulfuric acid are formed within the picosecond electron pulse via two parallel mechanisms: direct electron detachment by the electron pulse and oxidation by the radical cation of water H2O(•+). In highly concentrated solution when SO4(2-) is in contact with H2O(•+), the electron transfer becomes competitive against proton transfer with another water molecule. Therefore, H2O(•+) may act as an extremely strong oxidant. The maximum radiolytic yield of scavenged H2O(•+) is estimated to be 5.3 ± 0.1 × 10(-7) mol J(-1).

  10. One-electron oxidation of mitomycin C and its corresponding peroxyl radicals. A steady-state and pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Getoff, Nikola; Solar, Sonja; Quint, Ruth M.

    1997-12-01

    The one-electron oxidation of Mitomycin C (MMC) as well as the formation of the corresponding peroxyl radicals were investigated by both steady-state and pulse radiolysis. The steady-state MMC-radiolysis by OH-attack followed at both absorption bands showed different yields: at 218 nm G i (-MMC) = 3.0 and at 364 nm G i (-MMC) = 3.9, indicating the formation of various not yet identified products, among which ammonia was determined, G(NH 3) = 0.81. By means of pulse radiolysis it was established a total κ (OH + MMC) = (5.8 ± 0.2) × 10 9 dm 3 mol -1 s -1. The transient absorption spectrum from the one-electron oxidized MMC showed absorption maxima at 295 nm ( ɛ = 9950 dm 3 mol -1 cm t-1 ), 410 nm ( ɛ = 1450 dm 3 mol -1 cm -1) and 505 nm ( ɛ = 5420 dm 3 mol -1 cm -1). At 280-320 and 505 nm and above they exhibit in the first 150 μs a first order decay, κ1 = (0.85 ± 0.1) × 10 3 s -1, and followed upto ms time range, by a second order decay, 2 κ = (1.3 ± 0.3) × 10 8 dm 3 mol -1 s -1. Around 410 nm the kinetics are rather mixed and could not be resolved. The steady-state MMC-radiolysis in the presence of oxygen featured a proportionality towards the absorbed dose for both MMC-absorption bands, resulting in a G i (-MMC) = 1.5. Among several products ammonia-yield was determined G(NH 3) = 0.52. The formation of MMC-peroxyl radicals was studied by pulse radiolysis, likewise in neutral aqueous solution, but saturated with a gas mixture of 80% N 2O and 20% O 2. The maxima of the observed transient spectrum are slightly shifted compared to that of the one-electron oxidized MMC-species, namely: 290 nm ( ɛ = 10100 dm 3 mol -1 cm -1), 410 nm ( ɛ = 2900 dm 3 mol -1 cm -1) and 520 nm ( ɛ = 5500 dm 3 mol -1 cm -1). The O 2-addition to the MMC-one-electron oxidized transients was found to be at 290 to 410 nm gk(MMC·OH + O 2) = 5 × 10 7 dm 3 mol -1 s -1, around 480 nm κ = 1.6 × 10 8 dm 3 mol -1 s -1 and at 510 nm and above, κ = 3 × 10 8 dm 3 mol -1 s -1. The

  11. Implementation of laser induced fluorescence in a pulse radiolysis experiment--a new way to analyze resazurin-like reduction mechanisms.

    PubMed

    Balcerzyk, A; Baldacchino, G

    2014-04-07

    Resazurin (RNO) reduction by hydrated electrons produces a fluorescent molecule: resorufin (RN). To take advantage of RN fluorescence, a novel setup is designed by implementing fluorescence detection induced by laser in a pulse radiolysis experiment. Time resolved fluorescence spectra were recorded with a fast gated intensified CCD camera during the reduction of RNO from μs to ms. Two 532 nm laser types have been used to describe the short μs range by a 5 ns Q-switch laser and the μs-ms range by a CW DPSS laser. By fitting the simulated model to the experimental data a second order rate constant of 10(9) M(-1) s(-1) was re-evaluated. This method should be considered in the near future in many in situ and real time measurements for evaluating radical production.

  12. EPR and NMR detection of transient radicals and reaction products. [Radiolysis of methanol and aqueous potassium acetate

    SciTech Connect

    Trifunac, A.D.

    1981-01-01

    Magnetic resonance methods in radiation chemistry are illustrated. The most recent developments in pulsed EPR and NMR studies in pulse radiolysis are outlined with emphasis on the study of transient radicals and their reaction products. 12 figures.

  13. Guanosine radical reactivity explored by pulse radiolysis coupled with transient electrochemistry.

    PubMed

    Latus, A; Alam, M S; Mostafavi, M; Marignier, J-L; Maisonhaute, E

    2015-06-04

    We follow the reactivity of a guanosine radical created by a radiolytic electron pulse both by spectroscopic and electrochemical methods. This original approach allows us to demonstrate that there is a competition between oxidation and reduction of these intermediates, an important result to further analyse the degradation or repair pathways of DNA bases.

  14. The scavenging reactions of nitrogen dioxide radical and carbonate radical by tea polyphenol derivatives: a pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Miao, Jin-Ling; Wang, Wen-Feng; Pan, Jing-Xi; Lu, Chang-Yuan; Li, Rong-Qun; Yao, Si-De

    2001-02-01

    The reactions of tea polyphenol derivatives, including epicatechin (EC) and epigallocatechin gallate (EGCG), with nitrogen dioxide radical (NO 2rad ) and carbonate radical (CO 3rad - ) have been studied in detail using time-resolved pulse radiolysis technique. In all the cases, the corresponding phenoxyl radical was formed through electron transfer reaction. From the build-up kinetics of the phenoxyl radicals and the decay kinetics of CO 3rad - radical, the reaction rate constants of EC, EGCG with NO 2rad and CO 3rad - were determined to be 9.0×10 7, 1.2×10 8 and 5.6×10 8, 6.6×10 8 dm 3 mol -1 s -1, respectively. Therefore, tea polyphenol derivatives proved to be efficient scavengers of NO 2rad and CO 3rad - radicals.

  15. Effect of ionic micellar medium on kinetics and mechanism of oxidation of bovine serum albumin: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Joshi, Ravi; Mukherjee, Tulsi

    2010-09-01

    Effect of protein-micelle interaction on bovine serum albumin (BSA) oxidation by trichloromethyl peroxyl radical (CCl 3O 2·) in anionic sodium dodecyl sulfate (SDS) and cationic cetyltrimethyl ammonium bromide (CTAB) micellar media has been studied using nanosecond pulse radiolysis technique. Viscosity measurement and light scattering studies have suggested that SDS and CTAB micelles produce BSA-micelle aggregates of different sizes and polydispersity. Oxidation kinetics and transients have been affected both by anionic SDS and cationic CTAB micelles but in a different manner. Tryptophanyl-CCl 3O 2· adduct radical to tyrosyl radical transformation in BSA has been observed in anionic SDS micelles but not in cationic CTAB micelles. Similar studies have also been done with tryptophan and tyrosine amino acids, which undergo oxidation in BSA. The study suggests that Coulombic and hydrophobic interactions between micelles and protein affect the structure of the protein to shield its functional amino acids, like tryptophan and tyrosine, to neutral oxidizing radical.

  16. Free radical mechanisms for the oxidation of substituted ascorbates. A pulse radiolysis study of L-ascorbic acid-2-sulfate

    SciTech Connect

    Cabelli, D.E.; Comstock, D.A.; Bielski, B.H.J.

    1983-09-01

    The oxidations of L-ascorbate 2-sulfate by Br/sub 2//sup -/ and OH radicals generated in aqueous solutions (pH 4.5 to 9.5) were studied by pulse radiolysis. The (2-SO/sub 4/A)./sup -/ radical, generated in an electron transfer reaction between Br/sub 2//sup -/ and the parent compound, loses sulfate (tau approx. 500 ..mu..sec) to give ascorbate free radical (A./sup -/) with a G(A./sup -/) = 2.0. The oxidation of L-ascorbate 2sulfate by OH radicals is complex, yielding both (2-SO/sub 4/A)/sup -/ and OH radical adducts. Some of these transients subsequently yield A./sup -/. HPLC studies corroborate the overall mechanism postulated for the oxidation of L-ascorbate 2-sulfate by OH radicals.

  17. Pulse radiolysis of tetrazolium violet in aqueous and aqueous-alcoholic solutions under oxidative and reductive conditions

    NASA Astrophysics Data System (ADS)

    Kovács, A.; Wojnárovits, L.; Pálfi, T.; Emi-Reynolds, G.; Fletcher, J.

    2008-09-01

    The radiolytic reduction of colourless tetrazolium salts to coloured formazans in liquid and solid state is suggested for dosimetry purposes. In order to clarify the reaction mechanism, a pulse radiolysis study was conducted in aqueous and aqueous-alcoholic solutions under oxidative and reductive conditions. Under reducing conditions, fast formation of the electron adduct tetrazolinyl radical was observed: coloured formazan final product formed during the decay of electron adduct. Both the decay of the tetrazolinyl radical and the formation of the formazan were found to be second order. The spectra of the formazan were similar in neutral and alkaline solutions, but with higher absorbance in the latter solutions due to the higher molar absorption coefficient. Under oxidative conditions formazan did not form; hydroxylated products through OH-adducts were observed in the pH range studied.

  18. Temperature dependence of the rate constant for the bimolecular recombination of Cl-2 in water—A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Szala-Bilnik, J.; Pierscieniewska, P.; Wolszczak, M.; Swiatla-Wojcik, D.

    2014-04-01

    The rate constant for the disproportionation of Cl-2 in water has been determined for the temperature range 22-87 °C using pulse radiolysis of 0.1 M NaCl+1 mM HClO4 aqueous solution. The rate constant for the decay of Cl-2 has been found to be 2×(7.35±0.53)×108 M-1 s-1 at 22 °C (at zero ionic strength). The determined activation energy, Ea=10.89±0.37 kJ mol-1, is less than expected for diffusion-controlled reactions. A good fit to the Noyes equation (1/kobs=1/kdiff+1/kreact) has been obtained assuming the reaction step is activationless with kreact=A‧T.

  19. Seeking the mechanism responsible for fluoroquinolone photomutagenicity: a pulse radiolysis, steady-state, and laser flash photolysis study.

    PubMed

    Soldevila, Sonia; Consuelo Cuquerella, M; Lhiaubet-Vallet, Virginie; Edge, Ruth; Bosca, Francisco

    2014-02-01

    The mechanism responsible for the remarkable photomutagenicity of fluoroquinolone (FQ) antibiotics remains unknown. For this reason, it was considered worthwhile to study in detail the interactions between DNA and a dihalogenated FQ such as lomefloxacin (LFX; one of the most photomutagenic FQs) and its N-acetyl derivative ALFX. Studies of photosensitized DNA damage by (A)LFX, such as formation of DNA single-strand breaks (SSBs), together with pulse radiolysis, laser flash photolysis, and absorption and fluorescence measurements, have shown the important effects of the cationic character of the piperazinyl ring on the affinity of this type of drug for DNA. Hence, the formation of SSBs was detected for LFX, whereas ALFX and ciprofloxacin (a monofluorated FQ) needed a considerably larger dose of light to produce some damage. In this context, it was determined that the association constant (Ka) for the binding of LFX to DNA is ca. 2×10(3)M(-1), whereas in the case of ALFX it is only ca. 0.5×10(3)M(-1). This important difference is attributed to an association between the cationic peripheral ring of LFX and the phosphate moieties of DNA and justifies the DNA SSB results. The analysis of the transient species detected and the photomixtures has allowed us to establish the intermolecular processes involved in the photolysis of FQ in the presence of DNA and 2'-deoxyguanosine (dGuo). Interestingly, although a covalent binding of the dihalogenated FQ to dGuo occurs, the photodegradation of FQ…DNA complexes did not reveal any significant covalent attachment. Another remarkable outcome of this study was that (A)LFX radical anions, intermediates required for the onset of DNA damage, were detected by pulse radiolysis but not by laser flash photolysis. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. Fundamental reactions in TiO 2 nanocrystallite aqueous solutions studied by pulse radiolysis

    NASA Astrophysics Data System (ADS)

    Gao, Ruomei; Safrany, Agnes; Rabani, Joseph

    2002-12-01

    Reactions of the hydrated electron, H atoms, 2-propanol, and methanol radicals with the TiO 2 nano-particles have been studied either directly or by competition kinetics. The radicals were produced by radiolysis of 2-propanol, t-butanol, or methanol aqueous solutions in acid pH's. The reactions involve electron injection to the conduction band. As expected, the t-butanol radical is inert towards TiO 2 under our conditions, while the other reducing radicals react with TiO 2. The reactivity decreases in the order: e aq->H>CH 3COHCH 3>CH 2OH. Two TiO 2 nanocrystallite sizes, with average diameters of 1.0 and 4.7 nm were compared. For equal concentrations (in terms of TiO 2 molecules), the rate of electron injection shows relatively little dependency on particle size. The rates of interfacial electron transfer and transfer coefficient are also reported.

  1. Mesolysis Mechanisms of Aromatic Thioether Radical Anions Studied by Pulse Radiolysis and DFT Calculations.

    PubMed

    Yamaji, Minoru; Tojo, Sachiko; Fujitsuka, Mamoru; Sugimoto, Akira; Majima, Tetsuro

    2015-08-21

    The mesolysis mechanisms for eight aromatic thioether radical anions (ArCH2SAr'(•-)) generated during radiolysis in 2-methyltetrahydrofuran were studied by spectroscopic measurements and DFT calculation. Seven of ArCH2SAr'(•-) underwent mesolysis via dissociation of the σ-bond between the benzylic carbon and sulfur atoms, forming the corresponding radical and anion with the stepwise mechanism or concerted mechanism. Conversely, no mesolysis in the benzyl β-naphthyl sulfide radical anion was found. From the Arrhenius analysis of the mesolysis with the stepwise mechanism, apparent activation energies (ΔEexp) were determined and compared with those (ΔEcal) estimated by the DFT calculations. Two types of C-S bond dissociation are possible to give the C radical and S anion (ArCH2(•)/Ar'S(-)) and the C anion and S radical (ArCH2(-)/Ar'S(•)). The dissociation energies (BDE(ArCH2(•)/Ar'S(-)) and BDE(ArCH2(-)/Ar'S(•))) were estimated by the DFT calculations, and BDE(ArCH2(•)/Ar'S(-)) were found to be smaller than BDE(ArCH2(-)/Ar'S(•)). The formation of ArCH2(•)/Ar'S(-) was observed on the mesolysis of five ArCH2SAr'(•-), while one ArCH2SAr'(•-) provided ArCH2(-)/Ar'S(•). Chemical properties governing the mesolysis mechanisms of ArCH2SAr'(•-) are discussed.

  2. Laser pulse stacking method

    DOEpatents

    Moses, Edward I.

    1992-01-01

    A laser pulse stacking method is disclosed. A problem with the prior art has been the generation of a series of laser beam pulses where the outer and inner regions of the beams are generated so as to form radially non-synchronous pulses. Such pulses thus have a non-uniform cross-sectional area with respect to the outer and inner edges of the pulses. The present invention provides a solution by combining the temporally non-uniform pulses in a stacking effect to thus provide a more uniform temporal synchronism over the beam diameter.

  3. Laser pulse stacking method

    DOEpatents

    Moses, E.I.

    1992-12-01

    A laser pulse stacking method is disclosed. A problem with the prior art has been the generation of a series of laser beam pulses where the outer and inner regions of the beams are generated so as to form radially non-synchronous pulses. Such pulses thus have a non-uniform cross-sectional area with respect to the outer and inner edges of the pulses. The present invention provides a solution by combining the temporally non-uniform pulses in a stacking effect to thus provide a more uniform temporal synchronism over the beam diameter. 2 figs.

  4. Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran

    SciTech Connect

    Takamuku, S.; Kigawa, H.; Suematsu, H.; Susumu, T.; Tsumori, K.; Sakurai, H.

    1982-05-13

    One-electron reduction of dimethyl ..mu..-truxinate (..mu..-DMT), dimethyl ..beta..-truxinate (..beta..-DMT), and dimethyl ..cap alpha..-truxillate (..cap alpha..-DMT) has been investigated by pulse radiolysis and 77 K matrix ..gamma.. irradiation of the 2-methyltetrahydrofuran solutions. Cycloreversion of the radical anions formed by an electron attachment to these cyclobutanes was observed in all cases, even at 77 K. The orientation of the cycloreversion was dependent on the stereochemistry of the cyclobutanes, and the selectivity was reasonably explained by a so-called cis effect; the best possible release of steric hindrance decides the primary step of the reaction. In 77 K matrix ..gamma.. irradiation of ..cap alpha..-DMT, an intense IR absorption was found after the photobleaching of trapped electrons with light > 690 nm. In other DMTs, the IR absorption band was not observed while the cycloreversion of DMT by mobile electrons occurred. Thus, the IR band in the case of ..cap alpha..-DMT was assigned to an associated dimer anion due to the interaction between the radical anion and the neutral molecule pair of trans-methyl cinnamate orginally formed by the cycloreversion of ..cap alpha..-DMT. The dimer anion was presumed to be oriented in a head-to-tail structure in a solvent cage on the basis of the original configuration of ..cap alpha..-DMT.

  5. Favism inducing agents: a pulse radiolysis study of isouramil and convicine. Progress report, December 1, 1979 - November 30, 1980

    SciTech Connect

    Chevion, M.; Ilan, Y.A.

    1980-01-01

    Isouramil and covicine, substances implicated in precipitating favic crises in glucose-6-phosphate dehydrogenase deficient individuals, have been studied in N/sub 2/O-saturated aqueous solutions by pulse radiolysis, and the kinetics of the reactions of both substances with OH radicals were determined. The products of these reactions are addition intermediates absorbing above 330 nm. The decay of the intermediate(s) formed in the isouramil reaction is a biphasic one, while the decay of the corresponding intermediate for the convicine reaction is characterized by a single constant. By analogy to uracil, it is suggested that the OH radical is added to the double bond at either positions 5 or 6 of the pyrimidine ring forming two different intermediates. Each of these intermediates loses a molecule of water indicated by the observed biphasic decay reaction. For convicine on the other hand, position 5 is blocked by the O-gucosidic bond and the addition of the OH radical could take place only at position 6. Thus, a single intermediate is formed and its decay is a single-phase one. It has been shown that although free radicals could not be detected in the course of the reactions between isouramil and oxygen or with cellular components by electron paramagnetic resonance, isouramil can participate in a uni-electron transfer reacton and can form relatively stable intermediates. Thus, it is speculated that in the red blood cells isouramil could give rise to deleterious free radicals.

  6. Superoxide radical anion scavenging and dismutation by some Cu2+ and Mn2+ complexes: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Joshi, Ravi

    2017-10-01

    Copper (Cu) and manganese (Mn) ions are catalytic centers, in complexed form, in scavenging and dismutation process of superoxide radicals anion (O2.-) by superoxide dismutase enzyme. In the present work, fast reaction kinetics and mechanism of scavenging and dismutation of O2.- by Cu2+, Mn2+ and their complexes formed with some natural ligands have been studied using pulse radiolysis technique. Catechol, gentisic acid, tetrahydroxyquinone, tyrosine, tryptophan, embelin and bilirubin have been used as low molecular weight natural ligands for Cu2+ and Mn2+ to understand superoxide radical scavenging and dismutation reactions. These complexes have been found to be efficient scavengers of O2.- (k 107-109 M-1 s-1). The effects of nature of metal ion and ligand, and stoichiometry of complex on scavenging reaction rate constants are reported. Higher scavenging rate constants have been observed with complexes of: (1) Cu2+ as compared to Mn2+, and (2) at [ligand]/[metal] ratio of one as compared to two. A clear evidence of O2.- dismutation by free metal ions and some of the complexes has been observed. The study suggests that complexes of Cu2+ and Mn2+ with small natural ligands can also act as SOD mimics.

  7. Examination of the formation process of pre-solvated and solvated electron in n-alcohol using femtosecond pulse radiolysis

    NASA Astrophysics Data System (ADS)

    Toigawa, Tomohiro; Gohdo, Masao; Norizawa, Kimihiro; Kondoh, Takafumi; Kan, Koichi; Yang, Jinfeng; Yoshida, Yoichi

    2016-06-01

    The formation process of pre-solvated and solvated electron in methanol (MeOH), ethanol (EtOH), n-butanol (BuOH), and n-octanol (OcOH) were investigated using a fs-pulse radiolysis technique by observing the pre-solvated electron at 1400 nm. The formation time constants of the pre-solvated electrons were determined to be 1.2, 2.2, 3.1, and 6.3 ps for MeOH, EtOH, BuOH, and OcOH, respectively. The formation time constants of the solvated electrons were determined to be 6.7, 13.6, 22.2, and 32.9 ps for MeOH, EtOH, BuOH, and OcOH, respectively. The formation dynamics and structure of the pre-solvated and solvated electrons in n-alcohols were discussed based on relation between the obtained time constant and dielectric relaxation time constant from the view point of kinetics. The observed formation time constants of the solvated electrons seemed to be strongly correlated with the second component of the dielectric relaxation time constants, which are related to single molecule motion. On the other hand, the observed formation time constants of the pre-solvated electrons seemed to be strongly correlated with the third component of the dielectric relaxation time constants, which are related to dynamics of hydrogen bonds.

  8. One-electron oxidation of ergothioneine and analogues investigated by pulse radiolysis: redox reaction involving ergothioneine and vitamin C.

    PubMed Central

    Asmus, K D; Bensasson, R V; Bernier, J L; Houssin, R; Land, E J

    1996-01-01

    Redox reactions of endogenous and exogenous sulphur-containing compounds are involved in protection against oxidative damage arising from the incidence and/or treatment of many diseases, including cancer. We have investigated, via pulse radiolysis, the one-electron oxidation of ergothioneine, a molecule with antioxidant properties which is detected at millimolar concentrations in certain tissues and fluids subject to oxidative stress, including erythrocytes and plasma. The spectrum of the transient species, assigned to the product of one-electron oxidation, observed after reaction of ergothioneine with the oxidizing radicals OH., N3. and CCl3O2. has a maximum absorption at 520 nm and is very similar to that obtained by oxidation of analogous molecules such as 2-mercaptoimidazole, 1-methyl-2-mercaptoimidazole, S-methyl- and S,N-dimethyl-ergothioneine. In the presence of vitamin C, the oxidized form of ergothioneine is repaired by a rapid reduction (k = 6.3 x 10(8) M(-1).s(-1)) producing ascorbyl radicals. This co-operative interaction between ergothionine and ascorbate, similar to that previously observed between vitamin E and ascorbate, may contribute to essential biological redox protection. PMID:8615839

  9. Pulse radiolysis and steady-state analyses of the reaction between hydroethidine and superoxide and other oxidants

    PubMed Central

    Zielonka, Jacek; Sarna, Tadeusz; Roberts, Joan E.; Wishart, James F.; Kalyanaraman, B.

    2008-01-01

    Hydroethidine (HE) is a cell-permeable probe used for the intracellular detection of superoxide. Here we report the direct measurement of the rate constant between hydroethidine and superoxide radical anion using the pulse radiolysis technique. This reaction rate constant was calculated to be ca. 2·106 M-1s-1 in water:ethanol (1:1) mixture. The spectral characteristics of the intermediates indicated that the one-electron oxidation product of HE was different from the one-electron reduction product of ethidium (E+). The HPLC-electrochemical measurements of incubation mixtures containing HE and the oxygenated Fenton’s reagent (Fe2+/DTPA/H2O2) in the presence of aliphatic alcohols or formate as a superoxide generating system revealed 2-OH-E+ as a major product. Formation of 2-OH-E+ by the Fenton’s reagent without additives was shown to be superoxide dismutase-sensitive and we attribute the formation of superoxide radical anion to the one-electron reduction of oxygen by the DTPA-derived radical. Addition of tert-butanol, DMSO, and potassium bromide to the Fenton’s system caused inhibition of 2-OH-E+ formation. Results indicate that reducing and oxidizing radicals have differential effects on the formation of 2-OH-E+. PMID:17081495

  10. In stationary regime, electron transfer rates in RTIL media are diffusion controlled: experimental evidence from pulse radiolysis study.

    PubMed

    Manna, Biswajit; Ghosh, Rajib; Palit, Dipak K

    2013-05-02

    We report electron transfer (ET) process from the long-lived radical anions of pyrene and benzophenone to molecular acceptors, e.g., benzophenone and fluorenone, respectively, in two RTIL media, namely, [BMIM][PF6] and [BMIM][BF4], as well as a few other conventional organic solvents using the nanosecond pulse radiolysis technique. Decay of the donor radical anion and concomitant formation of the acceptor radical anion ensure a bimolecular ET process. The rate constants for the bimolecular ET process in both normal organic solvents and RTILs have been found to be nearly equal to diffusion controlled rate calculated for the corresponding solvent. For long-lived anions, having lifetimes longer than a few hundred nanoseconds, quenching occurs mainly in the stationary regime. In this regime, the ET rate is fully controlled by the rate of diffusion of the reactive species in those solvents. To the best of our knowledge, this is the first experimental evidence of the diffusion controlled ET process occurring in the stationary regime in RTIL media.

  11. Antioxidant activity and free radical scavenging reactions of gentisic acid: in-vitro and pulse radiolysis studies.

    PubMed

    Joshi, Ravi; Gangabhagirathi, R; Venu, S; Adhikari, S; Mukherjee, T

    2012-01-01

    Abstract Antioxidant activity of gentisic acid has been studied using fast chemical kinetics and two in vitro models, namely the isolated rat liver mitochondria (RLM) and the human erythrocytes. The presence of gentisic acid (GA) during irradiation significantly reduced the levels of gamma radiation induced damages to lipids and proteins in RLM. Further, GA imparted protection to the human erythrocytes against exposure to gamma radiation. Molecular mechanism of free radical scavenging reactions has been evaluated with the help of rate constants and transients obtained from gentisic acid using pulse radiolysis technique. GA efficiently scavenged hydroxyl radical (k = 1.1 × 10(10) dm(3)mol(-1)s(-1)) to produce reducing adduct radical (~76%) and oxidizing phenoxyl radical (~24%). GA has also scavenged organohaloperoxyl radical (k = 9.3 × 10(7) dm(3) mol(-1)s(-1)). Ascorbate has been found to repair phenoxyl radical of GA (k = 1.0 × 10(7) dm(3)mol(-1)s(-1)). Redox potential value of GA(•)/GA couple (0.774 V vs NHE) obtained by cyclic voltammetry is less than those of physiologically important oxidants, which supports the observed antioxidant capacity of GA. We, therefore, propose that the antioxidant and radioprotective properties of GA are exerted by its phenoxyl group. © 2012 Informa UK, Ltd.

  12. Proton Transfer of Guanine Radical Cations Studied by Time-Resolved Resonance Raman Spectroscopy Combined with Pulse Radiolysis.

    PubMed

    Choi, Jungkweon; Yang, Cheolhee; Fujitsuka, Mamoru; Tojo, Sachiko; Ihee, Hyocherl; Majima, Tetsuro

    2015-12-17

    The oxidation of guanine (G) is studied by using transient absorption and time-resolved resonance Raman spectroscopies combined with pulse radiolysis. The transient absorption spectral change demonstrates that the neutral radical of G (G(•)(-H(+))), generated by the deprotonation of G radical cation (G(•+)), is rapidly converted to other G radical species. The formation of this species shows the pH dependence, suggesting that it is the G radical cation (G(•+))' formed from the protonation at the N7 of G(•)(-H(+)). On one hand, most Raman bands of (G(•+))' are up-shifted relative to those of G, indicating the increase in the bonding order of pyrimidine (Pyr) and imidazole rings. The (G(•+))' exhibits the characteristic CO stretching mode at ∼1266 cm(-1) corresponding to a C-O single bond, indicating that the unpaired electron in (G(•+))' is localized on the oxygen of the Pyr ring.

  13. Kinetics and mechanism of superoxide radical reactions with some biologically important compounds in aqueous solutions. Pulse radiolysis

    NASA Astrophysics Data System (ADS)

    Revina, A. A.; Amiragova, M. I.; Volod'ko, V. V.; Vannikov, A. V.

    Microsecond pulse radiolysis of oxygenated aqueous solutions containing 0.02 mol dm -3 sodium formate and 2 mmol dm -3 phosphate buffer at pH 7 was used to generate superoxide anion radicals. The influence of some biologically important compounds upon the rate of O ⨪2 decay was monitored spectrophotometrically in the range of 245-300 nm. Hematoporphyrin (HP), hemin C (HC), catalase (Cat), cobalt sulfophthalocyanine (CoTSPc) were studied. Among the investigated compounds only Cat was found to show a high catalytic efficiency towards the self-decay of O ⨪2. A red shift of O ⨪2 absorption band and slowing down of its decay were observed to take place by adding HP or CoTSPc to the solutions containing formate ions in excess. This effect is associated with the formation of a transient superoxo-complex. An appearance of an intermediate species with absorption maxima at 350 nm and half-life of about 2s was observed to accompany the superoxo-complex of CoTSPc decay. In the aerated solution of HP the intensity of absorbance at 260 nm was found to be independent of the presence of formate ions.

  14. Pulse radiolysis study on the rutin and quercetin anions formation and their behaviours in N 2-saturated ethanol solution

    NASA Astrophysics Data System (ADS)

    Sun, Gang; Wang, Wenfeng; Wu, Jilan

    1999-07-01

    The reactions of solvated electron with rutin and quercetin in N 2-saturated ethanol solution have been studied by pulse radiolysis and γ-radiolysis. The results show that solvated electron can add to rutin and quercetin and produce corresponding radical anions which show a maximum UV absorbance band at 430 and 420 nm. The ɛ max of radical anions of rutin and quercetin are 3.5×10 3 mol -1 dm 3 cm -1 and 5.5×10 3 mol -1 dm 3 cm -1, respectively. The rate constants of build-up of radical anions of rutin and quercetin are 7.5(±0.9)×10 9 mol -1 dm 3 s -1 and 7.7(±0.6)×10 9 mol -1 dm 3 s -1, respectively. The decay of radical anions is induced by the protonation which contains a pseudo-first-order reaction and a second-order reaction. For the radical anion of rutin, the rate constants of decay are 1.1(±0.1)×10 4 s -1 and 2.7(±0.2)×10 9 mol -1 dm 3 s -1, respectively. For the radical anion of quercetin, the rate constants of decay are 1.5(±0.1)×10 4 s -1 and 4.0(±0.5)×10 9 mol -1 dm 3 s -1, respectively. The electron transfer between radical anions and acetaldehyde can occur at the rate constants of 8.9(±1.2)×10 7 mol -1 dm 3 s -1 for radical anion of rutin and 1.2(±0.1)×10 8 mol -1 dm 3 s -1 for radical anion of quercetin. The rate constants of their corresponding counter-reactions are 5.7(±0.8)×10 7 mol -1 dm 3 s -1 and 2.0(±0.6)×10 7 mol -1 dm 3 s -1, respectively. The equilibrium constants of electron transfer reactions are 1.6 and 6.0, respectively. The standard electrode potential of radical anions of rutin and quercetin are obtained to be -1.94 and -1.98 V.

  15. Pulse-radiolysis studies on the interaction of one-electron-reduced species with ascorbate oxidase in aqueous solution.

    PubMed Central

    O'Neill, P; Fielden, E M; Finazzi-Agrò, A; Avigliano, L

    1983-01-01

    The interaction of e-aq., CO2-. and one-electron reduced nitroaromatics (RNO2-.) with ascorbate oxidase (AAO) was studied in aqueous solution at pH 6.0 and 7.5 by using the technique of pulse radiolysis. From observations at 330, 410 and 610 nm, interaction of e-aq. and CO2-. with AAO results in non-specific reduction of the protein followed by reduction of Type 1 Cu in a rate-determining intramolecular step. Only a few per cent of the reducing equivalents ultimately results in reduction of Type 1 Cu. With large excesses of reducing equivalents (e-aq. and CO2-.) with respect to the copper concentration, the amount of Type 1 copper reduced never exceeds 50% of the total amount of Type 1 copper after a single radiation pulse. With less-powerful reducing agents, e.g. RNO2-. reduction of Type 1 Cu occurs via a bimolecular step, and there is no evidence for formation of radicals on protein residues. From observations at 330 nm it is evident that Type 2 and/or Type 3 Cu may also be reduced along with Type 1 Cu. Almost stoichiometric reduction of AAO by RNO2-. was observed, e.g. the protein accepts 6-7 reducing equivalents. It is inferred that the various types of redox couples Cu2+/Cu+ are in equilibrium and that intramolecular electron transfer between the different types of Cu is not rate-determining when using RNO2-. as reducing agent. PMID:6405732

  16. Design of a high pressure system for pulse radiolysis studies up to 400 MPa with flow regulation

    NASA Astrophysics Data System (ADS)

    NGuyen Le, D.-T.; Pin, S.; Anjoure, D.; Chopineau, P.; Baldacchino, G.

    2013-03-01

    This article reports details of a new setup including an optical flow cell and devices which can increase pressure up to 400 MPa by controlling the ramp rate. It is composed of two high pressure syringe pumps which can make liquids flowing up to 4 cm3/mn. The optical flow cell can contains aqueous solutions and allow carry out pulse radiolysis experiments with a pulsed 10-MeV electron beam by performing in situ and time resolved optical analysis, such as transient UV-visible absorption or fluorescence spectroscopy. A Labview-program has been developed to drive and monitor automatons which regulate pressure, make solution flow under pressure, carry out operations such as filling, emptying or cleaning the system under safe conditions. Two results are exhibited: 1/associated to phosphate buffer, the fluorescence spectrum of the fluorescein pH-sensor has been performed under pressure. Phosphate pKa is confirmed to be very sensitive to pressure increase even up to 300 MPa. 2/a time-resolved absorption spectroscopy of hydrated electron in deaerated water has been conducted up to 350 MPa with a continuous flow of sample. In presence of tertio-butanol and bisTris pH7-buffer in solution, the spectral shift of hydrated electron is finely reproduced. BisTris is also confirmed as insensitive buffer under high pressure and its reduction by hydrated electron remains constant with a rate constant of (4.6 ± 0.6) × 108 M-1 s-1.

  17. OH-radical induced degradation of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and 4-chloro-2-methylphenoxyacetic acid (MCPA): A pulse radiolysis and gamma-radiolysis study

    NASA Astrophysics Data System (ADS)

    Zona, Robert; Solar, Sonja; Sehested, Knud

    2012-02-01

    The reactions of rad OH, H rad and e aq- with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and 4-chloro-2-methylphenoxyacetic acid (MCPA) were studied by pulse radiolysis. The site of rad OH-radicals addition to the aromatic ring of 2,4,5-T was found to be—C1: ˜18%, C2/C4/C5: total ˜28% and C3/C6: total ˜41%. The overall rate constants with OH-radicals were k( rad OH+2,4,5-T)=6.4 (±0.5)×10 9 mol dm -3 s -1 and k( rad OH+MCPA)=8.5 (±0.8)×10 9 mol dm -3 s -1. The radiation induced decomposition of the pesticides, chloride- and product formation (phenolic compounds, aliphatic acids) was studied by gamma radiolysis as a function of dose. A mechanism for acetate formation is discussed. The presence of oxygen during irradiation affected the decomposition rate only indiscernibly, however, chloride elimination, ring fragmentation (formation of aliphatic acids), TOC- and toxicity reduction were strongly enhanced. For complete removal of 500 μmol dm -3 herbicides a dose of ˜4 kGy was required. Using air saturation during irradiation a reduction of 37-40% of the TOC was observable at 5 kGy, detoxification (luminescence inhibition <20%) was achieved with 10 kGy.

  18. Radiolysis of herbs

    NASA Astrophysics Data System (ADS)

    Jilan, Wu; Xujia, Zhang; Rongyao, Yuan; Yongke, He

    1995-08-01

    Radiolysis of 124 types of herbs was studied. The majority were stable under γ-irradiation with absorbed dose up to 10 kGy. Radiolytic decomposition was detected at 10 kGy for 16 types of herbs (12.9%) and at 5 kGy for 6 types (4.8%). No detectable radiolytic decomposition was found at <2 kGy. The model system study showed: 1, γ-radiolysis is different from thermohydrolysis and photolysis; 2, water adsorbed on herbs evidently affects the radiolytic decomposition of herbs. Pulse and γ-radiolysis of baicalin, 1,8-dihydroxyanthraquinone-β- D-glycoside, glycyrrhizin and corydalic-B showed that some new compounds were formed due to the attack of OH radical. The addition of fructose and glucose can inhibit the γ-radiolytic decomposition of herbs. Chemical clearance displays fruitful and hopeful prospect to disinfect herbs by γ-ray, but important measure and step should be adopted. That is: 1, the herbs must exist in dry state; 2, it is preferred to make bolus by mixing powdered Chinese medicine and honey, as the latter can inhibit the radiolysis of herbs; 3, the producer must pay attention to executing strictly manufacture procedure to reduce the microbiological contamination, thus subsequently lower the applied dose.

  19. A pulse-radiolysis study of the catalytic mechanism of the iron-containing superoxide dismutase from Photobacterium leiognathi.

    PubMed

    Lavelle, F; McAdam, M E; Fielden, E M; Roberts, P B

    1977-01-01

    The mechanism of the enzymic reaction of an iron-containing superoxide dismutase purified from the marine bacterium Photobacterium leiognathi was studied by using pulse radiolysis. Measurements of activity were done with two different preparations of enzyme containing either 1.6 or 1.15 g-atom of iron/mol. In both cases, identical values of the second-order rate constant for reaction between superoxide dismutase and the superoxide ion in the pH range 6.2-9.0 (k=5.5 X 10(8) M-1-S-1 at pH 8.0) were found. As with the bovine erythrocuprein, there was no evidence for substrate saturation. The effects of reducing agents (H2O2, sodium ascorbate or CO2 radicals) on the visible and the electron-paramagnetic-resonance spectra of the superoxide dismutase containing 1.6 g-atom of ferric iron/mol indicate that this enzyme contains two different types of iron. Turnover experiments demonstrate that only that fraction of the ferric iron that is reduced by H2O2 is involved in the catalysis, being alternately oxidized and reduced by O2; both the oxidation and the reduction steps have a rate constant equal to that measured under turnover conditions. These results are interpreted by assuming that the superoxide dismutase isolated from the organism contains 1 g-atom of catalytic iron/mol and a variable amount of non-catalytic iron. This interpretation is discused in relation to the stoicheiometry reported for iron-containing superoxide dismutases prepared from several other organisms.

  20. Hydroxyl radical scavenging by carnosine and Cu(II)-carnosine complexes: a pulse-radiolysis and spectroscopic study.

    PubMed

    Tamba, M; Torreggiani, A

    1999-09-01

    To obtain a wider insight into the general properties of carnosine and to provide support to its anti-oxidative role. This property is hypothesized to be linked to various mechanisms including free-radical scavenging and metal chelation (i.e. Cu(II)). Pulse-radiolysis experiments were performed by a 12 MeV electron linear accelerator (LINAC) on carnosine/copper(II) (2:1) and carnosine aqueous solutions at different pH. Raman spectra of solid samples were obtained by a Bruker IFS 66 spectrometer. As well as for free carnosine, in the presence of copper ions the interaction of carnosine with *OH radicals involves the imidazole group of the molecule. The oxidation of copper (II)-carnosine system by *OH radicals is related to the pH-dependent structure of the copper(II)-carnosine complex. Raman spectra indicate that at alkaline pH the formation of a dimeric species containing two carnosine molecules complexed to two Cu2+ ions takes place. This structure can address the *OH attack more selectively than carnosine itself to different sites of the imidazole ring. The formation of at least two different *OH-radical adducts occurs and positions C(2) and C(5) of the imidazole ring are the preferential sites for the *OH attack, as the heterocyclic ring is mainly present as its N(1)-protonated tautomeric form. These studies provide further evidence about the formation of carnosine-copper complexes and the predominance of a dimeric structure at slightly basic pH. The chelation of Cu(II) is not detrimental to the scavenging ability of carnosine. Raman spectra are helpful in identifying the structure of the copper(II)-carnosine complexes and in predicting the preferential sites for the *OH attack to the carnosine-copper system.

  1. Photoreduction of oxoisoaporphines by amines: laser flash and steady-state photolysis, pulse radiolysis, and TD-DFT studies.

    PubMed

    De la Fuente, Julio R; Aliaga, Christian; Poblete, Cristian; Zapata, Gerald; Jullian, Carolina; Saitz, Claudio; Cañete, Alvaro; Kciuk, Gabriel; Sobarzo-Sanchez, Eduardo; Bobrowski, Krzysztof

    2009-07-09

    Photoreduction of oxoisoaporphine (OIA) (1-aza-benzo-[de]anthracen-7-one) and its 5-methoxy (5-MeO-OIA) derivative by selected amines (two non-alpha-hydrogen-donating amines (1,4-diaza[2.2.2]-bicyclooctane (DABCO) and 2,2,6,6-tetramethylpiperidine (TMP)) and three alpha-hydrogen-donating amines (triethylamine (TEA), diethylmethylamine (DEMA), and dimethylethylamine (DMEA))) has been studied in deaerated neat acetonitrile solutions using laser flash and steady-state photolysis. The triplet excited states of OIA and 5-MeO-OIA are characterized by intense absorption maxima located at lambda(max) = 450 nm and lifetimes of 34.7 +/- 0.5 and 44.6 +/- 0.4 micros, respectively. In the presence of tertiary amines, both triplets are quenched with a rate constant that varies from the near diffusion limit (>10(9) M(-1) s(-1)) to a rather low value (approximately 10(7) M(-1) s(-1)) and shows the expected dependence on the reduction potential for one-electron-transfer reactions. The transient absorption spectra observed after quenching of the respective triplet states are characterized by distinct absorption maxima located at lambda(max) = 480 and 490 nm (for OIA and 5-MeO-OIA, respectively) and accompanied by broad shoulders in the range of 510-560 nm. They were assigned to either solvent-separated radical ion pairs and/or isolated radical anions. In the presence of alpha-hydrogen-donating amines these species undergo protonation that leads to the formation of neutral hydrogenated radicals A1H(*)/A2H(*) with two possible sites of protonation, N and O atoms. Pulse radiolysis and molecular modeling together with TD-DFT calculations were used to support the conclusions about the origin of transients.

  2. Yields and decay kinetics of the solvated electron in pulse radiolysis of 1-alkanols

    NASA Astrophysics Data System (ADS)

    Kalachandra, S.; Farhataziz; Foyt, David C.

    The products of the yields of the solvated electron in 1-alkanols, G(e alk-, and the extinction coefficient of e alk- at its absorption maximum, ɛ(e alk-) max, relative to the same product for the hydrated electron, G(e aq-)ɛ(e aq-) max, for a 60 nsec irradiation at room temperature are given in parentheses after the name of each 1-alkanol: methanol (0.38), ethanol (0.42), 1-propanol (0.33), 1-butanol (0.30), 1-pentanol (0.28), 1-hexanol (0.31), 1-heptanol (0.27), 1-octanol (0.29), 1-nonanol (0.26), and 1-decanol (0.24). The decay kinetics of e alk- after 60 or 400 nsec of pulse irradiation of 1-alkanols, C 1-C 10, fit competitive pseudo-first order and second order (initial concentrations of both reactants the same) processes. Except for 1-propanol to 1-pentanol, the observed second order specific rates are a function of the dose per pulse. A mechanism is proposed for the above given decay kinetics of e alk- in C 1C 10 1-alkanols.

  3. Picosecond Pulse Radiolysis of Propylene Carbonate as a Solute in Water and as a Solvent.

    PubMed

    Marignier, Jean-Louis; Torche, Fayçal; Le Caër, Sophie; Mostafavi, Mehran; Belloni, Jacqueline

    2016-03-10

    The ester propylene carbonate (PC) is a solvent with a high static dielectric constant where the charges generated by ionizing radiation are expected to be long-lived at room temperature. Time-resolved optical absorption spectroscopy after picosecond electron pulses reveals the formation of a UV band, within less than two nanoseconds, that is assigned to the radical anion PC(-•), arising from a fast attachment reaction of electrons onto PC. Assignment and reactivity of PC(-•) in neat solvent and solutions are discussed in relation with data obtained in solutions of PC in water under reducing or oxidizing conditions and in solutions in PC of aromatic scavengers with various reduction potentials. The fate of the electrons and the ionization yield in PC are compared with those of other solvents.

  4. Dynamics of radical cations of poly(4-hydroxystyrene) in the presence and absence of triphenylsulfonium triflate as determined by pulse radiolysis of its highly concentrated solution

    NASA Astrophysics Data System (ADS)

    Okamoto, Kazumasa; Ishida, Takuya; Yamamoto, Hiroki; Kozawa, Takahiro; Fujiyoshi, Ryoko; Umegaki, Kikuo

    2016-07-01

    Pulse radiolysis of highly concentrated poly(4-hydroxystyrene) (PHS) solutions in cyclohexanone and p-dioxane was performed both with and without an onium-type photoacid generator (PAG). With increasing PHS concentration, the rate constant of deprotonation of PHS radical cations was found to decrease. In the presence of PAG, the yield of the multimer radical cation of PHS was shown to decrease. We found that pairing between the anions produced by the attachment of dissociative electrons of PAGs and the monomer PHS radical cations restrict local molecular motions, leading to the formation of the multimer PHS radical cations.

  5. Measuring hydrogen peroxide due to water radiolysis using a modified horseradish peroxidase based biosensor as an alternative dosimetry method.

    PubMed

    Tavakoli, Hassan; Baghbanan, Amin Azam

    2015-08-01

    H2O2 generated during water radiolysis was measured electrochemically as an alternative dosimetry method. A biosensor was fabricated by immobilising modified horseradish peroxidase (HRP) on a glassy carbon electrode (GCE) followed by evaluation of its analytical parameters. Anthraquinone 2-carboxylic acid was used to modify HRP. To assess sensor performance, phosphate buffer solutions were irradiated with 0.510 Gy of gamma ray emitted from (60)Co. The results showed that this sensor can detect low quantities of hydrogen peroxide in water radiolysis. Sensitivity, detection limit and linear range of the biosensor were 260 nA/Gy, 0.392 Gy and 0.5-5 Gy, respectively. Long term stability studies showed that sensor responses were stable for at least a month. The cathodic peak current, as biosensor response, subsequently decreased to 20% of its initial value.

  6. Kinetic and spectral studies on transient species formed in pulse radiolysis of 2,6-diacetylpyridine in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Naik, D. B.; Mukherjee, T.

    2006-01-01

    Reactions of e -aq, rad OH radicals, H-atoms and reducing (CH 3) 2C rad OH/CO 2rad - radicals with 2,6-diacetylpyridine were studied using pulse radiolysis technique in aqueous solutions. At pH 9.2, e -aq reaction with 2,6-DAP ( k=2.1×1010 dm mol s) was found to generate a transient species having absorption maxima at 320 and 420 nm. Reaction of e -aq with 2,6-DAP was also studied at pH˜13.3. Semi-reduced species formed at pH˜13.3 were found to transfer electron to methyl viologen with 100% efficiency ( k=2.9×109 dm mol s), whereas at pH 9.2 an equilibrium was attained. Making use of this equilibrium, the one-electron reduction potential of 2,6-DAP has been estimated to be -0.513 V vs. NHE at pH 9.2. Following the change in absorption spectra of semi-reduced species at pH 9.2 and ˜13.3, p Ka for the protonation of 2,6-DAP radical anion (2,6-DAP rad - /2,6-DAPH rad ) has been determined to be ˜11.9. Acetone ketyl radicals were found to transfer electron to 2,6-DAP with rate constants of 2×10 9, 6.3×10 7 and 1.2×108 dm mol s at pHs˜13.3, 9.2 and 1, respectively. By making use of the changes in the absorbance of species formed in reaction with acetone ketyl radicals with 2,6-DAP, p Ka for the protonation of 2,6-DAPH rad (2,6-DAPH rad /2,6-DAPH 2rad + ) has been estimated to be ˜1.5. H-atoms were found to react with 2,6-DAP by addition pathway rather than electron transfer. rad OH radical reaction with 2,6-DAP ( k=1.8×109 dm mol s) at pH 9.2 was found to generate transient species having absorption maxima at 310 and 400 nm. At pH 1 also, the spectrum of the species formed in rad OH radical reaction with 2,6-DAP was similar to that formed at pH 9.2 whereas reaction of O rad - radicals with 2,6-DAP ( k=1.8×109 dm mol s) generated a transient species whose absorption spectrum was different.

  7. A new approach to the study of intramolecular electron-transfer reactions of metalloproteins: Pulse radiolysis of NO[sub 2]-modified tyrosine derivatives of plastocyanin

    SciTech Connect

    Govindaraju, K.; Christensen, H.E.M.; Lloyd, E.; Tomkinson, N.P.; Sykes, A.G. ); Olsen, M. ); Salmon, G.A. )

    1993-01-06

    Single NO[sub 2]-modified derivatives of plastocyanin, with modifications at Tyr83 (spinach) and Tyr83/Tyr62 (parsley, deletions at 57 and 58), have been prepared and characterized by peptide mapping. All three products give a TyrNO[sub 2] UV-vis absorbance band at 355 nm ([epsilon] = 3,900 M[sup [minus]1] cm[sup [minus]1]) at pH < 7.5, assigned to NO[sub 2], which shifts to 428 nm on increasing the pH to > 9.0 due to acid dissociation of the phenolic group. Pulse radiolysis experiments in which the reductant CO[sub 2][sup [sm bullet][minus

  8. The use of the methods of radiolysis to explore the mechanisms of free radical modifications in proteins.

    PubMed

    Houée-Levin, Chantal; Bobrowski, Krzysztof

    2013-10-30

    The method of radiolysis is based upon the interaction of ionising radiation with the solvent (water). One can form the same free radicals as in conditions of oxidative stress ((•)OH, O2(•)(-), NO2(•)…). Moreover, the quantity of reactive oxygen (ROS) or nitrogen (RNS) species formed in the irradiated medium can be calculated knowing the dose and the radiation chemical yield, G, thus this method is quantitative. The use of the method of radiolysis has provided a wealth of data, especially about the kinetics of the oxidation by various free radicals and their mechanisms, the identification of transients formed, their lifetimes and the possibility to repair them by the so-called antioxidants. In this review we have collected the most recent data about protein oxidation that might be useful to a proteomic approach. This article is part of a Special Issue entitled: Posttranslational Protein modifications in biology and Medicine. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Pulse measurement apparatus and method

    DOEpatents

    Marciante, John R.; Donaldson, William R.; Roides, Richard G.

    2011-10-25

    An embodiment of the invention is directed to a pulse measuring system that measures a characteristic of an input pulse under test, particularly the pulse shape of a single-shot, nano-second duration, high shape-contrast optical or electrical pulse. An exemplary system includes a multi-stage, passive pulse replicator, wherein each successive stage introduces a fixed time delay to the input pulse under test, a repetitively-gated electronic sampling apparatus that acquires the pulse train including an entire waveform of each replica pulse, a processor that temporally aligns the replicated pulses, and an averager that temporally averages the replicated pulses to generate the pulse shape of the pulse under test. An embodiment of the invention is directed to a method for measuring an optical or an electrical pulse shape. The method includes the steps of passively replicating the pulse under test with a known time delay, temporally stacking the pulses, and temporally averaging the stacked pulses. An embodiment of the invention is directed to a method for increasing the dynamic range of a pulse measurement by a repetitively-gated electronic sampling device having a rated dynamic range capability, beyond the rated dynamic range of the sampling device; e.g., enhancing the dynamic range of an oscilloscope. The embodied technique can improve the SNR from about 300:1 to 1000:1. A dynamic range enhancement of four to seven bits may be achieved.

  10. Effect of isopropyl alcohol on the surface localization and recombination of conduction-band electrons in Degussa P25 TiO sub 2. A pulse-radiolysis time-resolved microwave conductivity study. [Accelerated electrons

    SciTech Connect

    Warman, J.M.; Hass, M.P. de ); Pichat, P. ); Serpone, N. Concordia Univ., Montreal, Quebec )

    1991-10-31

    Conduction-band electrons, formed by pulse radiolysis of Degussa P25 TiO{sub 2} particles, have been monitored by time-resolved microwave conductivity and found to undergo equilibrium localization and eventual recombination at the particle surface. In the presence of isopropyl alcohol recombination is retarded due to surface hole scavenging. The particle bulk can then be pumped with mobile electrons, which survive for seconds.

  11. Lack of visible chromophore development in the pulse radiolysis oxidation of 5,6-dihydroxyindole-2-carboxylic acid oligomers: DFT investigation and implications for eumelanin absorption properties.

    PubMed

    Pezzella, Alessandro; Panzella, Lucia; Crescenzi, Orlando; Napolitano, Alessandra; Navaratnam, Suppiah; Edge, Ruth; Land, Edward J; Barone, Vincenzo; d'Ischia, Marco

    2009-05-15

    The structural factors underlying the peculiar optical properties and visible chromophore of eumelanin biopolymers are largely uncharted. It is known that synthetic eumelanins from 5,6-dihydroxyindole are black and display a featureless UV-visible absorption spectrum, whereas those from 5,6-dihydroxyindole-2-carboxylic acid (1) are lighter in color and exhibit a distinct band around 310 nm, but the origin of this difference has never been addressed in detail. Recently, we showed that 5,6-dihydroxyindole dimers generate on pulse radiolysis oxidation strongly absorbing transients with intense maxima in the 500-600 nm region, which have been attributed to planar extended quinone methide species. We now report the unexpectedly different behavior of three oligomers from 1, namely, the 4,4'-biindolyl 2, the 4,7'-biindolyl 3, and the 4,7':4',7''-terindolyl 4. Pulse radiolysis oxidation of 2-4 led initially to semiquinone intermediates exhibiting similar absorption maxima at 360-380 nm. Semiquinone absorption decay followed second-order kinetics (2k = 1.4 x 10(8), 3.2 x 10(8), and 1.4 x 10(8) M(-1) s(-1) for 2, 3, and 4, respectively) but did not lead to significant chromophore development in the visible region. Similar absorption traces were obtained from monomer 1. DFT calculations predicted 5,6-dihydroxyindolyl-5,6-indolequinone structures with significant dihedral twists across the interunit single bonds for the most stable two-electron oxidation products of 2 and 3. The computed absorption spectra consistently featured strong bands around 310 nm but little or no absorption in the visible region. It is suggested that the effective conjugation length in oligomeric/polymeric eumelanin components from 1 may be controlled by hindered rotation around inter-ring bonds preventing planarization of the continuous array of indole units. This may provide an explanation for the difference in the absorption properties of polymers from the two key eumelanin monomers.

  12. A pulse radiolysis investigation of the reactions of tributyl phosphate with the radical products of aqueous nitric acid irradiation.

    PubMed

    Mincher, Bruce J; Mezyk, Stephen P; Martin, Leigh R

    2008-07-17

    Tributyl phosphate (TBP) is the most common organic compound used in liquid-liquid separations for the recovery of uranium, neptunium, and plutonium from acidic nuclear fuel dissolutions. The goal of these processes is to extract the actinides while leaving fission products in the acidic, aqueous phase. However, the radiolytic degradation of TBP has been shown to reduce separation factors of the actinides from fission products and to impede the back-extraction of the actinides during stripping. As most previous investigations of the radiation chemistry of TBP have focused on steady state radiolysis and stable product identification, with dibutylphosphoric acid (HDBP) invariably being the major product, here we have determined room temperature rate constants for the reactions of TBP and HDBP with the hydroxyl radical [(5.00 +/- 0.05) x 10(9), (4.40 +/- 0.13) x 10(9) M(-1) s(-1)], hydrogen atom [(1.8 +/-0.2) x 10(8), (1.1 +/- 0.1) x 10(8) M(-1) s(-1)], nitrate radical [(4.3 +/- 0.7) x 10(6), (2.9 +/- 0.2) x 10(6) M(-1) s(-1)], and nitrite radical (<2 x 10 (5), <2 x 10(5) M(-1) s(-1)), respectively. These data are used to discuss the mechanism of TBP radical-induced degradation.

  13. Pulse radiolysis study of the formation and the reactivity of baicalin radical anion, and in comparison with rutin, quercetin and acyrlate ester radical anions in ethanol

    NASA Astrophysics Data System (ADS)

    Sun, Gang; Wang, Wenfeng; Wu, Jilan

    2007-06-01

    The reaction of solvated electrons with baicalin in N 2-saturated ethanol has been studied by pulse radiolysis. The results show that a solvated electron can add to baicalin and generate a baicalin radical anion with a maximum UV absorbance peak at 360 nm. Its molar extinction coefficient at this wavelength is 1.3×10 4 M -1 cm -1. The rate constant for the build-up of the baicalin radical anion is 1.3(±0.4)×10 10 M -1 s -1. Decay of the radical anion is induced by a proton transfer reaction and a recombination reaction, which involves a pseudo-first-order reaction with rate constant 2.6(±0.4)×10 3 s -1 and a second-order reaction with rate constant 1.3(±0.2)×10 9 M -1 s -1. The effect of acetaldehyde on the decay of the baicalin radical anion was also investigated. Electron transfer between the baicalin radical anion and acetaldehyde was not observed, probably due to the low rate of electron transfer between the baicalin radical anion and acetaldehyde. Reactivity of the rutin, quercetin, baicalin and ethyl acrylate radical anions are also compared.

  14. Temperature dependence of the rate constant for hydrogen atom reaction with Cl2-• in water by pulse radiolysis of aqueous HCl solution

    NASA Astrophysics Data System (ADS)

    Kazmierczak, L.; Szala-Bilnik, J.; Wolszczak, M.; Swiatla-Wojcik, D.

    2015-12-01

    The temperature dependence of the rate constant for the reaction of dichloride anion radical (Cl2- •) with atomic hydrogen (H•) in water up to 75 °C has been determined by pulse radiolysis of deaerated 0.1 M HCl solution. The room temperature value is (6.1±0.6)×109 M-1 s-1. The activation energy of (13.2±0.6) kJ mol-1 is less than 16.7 kJ mol-1, expected for the diffusion-controlled reaction. Based on the temperature dependence of the rate constant for the reactions H•+Cl2- • and H•+Cl2, derived in this work, and on that reported earlier (Szala-Bilnik et al., 2014) for Cl2- • + Cl2- • , we show that a value of (10±2) M-1 s-1 determined by Hartig and Getoff (1982) for k (H•+H2O) in water at 25 °C is overestimated by at least two orders of magnitude.

  15. Photoinduced chain reactions of alcohols in the presence of diphenyliodonium ion pairs with cyanometallates--steady state UV/visible spectroscopic and pulse radiolysis studies.

    PubMed

    Hennig, H; Brede, O; Billing, R; Schönewerk, J

    2001-05-18

    Diphenyliodonium ions (Ph2I+) form donor-acceptor ion pairs with suitable cyanometallates such as [Mo(CN)8]4-, [W(CN)8]4-, [Ru(CN)6]4- and [Os(CN)6]4-. Such ion pairs are characterized by new spectroscopic transitions due to second-sphere interactions between donor ([M(CN)x]4-, x=6, 8) and acceptor (Ph2I+) ions. Photochemical excitation of these ion-pair charge-transfer (IPCT) states leads to efficient electron transfer reactions that yield short-lived diphenyliodyl radicals (Ph2I*) and oxidized cyanometallates ([M(CN)x]3-). Diphenyliodyl radicals decay to iodobenzene and phenyl radicals. This very convenient source for generating phenyl radicals was applied to the photoinduced chain oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones, respectively. However, unexpected side reactions led to undesired chain-terminating reactions. Adduct formation of diphenyliodonium ions with alpha-hydroxyalkyl radicals was verified by pulse radiolysis studies. These relatively longlived adducts give rise to chain-terminating reactions because of interactions with [M(CN)x]4- complexes that lead to oxidized cyanometallates [M(CN)x]3- upon regeneration of the starting alcohols.

  16. Structural study of various substituted biphenyls and their radical anions based on time-resolved resonance Raman spectroscopy combined with pulse radiolysis.

    PubMed

    Choi, Jungkweon; Cho, Dae Won; Tojo, Sachiko; Fujitsuka, Mamoru; Majima, Tetsuro

    2015-02-05

    The structures of various para-substituted biphenyls (Bp-X; X = -OH, -OCH3, -CH3, -H, -CONH2, -COOH, and -CN) and their radical anions (Bp-X(•-)) were investigated by time-resolved resonance Raman spectroscopy combined with pulse radiolysis. The inter-ring C1-C1' stretching modes (ν6) of Bp-X were observed at ∼1285 cm(-1), whereas the ν6 modes of Bp-X(•-) with an electron-donating or -withdrawing substituent were significantly up-shifted. The difference (Δf) between the ν6 frequencies of Bp-X and Bp-X(•-) showed a significant dependence on the electron affinity of the substituent and exhibited a correlation with the Hammett substituent constants (σp). In contrast to Bp-H(•-) with a planar geometry, the theoretical and experimental results reveal that all Bp-X(•-) with an electron-donating or -withdrawing substituent have a slightly twisted structure. The twisted structure of Bp-X(•-) is due to the localization of the unpaired electron and negative charge density on one phenyl moiety in Bp-X(•-).

  17. Laser beam pulse formatting method

    DOEpatents

    Daly, Thomas P.; Moses, Edward I.; Patterson, Ralph W.; Sawicki, Richard H.

    1994-01-01

    A method for formatting a laser beam pulse (20) using one or more delay loops (10). The delay loops (10) have a partially reflective beam splitter (12) and a plurality of highly reflective mirrors (14) arranged such that the laser beam pulse (20) enters into the delay loop (10) through the beam splitter (12) and circulates therein along a delay loop length (24) defined by the mirrors (14). As the laser beam pulse (20) circulates within the delay loop (10) a portion thereof is emitted upon each completed circuit when the laser beam pulse (20) strikes the beam splitter (12). The laser beam pulse (20) is thereby formatted into a plurality of sub-pulses (50, 52, 54 and 56). The delay loops (10) are used in combination to produce complex waveforms by combining the sub-pulses (50, 52, 54 and 56) using additive waveform synthesis.

  18. Reactivity of H 2O 2 with radiation produced free radicals: Steady state radiolysis methods for estimating the rate constants

    NASA Astrophysics Data System (ADS)

    Kishore, Kamal; Moorthy, P. N.; Rao, K. N.

    A new steady state radiolysis method for the determination of the rate constants of reaction of H 2O 2 with solute radicals derived by reaction with radiation produced OH radicals is described. The values so obtained are comparable with the ones obtained by the method described by Soylemez and Balkas in the past. A method similar to the latter has been employed to determine the rate constant of reaction of H 2O 2 with solute radicals derived from e -aq reaction. In the case of the (CH 3) 2 COH radical which can be generated by either reaction of OH with isopropanol or e -aq with acetone, the three methods give values agreeing with each other within ± 15% (viz. 2.7 ± 0.4 × 10 5 dm 3 mol -1 s -1). The reaction of the solute radicals with H 2O 2 is considered in the light of known one-electron redox potentials, and the limitations of the applicability of the methods described here are discussed.

  19. Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection.

    PubMed

    Grills, David C; Farrington, Jaime A; Layne, Bobby H; Lymar, Sergei V; Mello, Barbara A; Preses, Jack M; Wishart, James F

    2014-04-16

    Using a new technique, which combines pulse radiolysis with nanosecond time-resolved infrared (TRIR) spectroscopy in the condensed phase, we have conducted a detailed kinetic and mechanistic investigation of the formation of a Mn-based CO2 reduction electrocatalyst, [Mn((t)Bu2-bpy)(CO)3]2 ((t)Bu2-bpy = 4,4'-(t)Bu2-2,2'-bipyridine), in acetonitrile. The use of TRIR allowed, for the first time, direct observation of all the intermediates involved in this process. Addition of excess [(n)Bu4N][HCO2] to an acetonitrile solution of fac-MnBr((t)Bu2-bpy)(CO)3 results in its quantitative conversion to the Mn-formate complex, fac-Mn(OCHO)((t)Bu2-bpy)(CO)3, which is a precatalyst for the electrocatalytic reduction of CO2. Formation of the catalyst is initiated by one-electron reduction of the Mn-formate precatalyst, which produces the bpy ligand-based radical. This radical undergoes extremely rapid (τ = 77 ns) formate dissociation accompanied by a free valence shift to yield the five-coordinate Mn-based radical, Mn(•)((t)Bu2-bpy)(CO)3. TRIR data also provide evidence that the Mn-centered radical does not bind acetonitrile prior to its dimerization. This reaction occurs with a characteristically high radical-radical recombination rate (2kdim = (1.3 ± 0.1) × 10(9) M(-1) s(-1)), generating the catalytically active Mn-Mn bound dimer.

  20. Pulse radiolysis and ultra-high-performance liquid chromatography/high-resolution mass spectrometry studies on the reactions of the carbonate radical with vitamin B12 derivatives.

    PubMed

    Dassanayake, Rohan S; Shelley, Jacob T; Cabelli, Diane E; Brasch, Nicola E

    2015-04-20

    The reactions of the carbonate radical anion (CO3 (.) (-) ) with vitamin B12 derivatives were studied by pulse radiolysis. The carbonate radical anion directly oxidizes the metal center of cob(II)alamin quantitively to give hydroxycobalamin, with a bimolecular rate constant of 2.0×10(9) M(-1) s(-1) . The reaction of CO3 (.) (-) with hydroxycobalamin proceeds in two steps. The second-order rate constant for the first reaction is 4.3×10(8) M(-1) s(-1) . The rate of the second reaction is independent of the hydroxycobalamin concentration and is approximately 3.0×10(3) s(-1) . Evidence for formation of corrinoid complexes differing from cobalamin by the abstraction of two or four hydrogen atoms from the corrin macrocycle and lactone ring formation has been obtained by ultra-high-performance liquid chromatography/high-resolution mass spectrometry (UHPLC/HRMS). A mechanism is proposed in which abstraction of a hydrogen atom by CO3 (.) (-) from a carbon atom not involved in the π conjugation system of the corrin occurs in the first step, resulting in formation of a Co(III) C-centered radical that undergoes rapid intramolecular electron transfer to form the corresponding Co(II) carbocation complex for about 50 % of these complexes. Subsequent competing pathways lead to formation of corrinoid complexes with two fewer hydrogen atoms and lactone derivatives of B12 . Our results demonstrate the potential of UHPLC combined with HRMS in the separation and identification of tetrapyrrole macrocycles with minor modifications from their parent molecule. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Reversible intramolecular hydrogen transfer between cysteine thiyl radicals and glycine and alanine in model peptides: absolute rate constants derived from pulse radiolysis and laser flash photolysis

    PubMed Central

    Nauser, Thomas; Casi, Giulio; Koppenol, Willem H.; Schöneich, Christian

    2008-01-01

    The intramolecular reaction of cysteine thiyl radicals with peptide and protein αC-H bonds represents a potential mechanism for irreversible protein oxidation. Here, we have measured absolute rate constants for these reversible hydrogen transfer reactions by means of pulse radiolysis and laser flash photolysis of model peptides. For N-Ac-CysGly6 and N-Ac-CysGly2AspGly3, Cys thiyl radicals abstract hydrogen atoms from Gly with kf = (1.0-1.1)×105 s-1, generating carbon-centered radicals, while the reverse reaction proceeds with kr = (8.0-8.9)×105 s-1. The forward reaction shows a normal kinetic isotope effect of kH/kD = 6.9, while the reverse reaction shows a significantly higher normal kinetic isotope effect of 17.6, suggesting a contribution of tunneling. For N-Ac-CysAla2AspAla3, cysteine thiyl radicals abstract hydrogen atoms from Ala with kf =(0.9-1.0)×104 s-1, while the reverse reaction proceeds with kr = 1.0×105 s-1. The order of reactivity, Gly > Ala, is in accord with previous studies on intermolecular reactions of thiyl radicals with these amino acids. The fact that kf < kr suggests some secondary structure of the model peptides, which prevents the adoption of extended conformations, for which calculations of homolytic bond dissociation energies would have predicted kf > kr. Despite kf < kr, model calculations show that intramolecular hydrogen abstraction by Cys thiyl radicals can lead to significant oxidation of other amino acids in the presence of physiologic oxygen concentrations. PMID:18973367

  2. Pulsed ultrasonic stir welding method

    NASA Technical Reports Server (NTRS)

    Ding, R. Jeffrey (Inventor)

    2013-01-01

    A method of performing ultrasonic stir welding uses a welding head assembly to include a plate and a rod passing through the plate. The rod is rotatable about a longitudinal axis thereof. In the method, the rod is rotated about its longitudinal axis during a welding operation. During the welding operation, a series of on-off ultrasonic pulses are applied to the rod such that they propagate parallel to the rod's longitudinal axis. At least a pulse rate associated with the on-off ultrasonic pulses is controlled.

  3. Mechanism of formation, spectrum and reactivity of half-reduced eight-iron Clostridium pasteurianum ferredoxin in pulse-radiolysis studies and the non-co-operativity of the four-iron clusters.

    PubMed Central

    Butler, J; Henderson, R A; Armstrong, F A; Sykes, A G

    1979-01-01

    Reduction of fully oxidized Clostridium pasteurianum 8-Feox.,ox. ferredoxin by using pulse-radiolysis techniques yields the half-reduced species 8-Feox.,red. ferredoxin. The subsequent oxidation of 8-Feox.,red. ferredoxin with Co(NH3)5Cl2+ was studied. From a comparison with stopped-flow studies on the 2:1 Co(NH3)5Cl2+ oxidation of 8-Fered.,red. ferredoxin to the 8-Feox.,ox. form it is concluded that there is no redox co-operativity between the two 4-Fe centres in these reactions. PMID:534509

  4. Chemical, pulse radiolysis and density functional studies of a new, labile 5,6-indolequinone and its semiquinone.

    PubMed

    Pezzella, Alessandro; Crescenzi, Orlando; Natangelo, Anna; Panzella, Lucia; Napolitano, Alessandra; Navaratnam, Suppiah; Edge, Ruth; Land, Edward J; Barone, Vincenzo; d'Ischia, Marco

    2007-03-02

    The chemical and spectroscopic characterization of 5,6-indolequinones and their semiquinones, key transient intermediates in the oxidative conversion of 5,6-dihydroxyindoles to eumelanin biopolymers, is a most challenging task. In the present paper, we report the characterization of a novel, relatively long-lived 5,6-indolequinone along with its semiquinone using an integrated chemical, pulse radiolytic, and computational approach. The quinone was obtained by oxidation of 5,6-dihydroxy-3-iodoindole (1a) with o-chloranil in cold ethyl acetate or aqueous buffer: it displayed electronic absorption bands around 400 and 600 nm, was reduced to 1a with Na2S2O4, and reacted with o-phenylenediamine to give small amounts of 3-iodo-1H-pyrrolo[2,3-b]phenazine (2). The semiquinone exhibited absorption maxima at 380 nm (sh) and 520 nm and was detected as the initial species produced by pulse radiolytic oxidation of 1a at pH 7.0. DFT investigations indicated the 6-phenoxyl radical and the N-protonated radical anion as the most stable tautomers for the neutral and anion forms of the semiquinone, respectively. Calculated absorption spectra in water gave bands at 350 (sh) and 500 nm for the neutral form and at 310 and 360 (sh) nm for the anion. Disproportionation of the semiquinone with fast second-order kinetics (2k = 1.1 x 1010 M-1 s-1) gave a chromophore with absorption bands resembling those of chemically generated 1a quinone. Computational analysis predicted 1a quinone to exist in vacuo as the quinone-methide tautomer, displaying low energy transitions at 380 and 710 nm, and in water as the o-quinone, with calculated absorption bands around 400 and 820 nm. A strong participation of a p orbital on the iodine atom in the 360-380 nm electronic transitions of the o-quinone and quinone-methide was highlighted. The satisfactory agreement between computational and experimental electronic absorption data would suggest partitioning of 1a quinone between the o-quinone and quinone

  5. Radiolysis of boiling water

    NASA Astrophysics Data System (ADS)

    Yang, Shuang; Katsumura, Yosuke; Yamashita, Shinichi; Matsuura, Chihiro; Hiroishi, Daisuke; Lertnaisat, Phantira; Taguchi, Mitsumasa

    2016-06-01

    γ-radiolysis of boiling water has been investigated. The G-value of H2 evolution was found to be very sensitive to the purity of water. In high-purity water, both H2 and O2 gases were formed in the stoichiometric ratio of 2:1; a negligible amount of H2O2 remained in the liquid phase. The G-values of H2 and O2 gas evolution depend on the dose rate: lower dose rates produce larger yields. To clarify the importance of the interface between liquid and gas phase for gas evolution, the gas evolution under Ar gas bubbling was measured. A large amount of H2 was detected, similar to the radiolysis of boiling water. The evolution of gas was enhanced in a 0.5 M NaCl aqueous solution. Deterministic chemical kinetics simulation elucidated the mechanism of radiolysis in boiling water.

  6. One-electron reduction of 9, 10-anthraquinone, 1-amino-9, 10-anthraquinone and 1-hydroxy-9, 10-anthraquinone in aqueous-isopropanol-acetone mixed solvent: A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Pal, H.; Mukherjee, T.; Mittal, J. P.

    1994-12-01

    The semiquinone radicals produced by one-electron reduction of 9, 10-anthraquinone, 1-amino-9, 10-anthraquinone and 1-hydroxy-9, 10-anthraquinone have been characterized in aqueous-organic mixed solvent comprising of 30.2 mol dm -3 water, 5 mol dm -3 isopropanol and 1 mol dm -3 acetone, using the pulse radiolysis technique. Spectroscopic characteristics, the kinetic parameters of formation and decay and one acid dissociation constants of the semiquinones and one-electron reduction potentials of the quinones have been estimated. The characteristics of the present semiquinone systems have been compared with those of other similar systems. The observed differences in characteristics of the semiquinones due to different substitutions have been analysed.

  7. Reactivity of hypotaurine and cysteine sulfinic acid toward carbonate radical anion and nitrogen dioxide as explored by the peroxidase activity of Cu,Zn superoxide dismutase and by pulse radiolysis.

    PubMed

    Baseggio Conrado, A; D'Angelantonio, M; Torreggiani, A; Pecci, L; Fontana, M

    2014-11-01

    Hypotaurine and cysteine sulfinic acid are known to be readily oxidized to the respective sulfonates, taurine and cysteic acid, by several oxidative agents that may be present in biological systems. In this work, the relevance of both the carbonate anion and nitrogen dioxide radicals in the oxidation of hypotaurine and cysteine sulfinic acid has been explored by the peroxidase activity of Cu,Zn superoxide dismutase (SOD) and by pulse radiolysis. The extent of sulfinate oxidation induced by the system SOD/H2O2 in the presence of bicarbonate (CO3(•-) generation), or nitrite ((•)NO2 generation) has been evaluated. Hypotaurine is efficiently oxidized by the carbonate radical anion generated by the peroxidase activity of Cu,Zn SOD. Pulse radiolysis studies have shown that the carbonate radical anion reacts with hypotaurine more rapidly (k = 1.1 × 10(9) M(-1)s(-1)) than nitrogen dioxide (k = 1.6 × 10(7) M(-1)s(-1)). Regarding cysteine sulfinic acid, it is less reactive with the carbonate radical anion (k = 5.5 × 10(7) M(-1)s(-1)) than hypotaurine. It has also been observed that the one-electron transfer oxidation of both sulfinates by the radicals is accompanied by the generation of transient sulfonyl radicals (RSO2(•)). Considering that the carbonate radical anion could be formed in vivo at high level from bicarbonate, this radical can be included in the oxidants capable of performing the last metabolic step of taurine biosynthesis. Moreover, the protective effect exerted by hypotaurine and cysteine sulfinate on the carbonate radical anion-mediated tyrosine dimerization indicates that both sulfinates have scavenging activity towards the carbonate radical anion. However, the formation of transient reactive intermediates during sulfinate oxidation by carbonate anion and nitrogen dioxide radical may at the same time promote oxidative reactions.

  8. Interfacial electron-transfer equilibria and flat-band potentials of. cap alpha. -Fe/sub 2/O/sub 3/ and TiO/sub 2/ colloids studied by pulse radiolysis

    SciTech Connect

    Dimitrijevic, N.M.; Savic, D.; Micic, O.I.; Nozik, A.J.

    1984-09-13

    The kinetics and equilibria of electron transfer between methylviologen cation radicals and ..cap alpha..-Fe/sub 2/O/sub 3/ or TiO/sub 2/ colloidal particles were studied with the pulse-radiolysis technique. The rates of electron transfer to both colloids are lower than those predicted for a diffusion-controlled reaction. For higher pHs (TiO/sub 2/, pH > 2; ..cap alpha..-Fe/sub 2/O/sub 3/, pH > 9) the established equilibrium MV/sup +/ in equilibrium MV/sup 2 +/ + (e/sup -/)/sub coll/ is strongly influenced by the MV/sup 2 +/ concentration and pH. The MV/sup +/ equilibrium concentration can be exploited to derive the flat-band potential of the semiconductor colloids. The method for determining the flat-band potential of the particles is independent of whether the injected electrons are free or trapped, and whether the electrons raise the bulk Fermi level toward the conduction band or just produce a space charge. The flat-band potentials for both colloids appear to be somewhat more negative (-0.1 to -0.2 V) than the corresponding single-crystal electrodes. Also, the flat-band potentials become slightly more negative with increasing radiation dose (initial MV/sup +/ concentration). The effect of absorbed radiation dose is explained by the corresponding changes in the ratio of oxidized to reduced forms of the redox couple, which in turn changes the adsorbed ionic charge on the semiconductor surface. For colloidal particles of TiO/sub 2/ stabilized by poly(vinyl alcohol) (PVA), the flat-band potentials were almost the same as those for PVA-free TiO/sub 2/ sols. The decrease of particle diameter from 800 to 70 A does not affect the value of the flat-band potentials for TiO/sub 2/ and ..cap alpha..-Fe/sub 2/O/sub 3/ colloids. 28 references, 9 figures.

  9. Magnetic Alignment of Pulsed Solenoids Using the Pulsed Wire Method

    SciTech Connect

    Arbelaez, D.; Madur, A.; Lipton, T.M.; Waldron, W.L.; Kwan, J.W.

    2011-04-01

    A unique application of the pulsed-wire measurement method has been implemented for alignment of 2.5 T pulsed solenoid magnets. The magnetic axis measurement has been shown to have a resolution of better than 25 {micro}m. The accuracy of the technique allows for the identification of inherent field errors due to, for example, the winding layer transitions and the current leads. The alignment system is developed for the induction accelerator NDCX-II under construction at LBNL, an upgraded Neutralized Drift Compression experiment for research on warm dense matter and heavy ion fusion. Precise alignment is essential for NDCX-II, since the ion beam has a large energy spread associated with the rapid pulse compression such that misalignments lead to corkscrew deformation of the beam and reduced intensity at focus. The ability to align the magnetic axis of the pulsed solenoids to within 100 pm of the induction cell axis has been demonstrated.

  10. Oxidation of amino-containing disulfides by Br/sub 2//sup -/ and OH: a pulse-radiolysis study. [1. 5 MeV electrons

    SciTech Connect

    Elliot, A.J.; McEachern, R.J.; Armstrong, D.A.

    1981-01-08

    The rate constant for reaction of Br/sub 2/ radicals with dithiodipropionic acid (approx. 4.2 x 10/sup 8/ mol/sup -1/dm/sup 3/s/sup -1/) was independent of pH in the range 6.6-11.0 and was approx. 4.5 times smaller than those for the neutral dimethyl and diethyl disulfides Br/sub 2//sup -/ only reacted with the disulfides of cysteamine, cysteine, and penicillamine with an appreciable rate (> 10/sup 8/mol/sup -1/dm/sup 3/s/sup -1/) when one or both of the amino groups were unprotonated. Homocystine was less sensitive to the degree of protonation. While the reaction of Br/sub 2/ radicals with dithiodipropionic acid yielded a transient (lambda/sub max/ approx. = 450 nm) which possessed the characteristics of a disulfide cation, the amino-containing disulfides cited above produced transients which adsorbed with a lambda/sub max/ near 380 nm. The latter transients decayed by second-order kinetics over the pH range studied, and they gave no evidence of reaction with OH/sup -/. These species have been tentatively identified as perthiyl (RSS.) radicals. Hydroxyl radicals produced composite spectra consisting of the 380-nm species and other transients which absorbed below 350 nm. Oxidized glutathione gave only weak absorptions on reaction with Br/sub 2/ and OH radicals. The yields of sulfydryl molecules have been measured for cystine and dithiodipropionic acid. The mechanisms of radiolysis are discussed in the light of present results and earlier studies.

  11. Radiolysis Process Model

    SciTech Connect

    Buck, Edgar C.; Wittman, Richard S.; Skomurski, Frances N.; Cantrell, Kirk J.; McNamara, Bruce K.; Soderquist, Chuck Z.

    2012-07-17

    Assessing the performance of spent (used) nuclear fuel in geological repository requires quantification of time-dependent phenomena that may influence its behavior on a time-scale up to millions of years. A high-level waste repository environment will be a dynamic redox system because of the time-dependent generation of radiolytic oxidants and reductants and the corrosion of Fe-bearing canister materials. One major difference between used fuel and natural analogues, including unirradiated UO2, is the intense radiolytic field. The radiation emitted by used fuel can produce radiolysis products in the presence of water vapor or a thin-film of water (including OH• and H• radicals, O2-, eaq, H2O2, H2, and O2) that may increase the waste form degradation rate and change radionuclide behavior. H2O2 is the dominant oxidant for spent nuclear fuel in an O2 depleted water environment, the most sensitive parameters have been identified with respect to predictions of a radiolysis model under typical conditions. As compared with the full model with about 100 reactions it was found that only 30-40 of the reactions are required to determine [H2O2] to one part in 10–5 and to preserve most of the predictions for major species. This allows a systematic approach for model simplification and offers guidance in designing experiments for validation.

  12. A pulse-radiolysis study on the kinetics of reaction of PW{sub 12}O{sub 40}{sup 4{minus}} heteropolytungstate blue with Np(VI) ions in aqueous acid solutions

    SciTech Connect

    Gogolev, A.V.; Shilov, V.P.; Fedoseev, A.M.

    1994-11-01

    Data on the kinetics of redox reactions with the participation of heteropoly compounds may be of interest in photochemistry, radiation chemistry, catalysis, and other branches of physical chemistry. The structure of heteropoly blues is the same as that of the initial heteropoly compounds. Because of this, the oxidation of blues by metal ions can proceed quite readily. Presently, data on the interaction of blues with 5f-element ions is lacking. As a part of a systematic study on the reactivity of free radicals and excited species to actinide ions, the authors used a pulse-radiolysis technique to determine the rate constant of the reaction: Np(VI) + PW{sub 12}O{sub 40}{sup 4{minus}} {yields} Np(V) + PW{sub 12}O{sub 40}{sup 3{minus}}, k{sub 1} = ? The ions of Np(VI) were chosen as oxidizing agents because of their relatively high redox potential (1.13 V), and the resemblance of the structure of Np(VI) and Np(V) ions.

  13. Radiolysis of berberine or palmatine in aqueous solution

    NASA Astrophysics Data System (ADS)

    Marszalek, Milena; Wolszczak, Marian

    2011-01-01

    The reactions of hydrated electron (eaq-), hydrogen atom (H rad ) (reducing species) and Cl2•-, Br2•-, N,O•H radicals (oxidizing species) with berberine or palmatine in aqueous solution have been studied by steady-state and pulse radiolysis. The spectra of transient intermediates, leading to the final products, are presented. The rate constants of the reaction of eaq- and rad OH radical with both alkaloids in the homogenous solution and in the presence of DNA are reported. It is demonstrated that the primary products of the reaction of berberine and palmatine with eaq- and radicals generated during radiolysis are unstable and undergo further reactions.

  14. Reaction mechanisms in the radiolysis of peptides, polypeptides and proteins

    SciTech Connect

    Garrison, W.M.

    1985-01-01

    The purpose of this review is to bring together and to correlate the wide variety of experimental studies that provide information on the reaction products and reaction mechanisms involved in the radiolysis of peptides, polypeptides and proteins (including chromosomal proteins) in both aqueous and solid-state systems. The comparative radiation chemistry of these systems is developed in terms of specific reactions of the peptide main-chain and the aliphatic, aromatic-unsaturated and sulfur-containing side-chains. Information obtained with the various experimental techniques of product analysis, competition kinetics, spin-trapping, pulse radiolysis and ESR spectroscopy is included. 147 refs.

  15. Pulsed Thrust Method for Hover Formation Flying

    NASA Technical Reports Server (NTRS)

    Hope, Alan; Trask, Aaron

    2003-01-01

    A non-continuous thrust method for hover type formation flying has been developed. This method differs from a true hover which requires constant range and bearing from a reference vehicle. The new method uses a pulsed loop, or pogo, maneuver sequence that keeps the follower spacecraft within a defined box in a near hover situation. Equations are developed for the hover maintenance maneuvers. The constraints on the hover location, pulse interval, and maximum/minimum ranges are discussed.

  16. Reduction potential of the sulfhydryl radical: Pulse radiolysis and laser flash photolysis studies of the formation and reactions of {sm_bullet}SH and HSSH{sm_bullet}{sup {minus}} in aqueous solutions

    SciTech Connect

    Das, T.N.; Huie, R.E.; Neta, P.; Padmaja, S.

    1999-07-08

    H{sub 2}S, which is a very toxic gas, has a large number of natural and anthropogenic sources, and the safe removal of this substance has been a matter of ongoing industrial concern. Formation and reactions of the {sm_bullet}SH/{sm_bullet}S{sup {minus}} and HSSH{sm_bullet}{sup {minus}}/HSS{sm_bullet}{sup 2{minus}} radicals in aqueous solutions have been studied by excimer laser flash photolysis and by pulse radiolysis. Acidic H{sub 2}S solutions can be photolyzed with 193 nm laser pulses and produce a transient species with {lambda}{sub max} at 240 nm, ascribed to the {sm_bullet}SH/{sm_bullet}S{sup {minus}} radical. Solutions of SH{sup {minus}} can be photolyzed also with 248 nm laser pulses to produce the {sm_bullet}SH/{sm_bullet}S{sup {minus}} reacts with SH{sup {minus}} ({kappa}{sub f} = 4 {times} 10{sup 9} L/mol s, {kappa}{sub r} = 5 {times} 10{sup 5} s{sup {minus}1}) to form HSSH{sm_bullet}{sup {minus}}/HSS{sm_bullet}{sup 2{minus}}, with {lambda}{sub max} at 380 nm. Both {sm_bullet}SH/{sm_bullet}S{sup {minus}} and HSSH{sm_bullet}{sup {minus}}/HSS{sm_bullet}{sup 2{minus}} react rapidly with O{sub 2}; the former produces SO{sub 2}{sm_bullet}{sup {minus}} ({kappa} = 5 {times} 10{sup 9} L/mol s), and the latter produces O{sub 2}{sm_bullet} ({kappa} = 4 {times} 10{sup 8} L/mol s). Both radicals react with olefinic compounds. The monomeric radical oxidizes Fe(CN){sub 6}{sup 4{minus}}, SO{sub 3}{sup 2{minus}}, ClO{sub 2}{sup {minus}}, and chlorpromazine. The dimeric radical is a weaker oxidant toward ferrocyanide but reduces N-methylpyridinium compounds. The reduction potential for the dimeric radical at pH 7 was determined from one-electron transfer equilibria with Mo(CN){sub 8}{sup 3{minus}} and with the 4-methoxyaniline radical cation and found to be 0.69 V vs NHE. From the equilibrium constant K = [HSS{sm_bullet}{sup 2{minus}}]/[SH{sup {minus}}][{sm_bullet}S{sup {minus}}] = 8 {times} 10{sup 3} L/mol, the reduction potential for ({sm_bullet}S{sup {minus

  17. Pulsed Electric Propulsion Thrust Stand Calibration Method

    NASA Technical Reports Server (NTRS)

    Wong, Andrea R.; Polzin, Kurt A.; Pearson, J. Boise

    2011-01-01

    The evaluation of the performance of any propulsion device requires the accurate measurement of thrust. While chemical rocket thrust is typically measured using a load cell, the low thrust levels associated with electric propulsion (EP) systems necessitate the use of much more sensitive measurement techniques. The design and development of electric propulsion thrust stands that employ a conventional hanging pendulum arm connected to a balance mechanism consisting of a secondary arm and variable linkage have been reported in recent publications by Polzin et al. These works focused on performing steady-state thrust measurements and employed a static analysis of the thrust stand response. In the present work, we present a calibration method and data that will permit pulsed thrust measurements using the Variable Amplitude Hanging Pendulum with Extended Range (VAHPER) thrust stand. Pulsed thrust measurements are challenging in general because the pulsed thrust (impulse bit) occurs over a short timescale (typically 1 micros to 1 millisecond) and cannot be resolved directly. Consequently, the imparted impulse bit must be inferred through observation of the change in thrust stand motion effected by the pulse. Pulsed thrust measurements have typically only consisted of single-shot operation. In the present work, we discuss repetition-rate pulsed thruster operation and describe a method to perform these measurements. The thrust stand response can be modeled as a spring-mass-damper system with a repetitive delta forcing function to represent the impulsive action of the thruster.

  18. Excited states and reduced and oxidized forms of a textile diazo dye, naphthol blue black. Spectral characterization using laser flash photolysis and pulse radiolysis studies

    NASA Astrophysics Data System (ADS)

    Nasr, Chouhaid; Vinodgopal, K.; Hotchandani, Surat; Chattopadhyay, A. K.; Kamat, Prashant V.

    1997-01-01

    The excited singlet and triplet states of a diazo textile dye (Naphthol Blue Black) have been investigated by pico and nanosecond flash photolysis. The excited singlet state shows a difference absorption maximum at 500 nm and has a lifetime of 25-30 ps in ethanol. The triplet excited state generated by triplet-triplet energy transfer shows an absorption maxima at 710-730 nm. The oxidized form as well as the reduced form of the diazo dye have been generated pulse radiolytically by reacting with azide and e aq radicals, respectively. Preliminary results of the photoelectrochemical irreversible reduction of Naphthol Blue Black in colloidal TiO 2 are also reported.

  19. Interaction of radicals from water radiolysis with melanin.

    PubMed

    Sarna, T; Pilas, B; Land, E J; Truscott, T G

    1986-08-06

    Melanins are considered to be natural photoprotectors in the melanocytes and keratinocytes of the skin. These pigments have also been suggested to play an important role in protection of melanin-containing cells against ionising radiation. Various mechanisms have been proposed to explain the protective role of melanin which invoke the radical scavenging properties of the polymer. In the present work the reactions of melanins with radicals generated in aqueous media by pulse radiolysis have been studied. Time-resolved changes in absorbance of the melanin or the radical species were recorded at selected wavelengths. Experiments were carried out on synthetic dopa- and 5-S-cysteinyldopa-melanins and a natural melanin in phosphate buffer (pH 7.4). Under the conditions employed, melanin reacted predominantly with either oxidising (OH., N3.) or reducing (eaq-, CO2-) species. We were also able to monitor the interaction of melanin with superoxide radical, which was reducing in this case. Detailed analysis of transient changes in melanin absorbance, detected at different wavelengths, was demonstrated to be a convenient method for studying redox processes of this substance, as shown by model experiments using ferricyanide and dithionite as oxidising and reducing agents, respectively. Among the radicals studied, OH. exhibited the strongest reactivity with melanins. Apparent rate constants for the reactions of radicals with autoxidative dopa-melanin (1.5 X 10(9) M-1 X s-1, 2.6 X 10(8) M-1 X s-1, 1.8 X 10(8) M-1 X s-1, 5 X 10(5) M-1 X s-1, 10(6)-10(7) M-1 X s-1 for OH., eaq-, N.3. O2- and CO2-, respectively) are reported. The reactivity of melanins with radicals from water radiolysis and their effect on pigment properties are discussed in terms of the structure and possible biological role of the pigments.

  20. Generic Sensor Modeling Using Pulse Method

    NASA Technical Reports Server (NTRS)

    Helder, Dennis L.; Choi, Taeyoung

    2005-01-01

    Recent development of high spatial resolution satellites such as IKONOS, Quickbird and Orbview enable observation of the Earth's surface with sub-meter resolution. Compared to the 30 meter resolution of Landsat 5 TM, the amount of information in the output image was dramatically increased. In this era of high spatial resolution, the estimation of spatial quality of images is gaining attention. Historically, the Modulation Transfer Function (MTF) concept has been used to estimate an imaging system's spatial quality. Sometimes classified by target shapes, various methods were developed in laboratory environment utilizing sinusoidal inputs, periodic bar patterns and narrow slits. On-orbit sensor MTF estimation was performed on 30-meter GSD Landsat4 Thematic Mapper (TM) data from the bridge pulse target as a pulse input . Because of a high resolution sensor s small Ground Sampling Distance (GSD), reasonably sized man-made edge, pulse, and impulse targets can be deployed on a uniform grassy area with accurate control of ground targets using tarps and convex mirrors. All the previous work cited calculated MTF without testing the MTF estimator's performance. In previous report, a numerical generic sensor model had been developed to simulate and improve the performance of on-orbit MTF estimating techniques. Results from the previous sensor modeling report that have been incorporated into standard MTF estimation work include Fermi edge detection and the newly developed 4th order modified Savitzky-Golay (MSG) interpolation technique. Noise sensitivity had been studied by performing simulations on known noise sources and a sensor model. Extensive investigation was done to characterize multi-resolution ground noise. Finally, angle simulation was tested by using synthetic pulse targets with angles from 2 to 15 degrees, several brightness levels, and different noise levels from both ground targets and imaging system. As a continuing research activity using the developed sensor

  1. Identification of radiolysis products of solid thiamphenicol.

    PubMed

    Marciniec, B; Stawny, M; Danikiewicz, W; Spólnik, G; Jaroszkiewicz, E; Needham, M

    2010-12-01

    Spectroscopic and chromatographic methods (HPLC, HPLC-MS, NMR) were used to observe, separate and identify products of radiolysis of thiamphenicol (TF), irradiated in the solid state at room temperature and atmospheric pressure with an electron beam from a linear accelerator to doses between 25 and 800 kGy. Nine products of radiolysis of thiamphenicol were identified, among them were TF amine, dichloroacetic acid, 4-methylsulfonylbenzoic acid, demono- and dedichloroderivative of TF, 2,2-dichloro-N-{3-hydroxy-1-[4-(methylsulfonyl)phenyl]-1-oxopropan-2-yl}acetamide and 3-({1,3-dihydroxy-1-[4-(methylsulfonyl)phenyl]propan-2-yl}amino)-3-oxopropanoic acid. The process of radiodegradation of TF was proposed as consisting of several parallel primary reactions (dehalogenation, oxidation of the OH group at C(1), hydrolysis of the amide bond, a rapture of the C(2)-C(3) bond of propan-1-ol) and secondary reactions (carboxylation and oxidation). The use of high doses, well above the sterilization dose of 25 kGy, allowed observation of changes of TF content as a function of radiation dose, calculation of radiolytic yield (G(-TF)) and kinetic parameters of the degradation reaction. It was found that the standard sterilizing dose lowers the content of TF by only 0.1% and the radiolytic efficacy of the process of radiodegradation is 0.76 molecules/100eV. Further increase in the dose lowers the content of TF to 92.1% for 800 kGy dose and leads to an increase in the value of G(-TF). It was also found that the summative process of radiodegradation of TF exposed to a beam of electrons of 10 kGy/s follows the first order reaction kinetics with a degradation constant of k=0.001s(-1). On the basis of the experiments conducted it can be stated that the radiolysis of TF in the presence of an E-beam, in substantia, follows multidirectional course in the same way as radiolysis of chloramphenicol. TF exposed to the standard sterilizing dose of 25 kGy degrades only by 0.1%, the amount

  2. Chaotic carrier pulse position modulation communication system and method

    DOEpatents

    Abarbanel, Henry D. I.; Larson, Lawrence E.; Rulkov, Nikolai F.; Sushchik, Mikhail M.; Tsimring, Lev S.; Volkovskii, Alexander R.

    2001-01-01

    A chaotic carrier pulse position modulation communication system and method is disclosed. The system includes a transmitter and receiver having matched chaotic pulse regenerators. The chaotic pulse regenerator in the receiver produces a synchronized replica of a chaotic pulse train generated by the regenerator in the transmitter. The pulse train from the transmitter can therefore act as a carrier signal. Data is encoded by the transmitter through selectively altering the interpulse timing between pulses in the chaotic pulse train. The altered pulse train is transmitted as a pulse signal. The receiver can detect whether a particular interpulse interval in the pulse signal has been altered by reference to the synchronized replica it generates, and can therefore detect the data transmitted by the receiver. Preferably, the receiver predicts the earliest moment in time it can expect a next pulse after observation of at least two consecutive pulses. It then decodes the pulse signal beginning at a short time before expected arrival of a pulse.

  3. PULSE RADIOLYSIS IN SUPERCRITICAL RARE GAS FLUIDS

    SciTech Connect

    HOLROYD,R.

    2007-01-01

    Recently, supercritical fluids have become quite popular in chemical and semiconductor industries for applications in chemical synthesis, extraction, separation processes, and surface cleaning. These applications are based on: the high dissolving power due to density build-up around solute molecules, and the ability to tune the conditions of a supercritical fluid, such as density and temperature, that are most suitable for a particular reaction. The rare gases also possess these properties and have the added advantage of being supercritical at room temperature. Information about the density buildup around both charged and neutral species can be obtained from fundamental studies of volume changes in the reactions of charged species in supercritical fluids. Volume changes are much larger in supercritical fluids than in ordinary solvents because of their higher compressibility. Hopefully basic studies, such as discussed here, of the behavior of charged species in supercritical gases will provide information useful for the utilization of these solvents in industrial applications.

  4. Radiolysis and photolysis studies on active transient species of berberine.

    PubMed

    Cheng, Ling-Li; Wang, Yu-Jia; Huang, Da-Hong; Yao, Si-De; Ding, Guo-Ji; Wang, Shi-Long; Jiao, Zheng

    2014-04-24

    In this paper, the photochemical and photobiological characters of the active radicals of berberine (BBR) was investigated for finding an efficient and safe photosensitizer with highly active transient products using in Photodynamic therapy (PDT) study. The active species of BBR was generated and identified by using pulse radiolysis method. In neutral aqueous solution, BBR react with hydrated electron and hydroxyl radical, forming the radical anion and neutral radical of BBR, and the related reaction rates were determined as 3.5×10(10) and 6.7×10(9) M(-1) s(-1), respectively. Further, the capability of BBR to photosensitize DNA cleavage was testified by laser flash photolysis (LFP) method, the results demonstrated that BBR neutral radical could react with guanine mononucleotide (K=1.9×10(9) M(-1) s(-1)) via electron transfer to give the guanine neutral radical. Additionally BBR selective cleavage single and double strand DNA at guanine moiety was observed. Finally, combining with the thermodynamic calculation, the possible photodamage mechanism of dGMP and DNA induced by BBR was clarified. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Assessment of pulse rate variability by the method of pulse frequency demodulation

    PubMed Central

    Hayano, Junichiro; Barros, Allan Kardec; Kamiya, Atsunori; Ohte, Nobuyuki; Yasuma, Fumihiko

    2005-01-01

    Background Due to its easy applicability, pulse wave has been proposed as a surrogate of electrocardiogram (ECG) for the analysis of heart rate variability (HRV). However, its smoother waveform precludes accurate measurement of pulse-to-pulse interval by fiducial-point algorithms. Here we report a pulse frequency demodulation (PFDM) technique as a method for extracting instantaneous pulse rate function directly from pulse wave signal and its usefulness for assessing pulse rate variability (PRV). Methods Simulated pulse wave signals with known pulse interval functions and actual pulse wave signals obtained from 30 subjects with a trans-dermal pulse wave device were analyzed by PFDM. The results were compared with heart rate and HRV assessed from simultaneously recorded ECG. Results Analysis of simulated data revealed that the PFDM faithfully demodulates source interval function with preserving the frequency characteristics of the function, even when the intervals fluctuate rapidly over a wide range and when the signals include fluctuations in pulse height and baseline. Analysis of actual data revealed that individual means of low and high frequency components of PRV showed good agreement with those of HRV (intraclass correlation coefficient, 0.997 and 0.981, respectively). Conclusion The PFDM of pulse wave signal provides a reliable assessment of PRV. Given the popularity of pulse wave equipments, PFDM may open new ways to the studies of long-term assessment of cardiovascular variability and dynamics. PMID:16259639

  6. Radiolysis of Bicarbonate and Carbonate Aqueous Solutions: Product Analysis and Simulation of Radiolytic Processes

    SciTech Connect

    Cai Zhongli; Li Xifeng; Katsumura, Yosuke; Urabe, Osamu

    2001-11-15

    An understanding of the radiation-induced effects in groundwater is essential to evaluate the safe geological disposal of spent fuel. In groundwater, the bicarbonate ion is the predominant and common anion; this work investigated radiation-induced chemical reactions of (bi)carbonate aqueous solutions with steady-state irradiation and pulse radiolysis methods. Aqueous solutions of sodium (bi)carbonate as high as 50 mmol.dm{sup -3} were used. The formation of formate, oxalate, and H{sub 2}O{sub 2} were measured under different conditions. A complete set of reaction steps and reliable kinetic data for the radiolysis of (bi)carbonate aqueous solutions at ionic strength close to the groundwater were proposed. Kinetic calculations were completed based on the proposed reaction steps and the kinetic data obtained in the present work. The results from the calculation are in good agreement with the experimental results. With these proposed reaction steps and kinetic data, computer simulation can be performed to predict the yield of radiolytic products of (bi)carbonate aqueous solutions as a function of irradiation time and used to evaluate the safety of geological disposal options of spent fuel.

  7. Pulsed source ion implantation apparatus and method

    DOEpatents

    Leung, Ka-Ngo

    1996-01-01

    A new pulsed plasma-immersion ion-implantation apparatus that implants ions in large irregularly shaped objects to controllable depth without overheating the target, minimizing voltage breakdown, and using a constant electrical bias applied to the target. Instead of pulsing the voltage applied to the target, the plasma source, for example a tungsten filament or a RF antenna, is pulsed. Both electrically conducting and insulating targets can be implanted.

  8. Pulsed source ion implantation apparatus and method

    DOEpatents

    Leung, K.N.

    1996-09-24

    A new pulsed plasma-immersion ion-implantation apparatus that implants ions in large irregularly shaped objects to controllable depth without overheating the target, minimizing voltage breakdown, and using a constant electrical bias applied to the target. Instead of pulsing the voltage applied to the target, the plasma source, for example a tungsten filament or a RF antenna, is pulsed. Both electrically conducting and insulating targets can be implanted. 16 figs.

  9. Stably operating pulse combustor and method

    DOEpatents

    Zinn, B.T.; Reiner, D.

    1990-05-29

    A pulse combustor apparatus is described which is adapted to burn either a liquid fuel or a pulverized solid fuel within a preselected volume of the combustion chamber. The combustion process is substantially restricted to an optimum combustion zone in order to attain effective pulse combustion operation. 4 figs.

  10. Stably operating pulse combustor and method

    DOEpatents

    Zinn, Ben T.; Reiner, David

    1990-01-01

    A pulse combustor apparatus adapted to burn either a liquid fuel or a pulverized solid fuel within a preselected volume of the combustion chamber. The combustion process is substantially restricted to an optimum combustion zone in order to attain effective pulse combustion operation.

  11. Pulse front adaptive optics: a new method for control of ultrashort laser pulses.

    PubMed

    Sun, Bangshan; Salter, Patrick S; Booth, Martin J

    2015-07-27

    Ultrafast lasers enable a wide range of physics research and the manipulation of short pulses is a critical part of the ultrafast tool kit. Current methods of laser pulse shaping are usually considered separately in either the spatial or the temporal domain, but laser pulses are complex entities existing in four dimensions, so full freedom of manipulation requires advanced forms of spatiotemporal control. We demonstrate through a combination of adaptable diffractive and reflective optical elements - a liquid crystal spatial light modulator (SLM) and a deformable mirror (DM) - decoupled spatial control over the pulse front (temporal group delay) and phase front of an ultra-short pulse was enabled. Pulse front modulation was confirmed through autocorrelation measurements. This new adaptive optics technique, for the first time enabling in principle arbitrary shaping of the pulse front, promises to offer a further level of control for ultrafast lasers.

  12. Apparatus and method for optical pulse measurement

    SciTech Connect

    Trebino, Rick P.; Tsang, Thomas; Fittinghoff, David N.; Sweetser, John N.; Krumbuegel, Marco A.

    1999-12-28

    Practical third-order frequency-resolved optical grating (FROG) techniques for characterization of ultrashort optical pulses are disclosed. The techniques are particularly suited to the measurement of single and/or weak optical pulses having pulse durations in the picosecond and subpicosecond regime. The relative quantum inefficiency of third-order nonlinear optical effects is compensated for through i) use of phase-matched transient grating beam geometry to maximize interaction length, and ii) use of interface-enhanced third-harmonic generation.

  13. Studies on oxidative radiolysis of ibuprofen in presence of potassium persulfate

    NASA Astrophysics Data System (ADS)

    Paul (Guin), Jhimli; Naik, D. B.; Bhardwaj, Y. K.; Varshney, Lalit

    2014-07-01

    The radiolysis of ibuprofen (IBP), a model pharmaceutical compound, was studied by gamma irradiation in an aqueous solution in the presence and absence of potassium persulfate (K2S2O8). The extent of mineralization was investigated by measuring the UV-visible spectra, decrease in the chemical oxygen demand (COD) and the total organic carbon (TOC) content of aqueous IBP solution at different doses. The gamma radiolysis, in the presence of K2S2O8, required much lesser dose compared to in the absence of K2S2O8 for the same extent of mineralization of aqueous IBP solution. The pulse radiolysis of IBP was carried out under different radiolytic conditions to understand the mechanism of efficient mineralization of IBP during gamma radiolysis in the presence of K2S2O8. It was found that unlike radOH radical, SO4rad - radical preferentially produces benzyl type of radicals via the formation of the benzene radical cation. The results concluded that the gamma radiolysis in presence of K2S2O8 could be one of the efficient advanced oxidation processes for degradation of pharmaceutical compounds present in the aqueous solution.

  14. Multiple laser pulse ignition method and apparatus

    DOEpatents

    Early, James W.

    1998-01-01

    Two or more laser light pulses with certain differing temporal lengths and peak pulse powers can be employed sequentially to regulate the rate and duration of laser energy delivery to fuel mixtures, thereby improving fuel ignition performance over a wide range of fuel parameters such as fuel/oxidizer ratios, fuel droplet size, number density and velocity within a fuel aerosol, and initial fuel temperatures.

  15. Method and apparatus for the production of pre pulse free smooth laser radiation pulses of variable pulse duration

    SciTech Connect

    Witte, K. J.; Fill, E.; Scrlac, W.

    1985-04-30

    The pulse duration of an iodine laser is adjusted between 400 ps and 20 ns primarily by changing the resonator length in the range of about 2 cm to about 100 cm and secondarily by the ratio of excitation energy to threshold energy of the laser. Iodine laser pulses without pre-pulse and substructure are achieved in that the gas pressure of the laser gas of the iodine laser is adapted to the resonator length in order to limit the band width of the amplification and thus the band width of the pulse to be produced. The longer are the laser pulses to be produced the lower is the pressure chosen. A prerequisite for the above results is that the excitation of the iodine laser occurs extremely rapidly. This is advantageously achieved by photo-dissociation of a perfluoroalkyl iodide as CF/sub 3/I by means of laser providing sufficiently short output pumping pulses, e.g. an excimer laser, as a KrF laser or XeCl laser or a frequency-multiplied Nd-glass or Nd-YAG laser, or a N/sub 2/ laser (in combination with t-C/sub 4/F/sub 9/I as laser medium). In addition to the substantial advantage of the easy variability of the pulse duration the method additionally has a number of further advantages, namely pre-pulse-free rise of the laser pulse up to the maximum amplitude; exchange of the laser medium between two pulses is not necessary at pulse repetition rates below about 1 hertz; high pulse repetion rates obtainable with laser gas regeneration; switching elements for isolating a laser oscillator from a subsequent amplifier cascade for the purpose of avoiding parasitic oscillations are not as critical as with flashlamp-pumped lasers.

  16. A new method to produce short pulses

    NASA Astrophysics Data System (ADS)

    Germer, Rudolf

    2005-03-01

    If a coaxial cable or a strip line has an open end, then the incoming signal is reflected there. Due to the propagation velocity, an incoming rectangular pulse has a length in space which depends on its length in time. If the pulse length is twice the cable length, then after the reflection at the end, the pulse energy is distributed in an electrical field along the cable. Input and output current are compensating. At this time, it is possible to take out the energy simultanously through several switched connections at the same time. The result is a shorter pulse of much higher power which can drive a load of low impedance or with the pulse transformer presented at the 25th ICHSPP give a short pulse of very high voltage. This concentration in time of the electrical energy is planed to be used for x-ray flash systems. If the input pulse is not rectangular, then it is possible to take off the energy at the time of best peak power. Bei einem Bandleiter oder Koaxialkabel mit offenem Ende wird das auf der Leitung laufende Signal reflektiert. Die Ausdehnung eines Rechteckimpulses auf einer solchen Leitung entspricht seiner Dauer und der Ausbreitungsgeschwindigkeit auf der Leitung. Wenn die Impulsausdehnung doppelt so gross ist wie die Leitungslange, dann kann die gesamte Energie des Impulses nach der Reflexion im elektrischen Feld gespeichert sein, Eingangs und Reflexionsstrom kompensieren sich. Zu dieser Zeit ist es moglich, fast die ganze Energie gleichzeitig seitlich durch einen ausgedehnten oder mit mehreren einzelnen Schaltern an einen niederohmigen Verbraucher weiterzuleiten oder mit einem Impulstransformator ( gezeigt auf dem 25. ICHSPP ) an dessen Impedanz anzupassen. Der Ausgangsimpuls ist sehr kurz und von vervielfachter Leistung. Diese zeitliche Energiekonzentration soll spater fur Rontgenbltzsysteme verwendet werden. Im Falle eines nicht rechteckformigen Eingangsimpulses kann die Energie wahrend der hochsten Spitzenleistung entnommen werden.

  17. In honour of N. Yngve Öhrn: surveying proton cancer therapy reactions with Öhrn's electron nuclear dynamics method. Aqueous clusters radiolysis and DNA-base damage by proton collisions

    NASA Astrophysics Data System (ADS)

    Mclaurin, Patrick M.; Privett, Austin J.; Stopera, Christopher; Grimes, Thomas V.; Perera, Ajith; Morales, Jorge A.

    2015-02-01

    Proton cancer therapy (PCT) utilises high-energy H+ projectiles to cure cancer. PCT healing arises from its DNA damage in cancerous cells, which is mostly inflicted by the products from PCT water radiolysis reactions. While clinically established, a complete microscopic understanding of PCT remains elusive. To help in the microscopic elucidation of PCT, Professor Öhrn's simplest-level electron nuclear dynamics (SLEND) method is herein applied to H+ + (H2O)3-4 and H+ + DNA-bases at ELab = 1.0 keV. These are two types of computationally feasible prototypes to study water radiolysis reactions and H+-induced DNA damage, respectively. SLEND is a time-dependent, variational, non-adiabatic and direct-dynamics method that adopts a nuclear classical-mechanics description and an electronic single-determinantal wavefunction. Additionally, our SLEND + effective-core-potential method is herein employed to simulate some computationally demanding PCT reactions. Due to these attributes, SLEND proves appropriate for the simulation of various types of PCT reactions accurately and feasibly. H+ + (H2O)3-4 simulations reveal two main processes: H+ projectile scattering and the simultaneous formation of H and OH fragments; the latter process is quantified through total integrals cross sections. H+ + DNA-base simulations reveal atoms and groups displacements, ring openings and base-to-proton electron transfers as predominant damage processes. The authors warmly dedicate this SLEND investigation in honour of Professor N. Yngve Öhrn on the occasion of his 80th birthday celebration during the 54th Sanibel Symposium in St. Simons' Island, Georgia, on February 16-21, 2014. Associate Professor Jorge A. Morales was a former chemistry PhD student under the mentorship of Professor Öhrn and Dr Ajith Perera took various quantum chemistry courses taught by Professor Öhrn during his chemistry PhD studies. Both Jorge and Ajith look back to those great times of their scientific formation under

  18. Laser pulse stretcher method and apparatus

    DOEpatents

    Hawkins, Jon K.; Williams, William A.

    1990-01-01

    The output of an oscillator stage of a laser system is monitored by a photocell which is coupled to a feedback section to control a Pockels Cell and change the light output of the oscillator stage. A synchronizing pulse is generated in timed relation to the initiation of operation of the oscillator stage and is applied to a forward feed section which cooperates with the feedback section to maintain the light output constant for an extended time interval.

  19. Laser pulse detection method and apparatus

    NASA Technical Reports Server (NTRS)

    Goss, W.; Janesick, J. R. (Inventor)

    1984-01-01

    A sensor is described for detecting the difference in phase of a pair of returned light pulse components, such as two components of a light pulse of an optical gyro. In an optic gyro, the two light components have passed in opposite directions through a coil of optical fiber, with the difference in phase of the returned light components determining the intensity of light shining on the sensor. The sensor includes a CCD (charge coupled device) that receives the pair of returned light components to generate a charge proportional to the number of photons in the received light. The amount of the charge represents the phase difference between the two light components. At a time after the transmission of the light pulse and before the expected time of arrival of the interfering light components, charge accumulating in the CCD as a result of reflections from components in the system, are repeatedly removed from the CCD, by transferring out charges in the CCD and dumping these charges.

  20. Laser pulse detection method and apparatus

    NASA Technical Reports Server (NTRS)

    Goss, Willis C. (Inventor); Janesick, James R. (Inventor)

    1987-01-01

    A sensor is described for detecting the difference in phase of a pair of returned light pulse components, such as the two components of a light pulse of an optical gyro. In an optic gyro, the two light components have passed in opposite directions through a coil of optical fiber, with the difference in phase of the returned light components determining the intensity of light shining on the sensor. The sensor includes a CCD (charge coupled device) that receives the pair of returned light components to generate a charge proportional to the number of photons in the received light. The amount of the charge represents the phase difference between the two light components. At a time after the transmission of the light pulse and before the expected time of arrival of the interfering light components, charge accumulating in the CCD as a result of reflections from optical components in the system, are repeatedly removed from the CCD, by transferring out charges in the CCD and dumping these charges.

  1. Optimal pulse design in quantum control: A unified computational method

    PubMed Central

    Li, Jr-Shin; Ruths, Justin; Yu, Tsyr-Yan; Arthanari, Haribabu; Wagner, Gerhard

    2011-01-01

    Many key aspects of control of quantum systems involve manipulating a large quantum ensemble exhibiting variation in the value of parameters characterizing the system dynamics. Developing electromagnetic pulses to produce a desired evolution in the presence of such variation is a fundamental and challenging problem in this research area. We present such robust pulse designs as an optimal control problem of a continuum of bilinear systems with a common control function. We map this control problem of infinite dimension to a problem of polynomial approximation employing tools from geometric control theory. We then adopt this new notion and develop a unified computational method for optimal pulse design using ideas from pseudospectral approximations, by which a continuous-time optimal control problem of pulse design can be discretized to a constrained optimization problem with spectral accuracy. Furthermore, this is a highly flexible and efficient numerical method that requires low order of discretization and yields inherently smooth solutions. We demonstrate this method by designing effective broadband π/2 and π pulses with reduced rf energy and pulse duration, which show significant sensitivity enhancement at the edge of the spectrum over conventional pulses in 1D and 2D NMR spectroscopy experiments. PMID:21245345

  2. Pulsed interrupter and method of operation

    DOEpatents

    Drake, Joel Lawton; Kratz, Robert

    2015-06-09

    Some embodiments provide interrupter systems comprising: a first electrode; a second electrode; a piston movably located at a first position and electrically coupled with the first and second electrodes establishing a closed state, the piston comprises an electrical conductor that couples with the first and second electrodes providing a conductive path; an electromagnetic launcher configured to, when activated, induce a magnetic field pulse causing the piston to move away from the electrical coupling with the first and second electrodes establishing an open circuit between the first and second electrodes; and a piston control system comprising a piston arresting system configured to control a deceleration of the piston following the movement of the piston induced by the electromagnetic launcher such that the piston is not in electrical contact with at least one of the first electrode and the second electrode when in the open state.

  3. Effects of microviscosity, dry electron scavenging, and protein mobility on the radiolysis of albumen hydrogel.

    PubMed

    Krise, Keith M; Milosavljevic, Bratoljub H

    2011-10-20

    Nanosecond pulse radiolysis experiments performed on the oxygen and nitrogen saturated thick fraction of egg white (which has an immeasurably high macroviscosity) produced a rate constant for hydrated electron reaction with oxygen equal to 1.7 × 10(10) M(-1) s(-1) at 18 °C, indicating that, due to the very low microviscosity, hydrated electrons are as mobile and reactive in the albumen hydrogel as in neat water. Also, the radiolytic yield for the hydrated electron (G-value) in the thick fraction of egg white (measured at the end of a 14 ns electron pulse) was found to be 86% of that determined in neat water, which can be attributed to the reaction of dry electrons with the protein constituents. Steady-state γ radiolysis studies on air-saturated thick and thin fraction (true solution) revealed that the immobility of egg white proteins disfavors reactions that result in molecular mass change.

  4. Method and apparatus for analog pulse pile-up rejection

    DOEpatents

    De Geronimo, Gianluigi

    2014-11-18

    A method and apparatus for pulse pile-up rejection are disclosed. The apparatus comprises a delay value application constituent configured to receive a threshold-crossing time value, and provide an adjustable value according to a delay value and the threshold-crossing time value; and a comparison constituent configured to receive a peak-occurrence time value and the adjustable value, compare the peak-occurrence time value with the adjustable value, indicate pulse acceptance if the peak-occurrence time value is less than or equal to the adjustable value, and indicate pulse rejection if the peak-occurrence time value is greater than the adjustable value.

  5. Method and apparatus for analog pulse pile-up rejection

    DOEpatents

    De Geronimo, Gianluigi

    2013-12-31

    A method and apparatus for pulse pile-up rejection are disclosed. The apparatus comprises a delay value application constituent configured to receive a threshold-crossing time value, and provide an adjustable value according to a delay value and the threshold-crossing time value; and a comparison constituent configured to receive a peak-occurrence time value and the adjustable value, compare the peak-occurrence time value with the adjustable value, indicate pulse acceptance if the peak-occurrence time value is less than or equal to the adjustable value, and indicate pulse rejection if the peak-occurrence time value is greater than the adjustable value.

  6. Method and circuit for shaping laser output pulses

    NASA Technical Reports Server (NTRS)

    Barnes, Norman P. (Inventor)

    1990-01-01

    The invention is a method and circuit for shaping laser pulses 17' in which a laser medium 12' in a laser resonator 10' that includes a Q-switch 14' and polarizer 13' which act in combination to control the loss of the resonator 10' and provide the laser output 17' representative of such loss. An optical diode 22' senses the level of the output pulse 17' and provides an output signal 23' that when amplified is used with a control voltage from a supply 29' provide a control signal 19' which is applied to Q-switch 14' to control the shape of the output pulse 17' by adjusting its length.

  7. Radiolysis of water in sealed aluminum capsules - Its prediction and inhibition.

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.

    1971-01-01

    This report presents the results of an investigation into methods of inhibiting the radiolysis of water in sealed aluminum capsules in the Plum Brook Reactor of NASA. Experimental design techniques are employed to identify the measured effects of eight variables and their interactions which control water decomposition and the resultant pressure buildup. Multiple regression analyses are used to develop predictive models for the pressure rise observed in an inpile capsule system. Predictive equations are derived for pressure rise due to the radiolysis of water with air as a cover gas or with helium cover gas containing air as an impurity or mixtures of hydrogen, oxygen, and nitrogen as impurities. Radiation induced reaction products of nitrogen and oxygen are identified as the key to radiolysis behavior. The prevention of radiolysis depends on the exclusion of air or mixtures of nitrogen and oxygen from the system. Pure inert gases, helium, neon, and argon prove to be satisfactory radiolysis inhibitors. This is demonstrated for helium by inpile tests lasting up to 14 days (one reactor cycle) in the Plum Brook Reactor.

  8. Radiolysis of water in sealed aluminum capsules - Its prediction and inhibition.

    NASA Technical Reports Server (NTRS)

    Sheibley, D. W.

    1971-01-01

    This report presents the results of an investigation into methods of inhibiting the radiolysis of water in sealed aluminum capsules in the Plum Brook Reactor of NASA. Experimental design techniques are employed to identify the measured effects of eight variables and their interactions which control water decomposition and the resultant pressure buildup. Multiple regression analyses are used to develop predictive models for the pressure rise observed in an inpile capsule system. Predictive equations are derived for pressure rise due to the radiolysis of water with air as a cover gas or with helium cover gas containing air as an impurity or mixtures of hydrogen, oxygen, and nitrogen as impurities. Radiation induced reaction products of nitrogen and oxygen are identified as the key to radiolysis behavior. The prevention of radiolysis depends on the exclusion of air or mixtures of nitrogen and oxygen from the system. Pure inert gases, helium, neon, and argon prove to be satisfactory radiolysis inhibitors. This is demonstrated for helium by inpile tests lasting up to 14 days (one reactor cycle) in the Plum Brook Reactor.

  9. Frequency-Domain Methods for Characterization of Pulsed Power Diagnostics

    SciTech Connect

    White, A D; Anderson, R A; Ferriera, T J; Goerz, D A

    2009-07-27

    This paper discusses methods of frequency-domain characterization of pulsed power sensors using vector network analyzer and spectrum analyzer techniques that offer significant simplification over time-domain methods, while mitigating or minimizing the effect of the difficulties present in time domain characterization. These methods are applicable to characterization of a wide variety of sensors.

  10. Neural network and area method interpretation of pulsed experiments

    SciTech Connect

    Dulla, S.; Picca, P.; Ravetto, P.; Canepa, S.

    2012-07-01

    The determination of the subcriticality level is an important issue in accelerator-driven system technology. The area method, originally introduced by N. G. Sjoestrand, is a classical technique to interpret flux measurement for pulsed experiments in order to reconstruct the reactivity value. In recent times other methods have also been developed, to account for spatial and spectral effects, which were not included in the area method, since it is based on the point kinetic model. The artificial neural network approach can be an efficient technique to infer reactivities from pulsed experiments. In the present work, some comparisons between the two methods are carried out and discussed. (authors)

  11. A Comparison of the ?-Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis

    SciTech Connect

    Zarzana, Chris A.; Groenewold, Gary S.; Mincher, Bruce J.; Mezyk, Stephen P.; Modolo, Giuseppe; Wildens, Andreas; Schmidt, Holgar; Wishart, James F.; Cook, Andrew R.

    2015-03-01

    Solutions of TODGA and T(EH)DGA in n-dodecane were subjected to ?-irradiation in the presence and absence of an aqueous nitric acid phase and analyzed using UHPLC-ESI-MS to determine the rates of radiolytic decay of the two extractants, as well as to identify radiolysis products. The DGA concentrations decreased exponentially with increasing dose, and the measured degradation rate constants were uninfluenced by the presence or absence of an acidic aqueous phase, or by chemical variations in the alkyl side-chains. The DGA degradation was attributed to reactions of the dodecane radical cation, whose kinetics were measured for TODGA using picosecond electron pulse radiolysis to be k2 = (9.72 ± 1.10) × 109 M-1 s-1. The identified radiolysis products suggest that the bonds most vulnerable to radiolytic attack are those in the diglycolamide center of these molecules and not on the side-chains.

  12. Pulsed Plasma Lubrication Device and Method

    NASA Technical Reports Server (NTRS)

    Hofer, Richard R. (Inventor); Bickler, Donald B. (Inventor); D'Agostino, Saverio A. (Inventor)

    2016-01-01

    Disclosed herein is a lubrication device comprising a solid lubricant disposed between and in contact with a first electrode and a second electrode dimensioned and arranged such that application of an electric potential between the first electrode and the second electrode sufficient to produce an electric arc between the first electrode and the second electrode to produce a plasma in an ambient atmosphere at an ambient pressure which vaporizes at least a portion of the solid lubricant to produce a vapor stream comprising the solid lubricant. Methods to lubricate a surface utilizing the lubrication device in-situ are also disclosed.

  13. Removal of chloroform from biodegradable therapeutic microspheres by radiolysis.

    PubMed

    Zielhuis, S W; Nijsen, J F W; Dorland, L; Krijger, G C; van Het Schip, A D; Hennink, W E

    2006-06-06

    Radioactive holmium-166 loaded poly(l-lactic acid) microspheres are promising systems for the treatment of liver malignancies. These microspheres are loaded with holmium acetylacetonate (HoAcAc) and prepared by a solvent evaporation method using chloroform. After preparation the microspheres (Ho-PLLA-MS) are activated by neutron irradiation in a nuclear reactor. It was observed that relatively large amounts of residual chloroform (1000-6000 ppm) remained in the microspheres before neutron irradiation. Since it is known that chloroform is susceptible for high-energy radiation, we investigated whether neutron and gamma irradiation could result in the removal of residual chloroform in HoAcAc-loaded and placebo PLLA-MS by radiolysis. To investigate this, microspheres with relatively high and low amounts of residual chloroform were subjected to irradiation. The effect of irradiation on the residual chloroform levels as well as other microsphere characteristics (morphology, size, crystallinity, molecular weight of PLLA and degradation products) were evaluated. No chloroform in the microspheres could be detected after neutron irradiation. This was also seen for gamma irradiation at a dose of 200 kGy phosgene, which can be formed as the result of radiolysis of chloroform, was not detected with gas chromatography-mass spectrometry (GC-MS). A precipitation titration showed that radiolysis of chloroform resulted in the formation of chloride. Gel permeation chromatography and differential scanning calorimetry showed a decrease in molecular weight of PLLA and crystallinity, respectively. However, no differences were observed between irradiated microsphere samples with high and low initial amounts of chloroform. In conclusion, this study demonstrates that neutron and gamma irradiation results in the removal of residual chloroform in PLLA-microspheres.

  14. Arterial pulse system: modern methods for traditional Indian medicine.

    PubMed

    Joshi, Aniruddha; Chandran, Sharat; Jayaraman, V K; Kulkarni, B D

    2007-01-01

    Ayurveda is one of the most comprehensive healing systems in the world and has classified the body system according to the theory of Tridosha to overcome ailments. Diagnosis similar to the traditional pulse-based method requires a system of clean input signals, and extensive experiments for obtaining classification features. In this paper we briefly describe our system of generating pulse waveforms and use various feature detecting methods to show that an arterial pulse contains typical physiological properties. The beat-to-beat variability is captured using a complex B-spline mother wavelet based peak detection algorithm. We also capture--to our knowledge for the first time--the self-similarity in the physiological signal, and quantifiable chaotic behavior using recurrence plot structures.

  15. Approximate Design Method for Single Stage Pulse Tube Refrigerators

    NASA Astrophysics Data System (ADS)

    Pfotenhauer, J. M.; Gan, Z. H.; Radebaugh, R.

    2008-03-01

    An approximate design method is presented for the design of a single stage Stirling type pulse tube refrigerator. The design method begins from a defined cooling power, operating temperature, average and dynamic pressure, and frequency. Using a combination of phasor analysis, approximate correlations derived from extensive use of REGEN3.2, a few `rules of thumb,' and available models for inertance tubes, a process is presented to define appropriate geometries for the regenerator, pulse tube and inertance tube components. In addition, specifications for the acoustic power and phase between the pressure and flow required from the compressor are defined. The process enables an appreciation of the primary physical parameters operating within the pulse tube refrigerator, but relies on approximate values for the combined loss mechanisms. The defined geometries can provide both a useful starting point, and a sanity check, for more sophisticated design methodologies.

  16. Radiolysis studies on the destruction of microcystin-LR in aqueous solution by hydroxyl radicals.

    PubMed

    Song, Weihua; Xu, Tielian; Cooper, William J; Dionysiou, Dionysios D; De la Cruz, Armah A; O'Shea, Kevin E

    2009-03-01

    In this study, steady-state and time-resolved radiolysis methods were used to determine the primary reaction pathways and kinetic parameters for the reactions of hydroxyl radical with microcystin-LR (MC-LR). The fundamental kinetic data is critical for the accurate evaluation of hydroxyl-radical based technologies for the destruction of this problematic class of cyanotoxins. The bimolecular rate constant for the reaction of hydroxyl radical with MC-LR is 2.3 (+/-0.1) x 10(10) M(-1)s(-1) based on time-resolved competition kinetics with SCN-at low conversions using pulsed radiolysis experiments. The reaction of hydroxyl radical with MC-LR can occur via a number of competing reaction pathways, including addition to the benzene ring and diene and abstraction of aliphatic hydrogen atoms. LC-MS analyses indicate the major products from the reaction of hydroxyl radicals with MC-LR involve addition of hydroxyl radical to the benzene ring and diene moieties of the Adda side chain. Transient absorption spectroscopy monitored between 260-500 nm, following pulsed hydroxyl radical generation, indicate the formation of a transient species with absorption maxima at 270 and 310 nm. The absorption maxima and lifetime of the transient species are characteristic of hydroxycyclohexadienyl radicals resulting from the addition of hydroxyl radical to the benzene ring. The rate constant for the formation of hydroxycyclohexadienyl radical is 1.0 (+/-0.1) x 10(10) M(-1)s(-1) accounting for approximately 40% of the primary reaction pathways. Representative rate constants and partitioning of hydroxyl radical reactions were assessed based on the reactivities of surrogate substrates and individual amino acids. Summation of the individual reactivities of hydroxyl radical at the different reactive sites (amino acids) leads to a rate constant of 2.1 x 10(10) M(-1) s(-1) in good agreementwith the rate constant determined in our studies. The relative magnitude of the rate constants for the reactions

  17. Radiolysis Studies on the Destruction of Microcystin-LR in Aqueous Solution by Hydroxyl Radicals

    PubMed Central

    Song, Weihua; Xu, Tielian; Cooper, William J.; Dionysiou, Dionysios D.; de la Cruz, Armah A.; O'Shea, Kevin E.

    2012-01-01

    In this study, steady state and time resolved radiolysis methods were used to determine the primary reaction pathways and kinetic parameters for the reactions of hydroxyl radical with microcystin-LR (MC-LR). The fundamental kinetic data is critical for the accurate evaluation of hydroxyl radical based technologies for the destruction of this problematic class of cyanotoxins. The bimolecular rate constant for the reaction of hydroxyl radical with MC-LR is 2.3 (± 0.1) × 1010 M−1s−1 based on time resolved competition kinetics with SCN− at low conversions using pulsed radiolysis experiments. The reaction of hydroxyl radical with MC-LR can occur via a number of competing reaction pathways, including addition to the benzene ring and diene and abstraction of aliphatic hydrogen atoms. LC-MS analyses indicate the major products from the reaction of hydroxyl radicals with MC-LR involve addition of hydroxyl radical to the benzene ring and diene moieties of the Adda side chain. Transient absorption spectroscopy monitored between 260–500 nm following pulsed hydroxyl radical generation indicate the formation of a transient species with absorption maxima at 270 and 310 nm. The absorption maxima and lifetime of the transient species are characteristic of hydroxycyclohexadienyl radicals resulting from the addition of hydroxyl radical to the benzene ring. The rate constant for the formation of hydroxycyclohexadienyl radical is 1.0 (± 0.1) × 1010 M−1s−1 accounting for ~40 % of the primary reaction pathways. Representative rate constants and partitioning of hydroxyl radical reactions were assessed based on the reactivities of surrogate substrates and individual amino acids. Summation of the individual reactivities of hydroxyl radical at the different reactive sites (amino acids) leads to a rate constant of 2.1 × 1010 M−1s-1 in good agreement with the rate constant determined in our studies. The relative magnitude of the rate constants for the reactions of hydroxyl

  18. Methods and devices for generation of broadband pulsed radiation

    DOEpatents

    Borguet, Eric; Isaienko, Oleksandr

    2013-05-14

    Methods and apparatus for non-collinear optical parametric ampliffication (NOPA) are provided. Broadband phase matching is achieved with a non-collinear geometry and a divergent signal seed to provide bandwidth gain. A chirp may be introduced into the pump pulse such that the white light seed is amplified in a broad spectral region.

  19. Method and apparatus for characterizing reflected ultrasonic pulses

    NASA Technical Reports Server (NTRS)

    Yost, William T. (Inventor); Cantrell, John H., Jr. (Inventor)

    1991-01-01

    The invention is a method of and apparatus for characterizing the amplitudes of a sequence of reflected pulses R1, R2, and R3 by converting them into corresponding electric signals E1, E2, and E3 to substantially the same value during each sequence thereby restoring the reflected pulses R1, R2, and R3 to their initial reflection values by timing means, an exponential generator, and a time gain compensator. Envelope and baseline reject circuits permit the display and accurate location of the time spaced sequence of electric signals having substantially the same amplitude on a measurement scale on a suitable video display or oscilloscope.

  20. Spur decay kinetics of the solvated electron in heavy water radiolysis.

    SciTech Connect

    Bartels, D. M.; Gosztola, D.; Jonah, C. D.; Chemistry

    2001-08-30

    Spur decay kinetics of the hydrated electron following picosecond pulse radiolysis of heavy water have been measured using a time-correlated absorption spectroscopy (TCAS) technique. The TCAS data collected for the first 40 ns of the decay was matched up with single-shot transient digitizer data out to microsecond time scales. The decay shape in heavy water looks exactly like the decay in light water except in the first 10 ns. The 'time zero' solvated electron yield in heavy water radiolysis must be approximately 7% larger than in light water, to match the best available scavenger product measurements. We propose an explanation in terms of the larger distances traveled by electrons in heavy water prior to localization. The implication is that presolvated H{sub 2}O{sup +} 'holes' are very efficient scavengers for the presolvated conduction band electrons.

  1. Gamma Ray Radiolysis of the FPEX Solvent

    SciTech Connect

    B. J. Mincher; S. P. Mezyk; D. R. Peterman

    2006-09-01

    Slide presentation. FPEX contains a calixarene for Cs extraction, a crown ether for Sr extraction, Cs7SB modifier, and TOA to aid in stripping, in Isopar L diluent. The radiation stability FPEX must be evaluated prior to process use. Radiolytic degradation of species in solution are due to reaction with the direct radiolysis products of the diluent. In Isopar L, the reactive species produced include e-, •H and alkane radicals, resulting in a reducing environment. However, in nitric acid, oxidizing hydroxyl (•OH) and nitro (•NO2) radicals dominate system chemistry. Thus, the nature of diluent and the presence of radical scavengers affect the results of irradiation. We report the preliminary results of a new program to investigate the radiolysis of FPEX using the 60Co irradiation of FPEX neat solvent, acid pre-equilibrated solvent and mixed aerated phases. The Cs and Sr distribution ratios were used as metrics.

  2. Effect of oxygen on the radiolysis of tyrosine in aqueous solutions

    SciTech Connect

    Cudina, I.; Josimovic, L.

    1987-02-01

    The effect of oxygen on the radiolysis of tyrosine in aqueous solutions was investigated by using gamma and pulsed electron irradiation. Steady-state radiolysis was reexamined and extended to include the effect of pH and determination of hydrogen peroxide. The loss of tyrosine, G(-Tyr), during irradiation and yields of 3,4-dihydroxyphenylalanine, G(DOPA), and hydrogen peroxide, G(H2O2), are determined in the pH range from 1 to 9. In the whole pH range used G(-Tyr) equals G(DOPA), and a higher G(H2O2) than expected was observed. In slightly acid and neutral media, both G(-Tyr) and G(DOPA) equal the yield of hydroxyl radicals, GOH, formed in the radiolysis of water, while the excess of hydrogen peroxide equals 1/2 GOH. Hence it was concluded that all tyrosine OH-adducts react with oxygen yielding peroxy radicals. In acid and alkaline media all measured yields decrease. This is caused by formation of tyrosine phenoxyl radicals (TyrO), which react with superoxide anion (O2-) and hydroperoxy (HO2) radicals regenerating tyrosine. By using pulse radiolysis K(TyrO + O2) less than or equal to 2 X 10(5) mol-1 dm3 s-1 and k(TyrO + O2-) = (1.7 +/- 0.2) X 10(9) mol-1 dm3 s-1 were determined. On the basis of the results, a reaction mechanism is proposed.

  3. DNA radiolysis. Mapping of the gene regulation domains

    NASA Astrophysics Data System (ADS)

    Spotheim-Maurizot, Mélanie; Franchet-Beuzit, Jenny; Isabelle, Valerie; Tartier, Laurence; Charlier, Michel

    1995-11-01

    Ionizing radiations induce strand breaks and modifications of nucleotides (base and/or sugar) in DNA. In aerated solution, the damages are mainly due to the attack of DNA by the hydroxyl radicals (OH ·) issued from the radiolysis of water. The lesions occur at every nucleotides along the DNA molecule. For γ-rays, β-rays and fast neutrons, we have determined at each nucleotide the probability of strand breakage at neutral pH and the probability of base and sugar modification leading also to strand breakage after an alkaline treatment. The method of sequencing gel electrophoresis was used for this purpose. We have shown that the probability of getting a radiation induced damage at a given nucleotide is modulated by: i) the chemical nature of this nucleotide, ii) the local conformation determined by the sequence of nucleotides and by DNA strandedness (single or double stranded), iii) the type of structure to which the nucleotide belongs (right-handed B- or left-handed Z-DNA) and iv) the presence of proteins specifically (e.g. repressors) or nonspecifically (histones or histone-like) bound to DNA. Therefore, radiolysis may be a convenient tool for mapping gene regulation domains in which DNA is often in non-canonical B forms or is in interaction with regulatory proteins.

  4. Efficient degradation of butylparaben by gamma radiolysis.

    PubMed

    Guin, Jhimli Paul; Bhardwaj, Y K; Varshney, Lalit

    2017-04-01

    Gamma radiolysis and ozonolysis are two competitive advanced oxidation processes for degradation of organic pollutants present in the ground water. In this paper, the gamma radiolytic degradation of an emerging organic pollutant Butylparaben (BP) in aqueous solution has been investigated for the first time at different absorbed doses. The effect of the absorbed dose rate in the degradation and mineralization of BP has been investigated. About 65% mineralization of BP was observed at absorbed dose of 70kGy and dose rate of 0.7kGyh(-1). Interestingly, turbidity appeared in the solution during radiolysis at doses higher than 2kGy, which disappeared again at very higher dose (~90kGy) making the solution again transparent. At lower dose rate of 0.175kGyh(-1) the turbidity was appeared at much lower dose about 1kGy. However, the dose rate showed no effect in the dose of the disappearance of the turbidity. The hydrophobic fragments insoluble in water were generated during the initial stage of gamma radiolysis and those were completely mineralized to CO2 and H2O by direct absorption of gamma radiation. About 90kGy dose was required to achieve ~90% mineralization of BP. On the contrary, maximum 50% mineralization was achieved after 5h of ozonation at the O3 flow rate of 0.5Lmin(-1) at pH 7.5 and it remained even constant upon prolonged ozonation. The oxygen-equivalent-chemical-oxidation-capacity (OCC) was used as the parameter to compare the % mineralization efficiencies of the two oxidative processes studied here and the gamma radiolysis was found to be more efficient between those processes. The phytotoxicity of the treated BP solution to agricultural seeds showed that the radiolytically generated fragments were less toxic compared to ozonolytically generated fragments. Thus gamma radiolysis is effective for reducing the organic burden and the toxicity of water polluted with emerging pollutants like BP. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Influence Pulse Duration Methodical Error of Determination of Thermal Translucent Materials Laser Flash Method

    NASA Astrophysics Data System (ADS)

    Katz, Mark M.; Katz, Ilija M.

    2016-02-01

    The analysis of errors in the determination of thermal diffusivity of a typical semiconductor material - Germany, due to radiative energy transfer in the heated layer of material, under conditions consistent with the implementation of the method under the influence of the laser pulse on the surface of the collimated laser pulse of finite duration.

  6. About the OH yield in the radiolysis of an aqueous/H2O2 system. Its optimisation for water treatment

    NASA Astrophysics Data System (ADS)

    Emmi, Salvatore S.; Caminati, Serena; Esposito, Biagio; Saracino, Michela

    2012-09-01

    Unless the radiolytic reducing species are neutralised or converted into oxidising species, an EB remediation system cannot be considered a true Advanced Oxidation Processes (AOP). A water/H2O2 system irradiated by UVC mercury lamps constitutes a widely used OH production method. Employing H2O2 in radiolysis as well, an enhancement of the oxidative efficiency of an EB treatment can be obtained. Pulse radiolysis measurements of an aerated aqueous/H2O2/KSCN system have been systematically undertaken to assess the optimal H2O2 concentration. By linearly fitting a competition kinetics relationship, it is found that the scavengeable extra-yield of OH is ΔG(OH)=0.24 μmol J-1 (R=0,9958), while the maximum experimental yield is measured G(OH)max=(0.52±0.02) μmol J-1 when [H2O2]=5-10 mM. Exceeding these concentrations the OH yield drops off.

  7. Long-laser-pulse method of producing thin films

    DOEpatents

    Balooch, Mehdi; Olander, Donald K.; Russo, Richard E.

    1991-01-01

    A method of depositing thin films by means of laser vaporization employs a long-pulse laser (Nd-glass of about one millisecond duration) with a peak power density typically in the range 10.sup.5 -10.sup.6 W/cm.sup.2. The method may be used to produce high T.sub.c superconducting films of perovskite material. In one embodiment, a few hundred nanometers thick film of YBa.sub.2 Cu.sub.3 O.sub.7-x is produced on a SrTiO.sub.3 crystal substrate in one or two pulses. In situ-recrystallization and post-annealing, both at elevated temperature and in the presence of an oxidizing agen The invention described herein arose in the course of, or under, Contract No. DE-C03-76SF0098 between the United States Department of Energy and the University of California.

  8. Comparison of pulse phase and thermographic signal reconstruction processing methods

    NASA Astrophysics Data System (ADS)

    Oswald-Tranta, Beata; Shepard, Steven M.

    2013-05-01

    Active thermography data for nondestructive testing has traditionally been evaluated by either visual or numerical identification of anomalous surface temperature contrast in the IR image sequence obtained as the target sample cools in response to thermal stimulation. However, in recent years, it has been demonstrated that considerably more information about the subsurface condition of a sample can be obtained by evaluating the time history of each pixel independently. In this paper, we evaluate the capabilities of two such analysis techniques, Pulse Phase Thermography (PPT) and Thermographic Signal Reconstruction (TSR) using induction and optical flash excitation. Data sequences from optical pulse and scanned induction heating are analyzed with both methods. Results are evaluated in terms of signal-tobackground ratio for a given subsurface feature. In addition to the experimental data, we present finite element simulation models with varying flaw diameter and depth, and discuss size measurement accuracy and the effect of noise on detection limits and sensitivity for both methods.

  9. Radiolysis of aqueous solutions of thiamine

    NASA Astrophysics Data System (ADS)

    Chijate, C.; Albarran, G.; Negron-Mendoza, A.

    1998-06-01

    The results of the radiolysis of aqueous solutions of thiamine (vitamin B 1) are presented. The yields for decomposition of thiamine and the product of radiolytic products were determined. The G values decrease as the dose increases. Some radiolytic products were identified. Decomposition of thiamine was slightly dependent on the presence of oxygen and on the pH of the solution. At pH 4.4 with a concentration of 2.5 × 10 -4 mol L -1 of thiamine in an oxygen free aqueous solution, the G 0 value for decomposition is 5.0.

  10. A new pulsed laser deposition technique: Scanning multi-component pulsed laser deposition method

    SciTech Connect

    Fischer, D.; Jansen, M.; Fuente, G. F. de la

    2012-04-15

    The scanning multi-component pulsed laser deposition (PLD) method realizes uniform depositions of desired coatings by a modified pulsed laser deposition process, preferably with a femto-second laser-system. Multi-component coatings (single or multilayered) are thus deposited onto substrates via laser induced ablation of segmented targets. This is achieved via horizontal line-scanning of a focused laser beam over a uniformly moving target's surface. This process allows to deposit the desired composition of the coating simultaneously, starting from the different segments of the target and adjusting the scan line as a function of target geometry. The sequence and thickness of multilayers can easily be adjusted by target architecture and motion, enabling inter/intra layer concentration gradients and thus functional gradient coatings. This new, simple PLD method enables the achievement of uniform, large-area coatings. Case studies were performed with segmented targets containing aluminum, titanium, and niobium. Under the laser irradiation conditions applied, all three metals were uniformly ablated. The elemental composition within the rough coatings obtained was fixed by the scanned area to Ti-Al-Nb = 1:1:1. Crystalline aluminum, titanium, and niobium were found to coexist side by side at room temperature within the substrate, without alloy formation up to 600 deg. C.

  11. A new pulsed laser deposition technique: scanning multi-component pulsed laser deposition method.

    PubMed

    Fischer, D; de la Fuente, G F; Jansen, M

    2012-04-01

    The scanning multi-component pulsed laser deposition (PLD) method realizes uniform depositions of desired coatings by a modified pulsed laser deposition process, preferably with a femto-second laser-system. Multi-component coatings (single or multilayered) are thus deposited onto substrates via laser induced ablation of segmented targets. This is achieved via horizontal line-scanning of a focused laser beam over a uniformly moving target's surface. This process allows to deposit the desired composition of the coating simultaneously, starting from the different segments of the target and adjusting the scan line as a function of target geometry. The sequence and thickness of multilayers can easily be adjusted by target architecture and motion, enabling inter/intra layer concentration gradients and thus functional gradient coatings. This new, simple PLD method enables the achievement of uniform, large-area coatings. Case studies were performed with segmented targets containing aluminum, titanium, and niobium. Under the laser irradiation conditions applied, all three metals were uniformly ablated. The elemental composition within the rough coatings obtained was fixed by the scanned area to Ti-Al-Nb = 1:1:1. Crystalline aluminum, titanium, and niobium were found to coexist side by side at room temperature within the substrate, without alloy formation up to 600 °C.

  12. Method and means of transmitting and receiving broad-band unipolar, ultrasonic pulses for ultrasonic inspection

    DOEpatents

    Thompson, D.O.; Hsu, D.K.

    1993-12-14

    The invention includes a means and method for transmitting and receiving broadband, unipolar, ultrasonic pulses for ultrasonic inspection. The method comprises generating a generally unipolar ultrasonic stress pulse from a low impedance voltage pulse transmitter along a low impedance electrical pathway to an ultrasonic transducer, and receiving the reflected echo of the pulse by the transducer, converting it to a voltage signal, and passing it through a high impedance electrical pathway to an output. The means utilizes electrical components according to the method. The means and method allow a single transducer to be used in a pulse/echo mode, and facilitates alternatingly transmitting and receiving the broadband, unipolar, ultrasonic pulses. 25 figures.

  13. Method and means of transmitting and receiving broad-band unipolar, ultrasonic pulses for ultrasonic inspection

    DOEpatents

    Thompson, Donald O.; Hsu, David K.

    1993-12-14

    The invention includes a means and method for transmitting and receiving broadband, unipolar, ultrasonic pulses for ultrasonic inspection. The method comprises generating a generally unipolar ultrasonic stress pulse from a low impedance voltage pulse transmitter along a low impedance electrical pathway to an ultrasonic transducer, and receiving the reflected echo of the pulse by the transducer, converting it to a voltage signal, and passing it through a high impedance electrical pathway to an output. The means utilizes electrical components according to the method. The means and method allow a single transducer to be used in a pulse/echo mode, and facilitates alternatingly transmitting and receiving the broadband, unipolar, ultrasonic pulses.

  14. A method to determine open pore volume with pulse decay

    NASA Astrophysics Data System (ADS)

    Cender, Thomas A.; Šimáček, Pavel; Advani, Suresh G.

    2014-09-01

    In determining permeability of porosity media using the pulse decay technique [W. F. Brace, J. B. Walsh, and W. T. Frangos, J. Geophys. Res. 73, 2225 (1968)], the reservoir boundary condition is explored to understand its influence on the rate of pressure decay. A methodology is proposed to calculate the porous volume of the sample. A universal scaling function is identified, which depends on the characteristic time, reservoir volume, and porous volume of the sample. Experimental validation shows porosity can be recovered with the proposed theory. Limitations of the method are discussed.

  15. Radiolysis of cyanocobalamin (vitamin B 12)

    NASA Astrophysics Data System (ADS)

    Juanchi, X.; Albarran, G.; Negron-Mendoza, A.

    2000-03-01

    Research on the radiolysis of vitamins is of considerable interest since these compounds are important nutritional constituents in foods and in dietetic supplements. In spite of these considerations there are few data and very often difficult to compare for the radiolytic behavior of vitamins. In this work we focused our attention on to the study of the radiolysis of cyanocobalamin (vitamin B 12) in solid state and in aqueous solutions. The procedure was followed by HPLC and UV-spectroscopy. The results obtained in aqueous solutions showed a dependence of the decomposition as a linear function of the dose. The G of decomposition for a 1×10 -5 M solution was 3.3. In the solid state the vitamin was very stable towards the irradiation in the conditions used in this study with a G=2.1×10 -3. A study made with Serratia marcescens as a microbiological contaminant showed that at the sterilization dose there is a destruction of the vitamin in aqueous solution. In the solid state the degree of decomposition was 7%.

  16. Perchlorate Formation by Radiolysis on Mars

    NASA Astrophysics Data System (ADS)

    Wilson, E. H.; Atreya, S. K.; Kaiser, R. I.; Mahaffy, P. R.

    2015-12-01

    With recent observations indicating the presence of perchlorate (ClO4-) in the Martian surface by the Phoenix lander and the Sample Analysis at Mars (SAM) on the Mars Science Laboratory (MSL) rover, we employ a one-dimensional chemical model to investigate the viability of perchlorate formation in the atmosphere of Mars, instigated by the radiolysis of the Martian surface by galactic cosmic rays. The surface-atmosphere interaction to produce Martian perchlorate involves the injection of chlorine oxides into the atmosphere through surface radiolysis and the subsequent chemical conversion to perchloric acid (HClO4), followed by surface deposition and mineralization to perchlorate. Considering the chlorine oxide, OClO, we find an effective mechanism for forming perchloric acid, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth. Through this mechanism, an OClO surface flux as low as 3.2*107 molecules cm-2 s-1 could produce enough HClO4 to explain the perchlorate concentration observed on Mars. These results could have wide-ranging implications in our understanding of chlorine chemistry on both Earth and Mars.

  17. A robust method for pulse peak determination in a digital volume pulse waveform with a wandering baseline.

    PubMed

    Jang, Dae-Geun; Farooq, Umar; Park, Seung-Hun; Hahn, Minsoo

    2014-10-01

    This paper presents a robust method for pulse peak determination in a digital volume pulse (DVP) waveform with a wandering baseline. A proposed new method uses a modified morphological filter (MMF) to eliminate a wandering baseline signal of the DVP signal with minimum distortion and a slope sum function (SSF) with an adaptive thresholding scheme to detect pulse peaks from the baseline-removed DVP signal. Further in order to cope with over-detected and missed pulse peaks, knowledge based rules are applied as a postprocessor. The algorithm automatically adjusts detection parameters periodically to adapt to varying beat morphologies and fluctuations. Compared with conventional methods (highpass filtering, linear interpolation, cubic spline interpolation, and wavelet adaptive filtering), our method performs better in terms of the signal-to-error ratio, the computational burden (0.125 seconds for one minute of DVP signal analysis with the Intel Core 2 Quad processor @ 2.40 GHz PC), the true detection rate (97.32% with an acceptance level of 4 ms ) as well as the normalized error rate (0.18%). In addition, the proposed method can detect true positions of pulse peaks more accurately and becomes very useful for pulse transit time (PTT) and pulse rate variability (PRV) analyses.

  18. Pulse

    MedlinePlus

    ... the underside of the opposite wrist, below the base of the thumb. Press with flat fingers until ... determine if the patient's heart is pumping. Pulse measurement has other uses as well. During or immediately ...

  19. Method of pressure pulse cleaning a tube bundle heat exchanger

    SciTech Connect

    Scharton, T.D.; Taylor, G.B.

    1987-04-07

    A method is described of removing the products of corrosion, oxidation, sedimentation and comparable chemical reactions collectively known as sludge which settle on the bottom of a tube bundle heat exchange and form a pile of sludge. The tube bundle heat exchanger is characterized by a tube bundle heat exchanger wall and a thick metal plate known as a tube sheet near the lower portion of the tube bundle heat exchanger wall's interior surface. The tube sheet serves to support the lower ends of a multiplicity of heat exchanger tubes within the tube bundle heat exchanger. The tube bundle heat exchange wall further comprises a multiplicity of small holes known as hand holes, manways, drain lines and vents, located around its circumference and above the tube sheet. The method is described of removing the pile of sludge which settles on the tube sheet comprising: a. locating at least one air-gun type pressure pulse shock wave source outside the tube bundle heat exchanger so as to be able to introduce pressure pulse shock waves through one or more of the multiplicity of hand holes, manways, drain lines and vents; and b. filling the tube bundle heat exchanger with a liquid to a level above the pile of sludge.

  20. Radiolysis Concerns for Water Shielding in Fission Surface Power Applications

    SciTech Connect

    Schoenfeld, Michael P.; Anghaie, Samim

    2008-01-21

    This paper presents an overview of radiolysis concerns with regard to water shields for fission surface power. A review of the radiolysis process is presented and key parameters and trends are identified. From this understanding of the radiolytic decomposition of water, shield pressurization and corrosion are identified as the primary concerns. Existing experimental and modeling data addressing concerns are summarized. It was found that radiolysis of pure water in a closed volume results in minimal, if any net decomposition, and therefore reduces the potential for shield pressurization and corrosion.

  1. Radiolysis Model Sensitivity Analysis for a Used Fuel Storage Canister

    SciTech Connect

    Wittman, Richard S.

    2013-09-20

    This report fulfills the M3 milestone (M3FT-13PN0810027) to report on a radiolysis computer model analysis that estimates the generation of radiolytic products for a storage canister. The analysis considers radiolysis outside storage canister walls and within the canister fill gas over a possible 300-year lifetime. Previous work relied on estimates based directly on a water radiolysis G-value. This work also includes that effect with the addition of coupled kinetics for 111 reactions for 40 gas species to account for radiolytic-induced chemistry, which includes water recombination and reactions with air.

  2. λ-Radiolysis of aqueous solution of glucosides

    NASA Astrophysics Data System (ADS)

    Rongyao, Yuan; Jilan, Wu

    In this paper, three types of aqueous solution of glucoside, baicalin (I), 1, 8-dihydroxyanthraquinone-β-D-glucoside (II) and glycyrrhizin (III), have been investigated. The yields of decomposition of glucosides are determined. Their G values decrease as doses increase. Some radiolysis products are identified. The influences of different radical scavengers such as, O 2, N 2O, KCNS and isopropanol, are observed. Radiolysis is mainly caused by OH radical. Radiation induced hydrolysis of glucosidic linkage is not the main process, the proportions of dissociated aglycon to total radiolysis products are less than 10%.

  3. Reaction mechanisms in the radiolysis of peptides, polypeptides, and proteins. I. Reactions of the peptide main-chain in model systems

    SciTech Connect

    Garrison, W.M.

    1982-08-01

    The object of this review is to bring together and to correlate our present knowledge of products and mechanisms in the radiolysis of peptides, polypeptides and proteins in both aqueous and solid-state systems. Results obtained with various experimental techniques such as product analysis, competition kinetics, ESR spectroscopy and pulse radiolysis are included. Here in part I the emphasis is on the various radiation-induced reactions of the peptide main-chain in model systems. In part II the emphasis is on the radiation chemistry of side-chain loci of the aliphatic, sulfur-containing, aromatic and other unsaturated amino acid residues in similar systems. And, in part III this information on model systems is used in interpreting the mechanisms of chemical change in the radiolysis of proteins in aqueous solution and in the solid state. 60 references.

  4. A pulse radiolysis study of zinc(II)-insulin.

    PubMed

    Elliot, A J; Wilkinson, F; Armstrong, D A

    1980-07-01

    Reactions of eaq with zinc(II)-insulin at pH 6.6 and 9.0 yielded relatively low disulphide anion absorptions, suggesting eaq reacts at other sites than S-S. A similar conclusion was reached for the reation of CO2 where an even lower yield of disulphide anion was found. However, here the disulphide anion yield increased with 'prepulsing'. Simultaneously the rate constant decreased, implying that a more reactive site was 'cleaned up'. While no reaction of Br2 with insulin was observed, both OH and Cl2 reacted rapidly and predominantly at the tyrosine residues. The second order rate constants, calculated in terms of insulin monomer concentrations, are reported for eaq, CO2 and Cl2. The transient spectra qualitatively support evidence regarding the accessibility of S-S bonds and tryosine residues in the various forms of insulin as predicted from earlier studies.

  5. Picosecond pulse radiolysis of the liquid diethyl carbonate.

    PubMed

    Torche, Fayçal; El Omar, Abdel Karim; Babilotte, Philippe; Sorgues, Sébastien; Schmidhammer, Uli; Marignier, Jean-Louis; Mostafavi, Mehran; Belloni, Jacqueline

    2013-10-24

    The diethyl carbonate, DEC, is an ester that is used as a solvent in Li-ion batteries, but its behavior under ionizing radiation was unknown. The transient optical absorption spectra, the decay kinetics, and the influence of various scavengers have been studied by using the picosecond laser-triggered electron accelerator ELYSE. In neat DEC, the intense near-IR (NIR) absorption spectrum is assigned to the solvated electron. It is overlapped in the visible range by another transient but longer-lived and less intense band that is assigned to the oxidized radical DEC(-H). The solvated electron molar absorption coefficients and radiolytic yield evolution from 25 ps, the geminate recombination kinetics, and the rate constants of electron transfer reactions to scavengers are determined. The radiolytic mechanism, indicating a certain radioresistance of DEC, is compared with that for other solvents.

  6. Radiolysis of rutin in aerated ethanolic solution

    NASA Astrophysics Data System (ADS)

    Deng, Wuguo; He, Yongke; Fang, Xingwang; Wu, Jilan

    1998-12-01

    Radiolysis of rutin was performed in aerated ethanolic solution. Two major radiolytic products (RP1, RP2) were isolated by HPLC, and their possible structures were deduced from their UV, IR and MS spectra, and elementary analysis as well. The G-values of RP1 and RP2 increase with increasing rutin concentration, and in all cases both of them equal the G-value of rutin consumption. The addition of rutin leads to the decrease of G(H 2O 2) but has little effect on G(CH 3CHO). Therefore the formation of RP1 and RP2 was proposed to be from further addition of HO%s rad 2 to the phenolic radical (generated from H-abstraction by HO%s rad 2) followed by fragmentation.

  7. The Radiolysis of AmVI Solutions

    SciTech Connect

    Bruce J. Mincher

    2013-06-01

    The reduction of bismuthate-produced AmVI by 60Co gamma-rays was measured using post-irradiation UV/Vis spectroscopy. The reduction of AmVI by radiolysis was rapid, producing AmV as the sole product. Relatively low absorbed doses in the ~0.3 kGy range quantitatively reduced a solution of 2.5 x 10-4 M AmVI. The addition of bismuthate to samples during irradiation did not appear to protect AmVI from radiolytic reduction during these experiments. It was also shown here that AmV is very stable toward radiation. The quantitative reduction of the AmVI concentration here corresponds to 1.4 hours of exposure to a process solution, however the actual americium concentrations will be higher and the expected contact times short when using centrifugal contactors. Thus, the reduction rate found in these initial experiments may not be excessive.

  8. Radiolysis: Icy Satellite Atmospheres and Surface Aging

    NASA Astrophysics Data System (ADS)

    Johnson, R. E.; Carlson, R. W.; Leblanc, F.; Shematovich, V. I.

    2001-11-01

    The jovian trapped particle radiation chemically alters the Galilean satellite surfaces, a process referred to as radiolysis. This leads to the chemical alteration and decomposition of the surface materials and the production of volatiles (Johnson 2001). Radiolysis likely accounts for the darkening of the polar regions of Io (Johnson 1997), the O2 (Calvin et al 1996), peroxide (Carlson et al 1999a) and, possibly, O3 (Noll et al 1996) in icy satellite surfaces, the radiolytic sulfur cycle on Europa (Carlson et al 1999b), the production of O2 (Hall et al. 1995) and alkali atmospheres (Brown and Hill, 1996) and, possibly, the production of the CO2 atmosphere at Callisto (Carlson 1999). Results for the radiolytic processing of likely surface materials will be used to create atmospheric models and to describe surface aging. Emphasis will be on Europa's surface and atmosphere. Brown, M.E. and R.E. Hill Nature 380,229(1996) Calvin, W., et al. GRL 23, 673(1996) Carlson, R.W., Science 283,820(1999) Carlson, R.W. et al., Science 286, 97(1999a) Carlson, R.W., et al. Science 283, 2062(1999b Hall, D.T. et al. Nature 373, 677(1995) Johnson, R.E., Icarus 128, 469 (1997) 469- 471. Johnson, R.E., et al., GRL 25, 3257(1998) Johnson, R.E., In,Chemical Dynamics in Extreme Environments (R.Dessler,Ed)390 (2001) Noll, K.S. et al., Science 273, 607(1996)

  9. Radiolysis of aqueous solutions of 2-aminoethanethiosulfuric acid. [Gamma radiation

    SciTech Connect

    Grachev, S.A.; Koroleva, I.K.; Kropachev, E.V.; Litvyakova, G.I.

    1982-07-10

    In the radiolysis products of aerated and deaerated solutions of the 2-aminoethanethiosulfuric acid the authors have identified cystamine monoxide, cystamine, taurine, mercamine, the sulfate ion, the sulfite ion, and the dithionate ion. The yields of these products under different conditions have been determined. Results indicated that the sulfate ion is formed both from the divalent and the hexavalent sulfur atom of the 2-aminoethanethiosulfuric acid moelcule. A possible radiolysis mechanism is discussed.

  10. Method of estimating pulse response using an impedance spectrum

    DOEpatents

    Morrison, John L; Morrison, William H; Christophersen, Jon P; Motloch, Chester G

    2014-10-21

    Electrochemical Impedance Spectrum data are used to predict pulse performance of an energy storage device. The impedance spectrum may be obtained in-situ. A simulation waveform includes a pulse wave with a period greater than or equal to the lowest frequency used in the impedance measurement. Fourier series coefficients of the pulse train can be obtained. The number of harmonic constituents in the Fourier series are selected so as to appropriately resolve the response, but the maximum frequency should be less than or equal to the highest frequency used in the impedance measurement. Using a current pulse as an example, the Fourier coefficients of the pulse are multiplied by the impedance spectrum at corresponding frequencies to obtain Fourier coefficients of the voltage response to the desired pulse. The Fourier coefficients of the response are then summed and reassembled to obtain the overall time domain estimate of the voltage using the Fourier series analysis.

  11. The radiolysis and radioracemization of amino acids on clays

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Hall, H.; Chow, G.; Yi, L.; Lemmon, R. M.

    1985-01-01

    The effects of the surfaces of kaolinite and bentonite clays on the radiolysis and radioracemization of L-leucine and its hydrochloride salt have been investigated experimentally. L-leucine and its hydrochloride salt were deposited on the clays and the amino acid/clay preparations were irradiated by a Co-60 gamma-ray source which induced 2-89 percent radiolysis. The efficiency of radiolysis and radioracemization were measured using gas chromatography. Results were obtained for leucine in 0.1 M aqueous solution for comparison with the clay-deposted leucine and leucine hydrochloride. It is found that radiolysis and radioracemization in the samples occurred according to a pseudo-first-order rate law. Comparison of the specific rate constants showed that leucine and its hydrochloride salt were the most resistant to both radiolysis and radioracemization, followed by leucine and its hydrochloride salt on kaolin. Leucine and its HCl salt on bentonite, and leucine in aqueous solution were found to be the least resistant to radiolysis and radioracemization. The experimental results are intepreted with respect to the Vester-Ulbricht mechanism for the origin of optical activity.

  12. The radiolysis and radioracemization of amino acids on clays

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Hall, H.; Chow, G.; Yi, L.; Lemmon, R. M.

    1985-01-01

    The effects of the surfaces of kaolinite and bentonite clays on the radiolysis and radioracemization of L-leucine and its hydrochloride salt have been investigated experimentally. L-leucine and its hydrochloride salt were deposited on the clays and the amino acid/clay preparations were irradiated by a Co-60 gamma-ray source which induced 2-89 percent radiolysis. The efficiency of radiolysis and radioracemization were measured using gas chromatography. Results were obtained for leucine in 0.1 M aqueous solution for comparison with the clay-deposted leucine and leucine hydrochloride. It is found that radiolysis and radioracemization in the samples occurred according to a pseudo-first-order rate law. Comparison of the specific rate constants showed that leucine and its hydrochloride salt were the most resistant to both radiolysis and radioracemization, followed by leucine and its hydrochloride salt on kaolin. Leucine and its HCl salt on bentonite, and leucine in aqueous solution were found to be the least resistant to radiolysis and radioracemization. The experimental results are intepreted with respect to the Vester-Ulbricht mechanism for the origin of optical activity.

  13. Gas production in the radiolysis of poly(vinyl chloride).

    PubMed

    LaVerne, Jay A; Carrasco-Flores, Eduardo A; Araos, M S; Pimblott, Simon M

    2008-04-17

    The yields of H2 and Cl- were determined in the radiolysis of deaerated, aerated, and water mixtures of poly(vinyl chloride) (PVC) powders with gamma-rays and 5 MeV He ions. H2 yields with gamma-rays are low at about 0.25 molecule/100 eV and they double with He ion radiolysis indicating a second order formation process. The production of H2 in the gamma-radiolysis of water-PVC mixtures is much greater than expected from the weight fraction of the components and is due to acidification of the aqueous phase by the evolution of HCl from the polymer. Cl- yields in the gamma-radiolysis of PVC with number average weights of 22,000, 47,000, and 99,000 Daltons are 19.6, 33.8, and 32.5 atoms/100 eV. Cl- continuously evolves from the polymer for days following radiolysis. The extremely large yields suggest that a chain process involving radicals stabilized on the polymeric chain are responsible. Reflectance UV/vis and infrared spectroscopy show subtle changes in the PVC with radiolysis while UV/vis absorption spectra clearly indicate the formation of polyenes with 1 to 11 units. Cl- formation is probably initiated by Cl radical production followed by an electron rearrangement mechanism along the PVC chain to produce more Cl- and polyenes.

  14. Selecting ethanol as a model organic solvent in radiation chemistry—I. Radiolysis of acetone-ethanol system

    NASA Astrophysics Data System (ADS)

    Haofang, Jin; Jilan, Wu; Xianming, Pan; Xujia, Zhang

    1996-04-01

    Radiolysis of acetone-ethanol solution [Zhang, Wu and Zhou (1994) Radiat. Phys. Chem.43, 335] has been further studied in this work. The dependences of G values of the final γ radiolytic products such as H 2, 2,3-butanediol and acetaldehyde on acetone concentrations in liquid ethanol were obtained. New information was provided that except the detected new product 2-methyl-2,3-butanedio (Zhang et al., 1994), another new final product isopropanol was also found and material balance between intermediates and major final products was obtained. In addition, a ratio of rate constants k(e s- + CH 3CHO)/ k(e s- + CH 3COCH 3) = 0.96 was calculated by computer simulation, which is in good agreement with the result obtained from pulse radiolysis experiments [Milinchuk and Tupikov (1989) Organic Radiation Chemistry Handbook].

  15. Multi-wavelength photoplethysmography method for skin arterial pulse extraction

    PubMed Central

    Liu, Jing; Yan, Bryan Ping-Yen; Dai, Wen-Xuan; Ding, Xiao-Rong; Zhang, Yuan-Ting; Zhao, Ni

    2016-01-01

    In this work, we present a multi-wavelength (MW) PPG method exploiting the wavelength dependence of light penetration in skin tissue to provide depth resolution of skin blood pulsation. The MW PPG system requires two to three light sources in different wavelengths and extracts the arterial blood pulsation through a multi-wavelength multi-layer light-skin interaction model, which removes the capillary pulsation (determined from the short-wavelength PPG signal) from the long-wavelength PPG signal using absorption weighting factors that are quasi-analytically calibrated. The extracted pulsations are used to calculate blood pressure (BP) through pulse transit time (PTT), and the results are compared with those obtained from the single wavelength PPG method. The comparative study is clinically performed on 20 subjects including 10 patients diagnosed with cardiovascular diseases and 10 healthy subjects. The result demonstrates that the MW PPG method significantly improves the measurement accuracy of systolic BP (SBP), reducing the mean absolute difference between the reference and the estimated SBP values from 5.7 mmHg (for single-wavelength PPG) to 2.9 mmHg (for three-wavelength PPG). PMID:27867733

  16. Monitoring of concrete structures using the ultrasonic pulse velocity method

    NASA Astrophysics Data System (ADS)

    Karaiskos, G.; Deraemaeker, A.; Aggelis, D. G.; Van Hemelrijck, D.

    2015-11-01

    Concrete is the material most produced by humanity. Its popularity is mainly based on its low production cost and great structural design flexibility. Its operational and ambient loadings including environmental effects have a great impact in the performance and overall cost of concrete structures. Thus, the quality control, the structural assessment, the maintenance and the reliable prolongation of the operational service life of the existing concrete structures have become a major issue. In the recent years, non-destructive testing (NDT) is becoming increasingly essential for reliable and affordable quality control and integrity assessment not only during the construction of new concrete structures, but also for the existing ones. Choosing the right inspection technique is always followed by a compromise between its performance and cost. In the present paper, the ultrasonic pulse velocity (UPV) method, which is the most well known and widely accepted ultrasonic concrete NDT method, is thoroughly reviewed and compared with other well-established NDT approaches. Their principles, inherent limitations and reliability are reviewed. In addition, while the majority of the current UPV techniques are based on the use of piezoelectric transducers held on the surface of the concrete, special attention is paid to a very promising technique using low-cost and aggregate-size piezoelectric transducers embedded in the material. That technique has been evaluated based on a series of parameters, such as the ease of use, cost, reliability and performance.

  17. Method and apparatus for stabilizing pulsed microwave amplifiers

    DOEpatents

    Hopkins, D.B.

    1993-01-26

    Phase and amplitude variations at the output of a high power pulsed microwave amplifier arising from instabilities of the driving electron beam are suppressed with a feed-forward system that can stabilize pulses which are too brief for regulation by conventional feedback techniques. Such variations tend to be similar during successive pulses. The variations are detected during each pulse by comparing the amplifier output with the low power input signal to obtain phase and amplitude error signals. This enables storage of phase and amplitude correction signals which are used to make compensating changes in the low power input signal during the following amplifier output pulse which suppress the variations. In the preferred form of the invention, successive increments of the correction signals for each pulse are stored in separate channels of a multi-channel storage. Sequential readout of the increments during the next pulse provides variable control voltages to a voltage controlled phase shifter and voltage controlled amplitude modulator in the amplifier input signal path.

  18. Method and apparatus for stabilizing pulsed microwave amplifiers

    DOEpatents

    Hopkins, Donald B.

    1993-01-01

    Phase and amplitude variations at the output of a high power pulsed microwave amplifier arising from instabilities of the driving electron beam are suppressed with a feed-forward system that can stabilize pulses which are too brief for regulation by conventional feedback techniques. Such variations tend to be similar during successive pulses. The variations are detected during each pulse by comparing the amplifier output with the low power input signal to obtain phase and amplitude error signals. This enables storage of phase and amplitude correction signals which are used to make compensating changes in the low power input signal during the following amplifier output pulse which suppress the variations. In the preferred form of the invention, successive increments of the correction signals for each pulse are stored in separate channels of a multi-channel storage. Sequential readout of the increments during the next pulse provides variable control voltages to a voltage controlled phase shifter and voltage controlled amplitude modulator in the amplifier input signal path.

  19. Method of estimating tissue attenuation using wideband ultrasonic pulse and apparatus for use therein

    SciTech Connect

    Flax, S.W.

    1986-11-11

    This patent describes a method of estimating tissue attenuation of ultrasound energy comprising the steps of: transmitting a wide band ultrasonic pulse into the tissue, the pulse having a frequency spectrum with a center frequency, detecting the pulse as reflected by the tissue, estimating decay of a measure of amplitude of the reflected pulse between two levels in the tissue to approximate the slope of the decay, estimating center frequency of the reflected pulse between the two levels, and obtaining tissue attenuation from the approximated slope of a measure of amplitude and the center frequency.

  20. New methods of generation of ultrashort laser pulses for ranging

    NASA Technical Reports Server (NTRS)

    Jelinkova, Helena; Hamal, Karel; Kubecek, V.; Prochazka, Ivan

    1993-01-01

    To reach the millimeter satellite laser ranging accuracy, the goal for nineties, new laser ranging techniques have to be applied. To increase the laser ranging precision, the application of the ultrashort laser pulses in connection with the new signal detection and processing techniques, is inevitable. The two wavelength laser ranging is one of the ways to measure the atmospheric dispersion to improve the existing atmospheric correction models and hence, to increase the overall system ranging accuracy to the desired value. We are presenting a review of several nonstandard techniques of ultrashort laser pulses generation, which may be utilized for laser ranging: compression of the nanosecond pulses using stimulated Brillouin and Raman backscattering; compression of the mode-locked pulses using Raman backscattering; passive mode-locking technique with nonlinear mirror; and passive mode-locking technique with the negative feedback.

  1. Apparatus and method for characterizing ultrafast polarization varying optical pulses

    DOEpatents

    Smirl, Arthur; Trebino, Rick P.

    1999-08-10

    Practical techniques are described for characterizing ultrafast potentially ultraweak, ultrashort optical pulses. The techniques are particularly suited to the measurement of signals from nonlinear optical materials characterization experiments, whose signals are generally too weak for full characterization using conventional techniques.

  2. Methods of Attosecond X-Ray Pulse Generation

    SciTech Connect

    Zholents, Alexander

    2005-05-08

    We review several proposals for generation of solitary attosecond pulses using two types of free electron lasers which are envisioned as future light sources for studies of ultra-fast dynamics using soft and hard x-rays.

  3. Further Methods for the Generation of Ultrashort Optical Pulses

    NASA Astrophysics Data System (ADS)

    Hirlimann, C.

    Up to the beginning of the sixties, the shortest measurable time duration was of the order of one nanosecond (10-9 s). Short pulses were produced through the generation of short electrical discharges. After the laser was invented in 1960, the situation quite rapidly changed. In 1965, the picosecond (10-12 s) regime was reached by placing a saturable absorber inside a laser cavity. Twenty years of continuous progress led to the production of light pulses of less than 10 femtoseconds. In the race towards ever shorter pulses, recent developments in the generation of tabletop X-ray lasers have opened the way to dynamical studies in the attosecond (10-18 s)regime [4.1-2]. In the meantime, progress was made on the tunability of the pulsed-laser sources. Today's tunability extends from the near ultraviolet to the near infrared [4.2-6].

  4. Radiolysis of water with aluminum oxide surfaces

    NASA Astrophysics Data System (ADS)

    Reiff, Sarah C.; LaVerne, Jay A.

    2017-02-01

    Aluminum oxide, Al2O3, nanoparticles with water were irradiated with γ-rays and 5 MeV He ions followed by the determination of the production of molecular hydrogen, H2, and characterization of changes in the particle surface. Surface analysis techniques included: diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), nitrogen absorption with the Brunauer - Emmett - Teller (BET) methodology for surface area determination, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Production of H2 by γ-ray radiolysis was determined for samples with adsorbed water and for Al2O3 - water slurries. For Al2O3 samples with adsorbed water, the radiation chemical yield of H2 was measured as 80±20 molecules/100 eV (1 molecule/100 eV=1.04×10-7 mol/J). The yield of H2 was observed to decrease as the amount of water present in the Al2O3 - water slurries increased. Surface studies indicated that the α-phase Al2O3 samples changed phase following irradiation by He ions, and that the oxyhydroxide layer, present on the pristine sample, is removed by γ-ray and He ion irradiation.

  5. Radical Cations and Acid Protection during Radiolysis

    SciTech Connect

    Bruce J. Mincher; Christopher A. Zarzana; Stephen P. Mezyk

    2016-09-01

    Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO3. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

  6. Combinations of Aromatic and Aliphatic Radiolysis.

    PubMed

    LaVerne, Jay A; Dowling-Medley, Jennifer

    2015-10-08

    The production of H(2) in the radiolysis of benzene, methylbenzene (toluene), ethylbenzene, butylbenzene, and hexylbenzene with γ-rays, 2-10 MeV protons, 5-20 MeV helium ions, and 10-30 MeV carbon ions is used as a probe of the overall radiation sensitivity and to determine the relative contributions of aromatic and aliphatic entities in mixed hydrocarbons. The addition of an aliphatic side chain with progressively from one to six carbon lengths to benzene increases the H(2) yield with γ-rays, but the yield seems to reach a plateau far below that found from a simple aliphatic such as cyclohexane. There is a large increase in H(2) with LET (linear energy transfer) for all of the substituted benzenes, which indicates that the main process for H(2) formation is a second-order process and dominated by the aromatic entity. The addition of a small amount of benzene to cyclohexane can lower the H(2) yield from the value expected from a simple mixture law. A 50:50% volume mixture of benzene-cyclohexane has essentially the same H(2) yield as cyclohexylbenzene at a wide variation in LET, suggesting that intermolecular energy transfer is as efficient as intramolecular energy transfer.

  7. Which calibration-pulse location method is robust?. [for satellite imaging instruments

    NASA Technical Reports Server (NTRS)

    Gunther, F. J.

    1985-01-01

    The Threshold method, with high threshold and contiguous-block parameter values, was found to be a robust method of locating calibration pulses in the presence of light-leak and shutter-edge pulses within the calibration window. Tests used digitized calibration-window background and light-pulse data from the Landsat-5 Thematic Mapper (TM) instrument, analyzed by special software on an Apple II+ personal computer and on a VAX 11/780 minicomputer.

  8. The radiolysis and radioracemization of amino acids on silica surfaces

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Lemmon, R. M.

    1981-01-01

    Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.

  9. The radiolysis and radioracemization of amino acids on silica surfaces

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Lemmon, R. M.

    1981-01-01

    Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.

  10. Plutonium and Americium Alpha Radiolysis of Nitric Acid Solutions.

    PubMed

    Horne, Gregory P; Gregson, Colin R; Sims, Howard E; Orr, Robin M; Taylor, Robin J; Pimblott, Simon M

    2017-02-02

    The yield of HNO2, as a function of absorbed dose and HNO3 concentration, from the α-radiolysis of aerated HNO3 solutions containing plutonium or americium has been investigated. There are significant differences in the yields measured from solutions of the two different radionuclides. For 0.1 mol dm(-3) HNO3 solutions, the radiolytic yield of HNO2 produced by americium α-decay is below the detection limit, whereas for plutonium α-decay the yield is considerably greater than that found previously for γ-radiolysis. The differences between the solutions of the two radionuclides are a consequence of redox reactions involving plutonium and the products of aqueous HNO3 radiolysis, in particular H2O2 and HNO2 and its precursors. This radiation chemical behavior is HNO3 concentration dependent with the differences between plutonium and americium α-radiolysis decreasing with increasing HNO3 concentration. This change may be interpreted as a combination of α-radiolysis direct effects and acidity influencing the plutonium oxidation state distribution, which in turn affects the radiation chemistry of the system.

  11. Apparatus for and method of operating a cylindrical pulsed induction mass launcher

    DOEpatents

    Cowan, Jr., Maynard; Duggin, Billy W.; Widner, Melvin M.

    1992-01-01

    An electromagnetic cylindrical projectile mass launcher and a method of operation is provided which includes a cylindrical projectile having a conducting armature, a cylindrical barrel in which the armature is received, a plurality of electromagnetic drive coil stages, a plurality of pulse energy sources, and a pulsed power arrangement for generating magnetic pulses forming a pulsed magnetic wave along the length of the launcher barrel. The pulsed magnetic wave provides a propelling force on the projectile along the drive coil. The pulsed magnetic wave of the drive coil stages is advanced along the armature faster than the projectile to thereby generate an induced current wave in the armature. The pulsed generation of the magnetic wave minimizes electromagnetic heating of the projectile and provides for smooth acceleration of the projectile through the barrel of the launcher.

  12. Apparatus for and method of operating a cylindrical pulsed induction mass launcher

    DOEpatents

    Cowan, M. Jr.; Duggin, B.W.; Widner, M.M.

    1992-06-30

    An electromagnetic cylindrical projectile mass launcher and a method of operation is provided which includes a cylindrical projectile having a conducting armature, a cylindrical barrel in which the armature is received, a plurality of electromagnetic drive coil stages, a plurality of pulse energy sources, and a pulsed power arrangement for generating magnetic pulses forming a pulsed magnetic wave along the length of the launcher barrel. The pulsed magnetic wave provides a propelling force on the projectile along the drive coil. The pulsed magnetic wave of the drive coil stages is advanced along the armature faster than the projectile to thereby generate an induced current wave in the armature. The pulsed generation of the magnetic wave minimizes electromagnetic heating of the projectile and provides for smooth acceleration of the projectile through the barrel of the launcher. 2 figs.

  13. METHOD AND APPARATUS FOR PULSING A CHARGED PARTICLE BEAM

    DOEpatents

    Aaland, K.; Kuenning, R.W.; Harmon, R.K.

    1961-05-01

    A system is offered for pulsing a continuous beam of charged particles to form beam pulses that are consistently rectangular and of precise time durations which may be varied over an extremely wide range at a widely variable range of repetition rates. The system generally comprises spaced deflection plates on opposite sides of a beam axis in between which a unidirectional bias field is established to deflect the beam for impingement on an off-axis collector. The bias field is periodically neutralized by the application of fast rise time substantially rectangular pulses to one of the deflection plates in opposition to the bias field and then after a time delay to the other deflection plate in aiding relation to the bias field and during the flat crest portion of the bias opposing pulses. The voltage distribution of the resulting deflection field then includes neutral or zero portions which are of symmetrical substantially rectangular configuration relative to time and during which the beam axially passes the collector in the form of a substantially rectangular beam pulse.

  14. Electrochemical synthesis of nanosized hydroxyapatite by pulsed direct current method

    SciTech Connect

    Nur, Adrian; Rahmawati, Alifah; Ilmi, Noor Izzati; Affandi, Samsudin; Widjaja, Arief

    2014-02-24

    Synthesis of nanosized of hydroxyapatite (HA) by electrochemical pulsed direct current (PDC) method has been studied. The aim of this work is to study the influence of various PDC parameters (pH initial, electrode distance, duty cycle, frequency, and amplitude) on particle surface area of HA powders. The electrochemical synthesis was prepared in solution Ca{sup 2+}/EDTA{sup 4−}/PO{sub 4}{sup 3+} at concentration 0.25/0.25/0.15 M for 24 h. The electrochemical cell was consisted of two carbon rectangular electrodes connected to a function generator to produce PDC. There were two treatments for particles after electrosynthesized, namely without aging and aged for 2 days at 40 °C. For both cases, the particles were filtered and washed by demineralized water to eliminate the impurities and unreacted reactants. Then, the particles were dried at 100 °C for 2 days. The dried particles were characterized by X-ray diffraction, surface area analyzer, scanning electron microscopy (SEM), Fourier transform infrared spectra and thermogravimetric and differential thermal analysis. HA particles can be produced when the initial pH > 6. The aging process has significant effect on the produced HA particles. SEM images of HA particles showed that the powders consisted of agglomerates composed of fine crystallites and have morphology plate-like and sphere. The surface area of HA particles is in the range of 25 – 91 m{sup 2}/g. The largest particle surface area of HA was produced at 4 cm electrode distance, 80% cycle duty, frequency 0.1 Hz, amplitude 9 V and with aging process.

  15. Investigation on Novel Methods to Increase Specific Thrust in Pulse Detonation Engines via Imploding Detonations

    DTIC Science & Technology

    2009-12-01

    NOVEL METHODS TO INCREASE SPECIFIC THRUST IN PULSE DETONATION ENGINES VIA IMPLODING DETONATIONS by Ivan Chin Kian Ho December 2009 Thesis...Increase Specific Thrust in Pulse Detonation Engines via Imploding Detonations 6. AUTHOR(S) Ivan Chin Kian Ho 5. FUNDING NUMBERS 7. PERFORMING...long run distance for transition to detonation, thus, potentially affecting specific thrust . Novel methods via imploding detonations were

  16. Method for generating high-energy and high repetition rate laser pulses from CW amplifiers

    SciTech Connect

    Zhang, Shukui

    2013-06-18

    A method for obtaining high-energy, high repetition rate laser pulses simultaneously using continuous wave (CW) amplifiers is described. The method provides for generating micro-joule level energy in pico-second laser pulses at Mega-hertz repetition rates.

  17. Method for spatially modulating X-ray pulses using MEMS-based X-ray optics

    DOEpatents

    Lopez, Daniel; Shenoy, Gopal; Wang, Jin; Walko, Donald A.; Jung, Il-Woong; Mukhopadhyay, Deepkishore

    2015-03-10

    A method and apparatus are provided for spatially modulating X-rays or X-ray pulses using microelectromechanical systems (MEMS) based X-ray optics. A torsionally-oscillating MEMS micromirror and a method of leveraging the grazing-angle reflection property are provided to modulate X-ray pulses with a high-degree of controllability.

  18. Experimental validation of a high voltage pulse measurement method.

    SciTech Connect

    Cular, Stefan; Patel, Nishant Bhupendra; Branch, Darren W.

    2013-09-01

    This report describes X-cut lithium niobates (LiNbO3) utilization for voltage sensing by monitoring the acoustic wave propagation changes through LiNbO3 resulting from applied voltage. Direct current (DC), alternating current (AC) and pulsed voltage signals were applied to the crystal. Voltage induced shift in acoustic wave propagation time scaled quadratically for DC and AC voltages and linearly for pulsed voltages. The measured values ranged from 10 - 273 ps and 189 ps 2 ns for DC and non-DC voltages, respectively. Data suggests LiNbO3 has a frequency sensitive response to voltage. If voltage source error is eliminated through physical modeling from the uncertainty budget, the sensors U95 estimated combined uncertainty could decrease to ~0.025% for DC, AC, and pulsed voltage measurements.

  19. Summary Report on Gamma Radiolysis of TBP/n-dodecane in the Presence of Nitric Acid Using the Radiolysis/Hydrolysis Test Loop

    SciTech Connect

    Dean R. Peterman; Bruce J. Mincher; Catherine L. Riddle; Richard D. Tillotson

    2010-08-01

    processes containing TBP that are being developed to support advanced aqueous separations processes. Initial experimental results are consistent with existing literature reports regarding TBP/n-dodecane radiolysis. Additionally, the gamma dose rate has been characterized within the test loop and analytical methods have been developed for the characterization and quantification of radiolytic degradation products.

  20. Modeling of water radiolysis at spallation neutron sources

    SciTech Connect

    Daemen, L.L.; Kanner, G.S.; Lillard, R.S.; Butt, D.P.; Brun, T.O.; Sommer, W.F.

    1998-12-01

    In spallation neutron sources neutrons are produced when a beam of high-energy particles (e.g., 1 GeV protons) collides with a (water-cooled) heavy metal target such as tungsten. The resulting spallation reactions produce a complex radiation environment (which differs from typical conditions at fission and fusion reactors) leading to the radiolysis of water molecules. Most water radiolysis products are short-lived but extremely reactive. When formed in the vicinity of the target surface they can react with metal atoms, thereby contributing to target corrosion. The authors describe the results of calculations and experiments performed at los alamos to determine the impact on target corrosion of water radiolysis in the spallation radiation environment. The computational methodology relies on the use of the Los Alamos radiation transport code, LAHET, to determine the radiation environment, and the AEA code, FACSIMILE, to model reaction-diffusion processes.

  1. Apparatus for and method of operating a cylindrical pulsed induction mass launcher

    SciTech Connect

    Cowan, M. Jr.; Duggin, B.W.; Widner, M.M.

    1990-12-06

    In accordance with the one aspect of the invention, an electromagnetic projectile launcher is provided which comprises: a conducting projectile, a barrel that receives the projectile, a plurality of electromagnetic drive coils, a plurality of pulsed energy sources, and pulse power means for generating a sequence of pulses forming a pulsed magnetic wave within the drive coil for propelling the projectile along the barrel, wherein the pulsed magnetic wave of the drive coil is advanced along the barrel faster than the projectile to thereby induce a current wave in the armature of the projectile and thereby minimize electromagnetic heating of the projectile and provide nearly constant acceleration of the projectile. In accordance with another aspect of the invention, a method is provided for propelling a projectile within a pulsed induction electromagnetic coil launcher, wherein the method comprises the steps of: generating a sequence of pulses forming a pulsed magnetic wave within the coil launcher, applying the pulsed magnetic wave initially at the aft end of the projectile to accelerate the projectile within the coil launcher, and advancing the position of the pulsed magnetic wave relative to the projectile to thereby generate an induced current wave in the armature, such that electromagnetic heating of the projectile is minimized and acceleration is nearly constant.

  2. Systolic Blood Pressure Accuracy Enhancement in the Electronic Palpation Method Using Pulse Waveform

    DTIC Science & Technology

    2007-11-02

    1 of 4 SYSTOLIC BLOOD PRESSURE ACCURACY ENHANCEMENT IN THE ELECTRONIC PALPATION METHOD USING PULSE WAVEFORM H. S. S. Sorvoja1, R. A. Myllylä1...systolic blood pressure measurements based on pulse waveform. A set of measurement was carried out with elderly cardiac surgery patients. The experiments... blood pressure . Systolic pressure errors were defined and correlations with other specific values, like pressure rise time, pulse wave velocity

  3. Formation of stable radicals in the radiolysis of hexafluoropropylene

    SciTech Connect

    Allayarov, S.R.; Barkalov, I.M.; Lebedeva, M.Yu.; Loginova, N.N.; Mikhailov, A.I.

    1986-08-20

    The radiolysis of the dimer (perfluoro-4-methyl-2-pentene) and trimer (perfluoro-2,4-dimethyl-3-ethyl-2-pentene) of hexafluoropropylene (HFP) gives thermally stable perfluoroalkyl radicals. The stability of these radicals is apparently related to the steric isolation of the unpaired electron. The formation of a growing oligomer chain perfluoroalkyl radical which is stable in the liquid phase is observed upon the radiolysis of hexafluoropropylene. The radio-chemical yield of such a radical G approx. 0.05 x 10/sup -2/ eV. The low capacity of hexafluoropropylene to undergo homopolymerization is related to the formation of similar inactive radicals.

  4. The radiolysis and racemization of leucine on proton irradiation

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Lemmon, R. M.; Conzett, H. E.

    1982-01-01

    D- and L-Leucine have been subjected to 39-55 percent radiolysis using 0.11 MeV protons, both with the proton beam passing through the sample or being absorbed by it and with quenching the sample immediately on completion of irradiation or after a 21-day interval. Racemization was small (1.1-1.7 percent) and comparable in all cases, suggesting that radioracemization and secondary degradative effects were not important factors in the recent unsuccessful attempts to induce optical activity in DL-Leucine by partial radiolysis using 0-11 MeV longitudinally polarized protons.

  5. The radiolysis and racemization of leucine on proton irradiation

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Lemmon, R. M.; Conzett, H. E.

    1982-01-01

    D- and L-Leucine have been subjected to 39-55 percent radiolysis using 0.11 MeV protons, both with the proton beam passing through the sample or being absorbed by it and with quenching the sample immediately on completion of irradiation or after a 21-day interval. Racemization was small (1.1-1.7 percent) and comparable in all cases, suggesting that radioracemization and secondary degradative effects were not important factors in the recent unsuccessful attempts to induce optical activity in DL-Leucine by partial radiolysis using 0-11 MeV longitudinally polarized protons.

  6. Apparatus and method for characterizing ultrafast polarization varying optical pulses

    DOEpatents

    Smirl, A.; Trebino, R.P.

    1999-08-10

    Practical techniques are described for characterizing ultrafast potentially ultraweak, ultrashort optical pulses. The techniques are particularly suited to the measurement of signals from nonlinear optical materials characterization experiments, whose signals are generally too weak for full characterization using conventional techniques. 2 figs.

  7. A Novel Sterilization Method Using Pulsed Discharge Plasma

    NASA Astrophysics Data System (ADS)

    Wang, Xi-lu; Akira, Mizuno; Shijin, Katsura

    1998-01-01

    Pulsed discharge plasma(PDP) has been used to kill bacteria and the curves of the survival rate of bacteria against treatment time are obtained. Irreversible structural change in the cell membrane is caused by PDP and the cell is thus killed. The sterilization mechanism is analyzed.

  8. Summary of TRUEX Radiolysis Testing Using the INL Radiolysis Test Loop

    SciTech Connect

    Dean R. Peterman; Lonnie G. Olson; Rocklan G. McDowell; Gracy Elias; Jack D. Law

    2012-03-01

    The INL radiolysis and hydrolysis test loop has been used to evaluate the effects of hydrolytic and radiolytic degradation upon the efficacy of the TRUEX flowsheet for the recovery of trivalent actinides and lanthanides from acidic solution. Repeated irradiation and subsequent re-conditioning cycles did result in a significant decrease in the concentration of the TBP and CMPO extractants in the TRUEX solvent and a corresponding decrease in americium and europium extraction distributions. However, the build-up of solvent degradation products upon {gamma}-irradiation, had little impact upon the efficiency of the stripping section of the TRUEX flowsheet. Operation of the TRUEX flowsheet would require careful monitoring to ensure extraction distributions are maintained at acceptable levels.

  9. TRUEX Radiolysis Testing Using the INL Radiolysis Test Loop: FY-2012 Status Report

    SciTech Connect

    Dean R. Peterman; Lonnie G. Olson; Richard D. Tillotson; Rocklan G. McDowell; Jack D. Law

    2012-09-01

    The INL radiolysis test loop has been used to evaluate the affect of radiolytic degradation upon the efficacy of the strip section of the TRUEX flowsheet for the recovery of trivalent actinides and lanthanides from acidic solution. The nominal composition of the TRUEX solvent used in this study is 0.2 M CMPO and 1.4 M TBP dissolved in n-dodecane and the nominal composition of the TRUEX strip solution is 1.5 M lactic acid and 0.050 M diethylenetriaminepentaacetic acid. Gamma irradiation of a mixture of TRUEX process solvent and stripping solution in the test loop does not adversely impact flowsheet performance as measured by stripping americium ratios. The observed increase in americium stripping distribution ratios with increasing absorbed dose indicates the radiolytic production of organic soluble degradation compounds.

  10. Method and apparatus for producing durationally short ultraviolet or X-ray laser pulses

    DOEpatents

    MacGowan, Brian J.; Matthews, Dennis L.; Trebes, James E.

    1988-01-01

    A method and apparatus is disclosed for producing ultraviolet or X-ray laser pulses of short duration (32). An ultraviolet or X-ray laser pulse of long duration (12) is progressively refracted, across the surface of an opaque barrier (28), by a streaming plasma (22) that is produced by illuminating a solid target (16, 18) with a pulse of conventional line focused high power laser radiation (20). The short pulse of ultraviolet or X-ray laser radiation (32), which may be amplified to high power (40, 42), is separated out by passage through a slit aperture (30) in the opaque barrier (28).

  11. Method and apparatus for producing durationally short ultraviolet or x-ray laser pulses

    DOEpatents

    MacGowan, B.J.; Matthews, D.L.; Trebes, J.E.

    1987-05-05

    A method and apparatus is disclosed for producing ultraviolet or x- ray laser pulses of short duration. An ultraviolet or x-ray laser pulse of long duration is progressively refracted, across the surface of an opaque barrier, by a streaming plasma that is produced by illuminating a solid target with a pulse of conventional line focused high power laser radiation. The short pulse of ultraviolet or x-ray laser radiation, which may be amplified to high power, is separated out by passage through a slit aperture in the opaque barrier.

  12. Method and apparatus for providing pulse pile-up correction in charge quantizing radiation detection systems

    DOEpatents

    Britton, Jr., Charles L.; Wintenberg, Alan L.

    1993-01-01

    A radiation detection method and system for continuously correcting the quantization of detected charge during pulse pile-up conditions. Charge pulses from a radiation detector responsive to the energy of detected radiation events are converted to voltage pulses of predetermined shape whose peak amplitudes are proportional to the quantity of charge of each corresponding detected event by means of a charge-sensitive preamplifier. These peak amplitudes are sampled and stored sequentially in accordance with their respective times of occurrence. Based on the stored peak amplitudes and times of occurrence, a correction factor is generated which represents the fraction of a previous pulses influence on a preceding pulse peak amplitude. This correction factor is subtracted from the following pulse amplitude in a summing amplifier whose output then represents the corrected charge quantity measurement.

  13. Method of eliminating effects of spurious free induction decay NMR signal caused by imperfect 180 degrees pulses

    SciTech Connect

    Bottomley, P.A.; Edelstein, W.A.

    1984-11-20

    A method for eliminating the effects of a spurious free induction decay (FID) NMR signal due to imperfect 180/sup 0/ RF pulses comprises applying a large magnitude, short duration magnetic field gradient pulse, termed the ''crusher'' pulse immediately following the 180/sup 0/ pulse. When the method is employed with NMR pulse sequences in which the 180/sup 0/ pulse is part of a spin echo type refocusing RF pulse sequence, the 180/sup 0/ pulse is preceded by a magnetic field gradient pulse termed the ''primer'', having an equal integral with respect to time as the crusher pulse. The method is effective in removing NMR image artifacts produced by spurious FID in both planar and three-dimensional NMR imaging methods.

  14. Method and apparatus for sputtering utilizing an apertured electrode and a pulsed substrate bias

    NASA Technical Reports Server (NTRS)

    Przybyszewski, J. S.; Shaltens, R. K. (Inventor)

    1973-01-01

    The method and equipment used for sputtering by use of an apertured electrode and a pulsed substrate bias are discussed. The technique combines the advantages of ion plating with the versatility of a radio frequency sputtered source. Electroplating is accomplished by passing a pulsed high voltage direct current to the article being plated during radio frequency sputtering.

  15. Valine radiolysis by MeV ions

    NASA Astrophysics Data System (ADS)

    Da Silveira, Enio

    2016-07-01

    Valine, (CH3)2 CHCH (NH2) COOH, is a protein amino acid that has been identified in extraterrestrial environments and in the Murchison meteorite [1]. The knowledge of half-lives of small organic molecules under ionizing radiation is important for the setup of models describing the spread out of prebiotics across the Solar System or the Galaxy. We have investigated typical effects of MeV cosmic ray ions on prebiotic molecules in laboratory by impinging ions produced by the PUC-Rio Van de Graaff accelerator. Pure valine films, deposited by evaporation on KBr substrates, were irradiated by H ^{+}, He ^{+} and N ^{+} ion beams, from 0.5 to 1.5 MeV and up to a fluence of 10 ^{15} projectiles/cm ^{2}. The sample temperature was varied from 10 K to 300 K. The irradiation was interrupted several times for Mid-FTIR analysis of the sample. The main findings are: 1- The column density of the valine decreases exponentially with fluence. 2- In some cases, a second exponential appears in the beginning of irradiation; this feature has been attributed to sample compaction by the ion beam [2]. 3- Destruction cross sections of valine are in the 10 ^{-15} cm ^{2} range, while compaction cross sections are in the 10 ^{-14} cm ^{2} range. 4- Destruction cross section increases with the stopping power of the beam and also with the sample temperature. 5- Surprisingly, during the radiolysis of valine, just CO _{2} is seen by as a daughter molecule formed in the bulk. 6- After long beam fluence, also a CO peak appears in the infrared spectrum; this species is however interpreted as a fragment of the formed CO2 molecules. 7- Considering the flux ratio between laboratory experiments and actual galactic cosmic rays, half-life of valine is predicted for ISM conditions [3]. This work on pure valine is the first measurement of a series. New experiments are planned for determining cross sections of valine dissolved in H _{2}O or CO _{2}, inspired by the study performed for glycine [4]. [1] P

  16. An efficient pulse compression method of chirp-coded excitation in medical ultrasound imaging.

    PubMed

    Yoon, Changhan; Lee, Wooyoul; Chang, Jin; Song, Tai-kyong; Yoo, Yangmo

    2013-10-01

    Coded excitation can improve the SNR in medical ultrasound imaging. In coded excitation, pulse compression is applied to compress the elongated coded signals into a short pulse, which typically requires high computational complexity, i.e., a compression filter with a few hundred coefficients. In this paper, we propose an efficient pulse compression method of chirp-coded excitation, in which the pulse compression is conducted with complex baseband data after downsampling, to lower the computational complexity. In the proposed method, although compression is conducted with the complex data, the L-fold downsampling is applied for reducing both data rates and the number of compression filter coefficients; thus, total computational complexity is reduced to the order of 1/L(2). The proposed method was evaluated with simulation and phantom experiments. From the simulation and experiment results, the proposed pulse compression method produced similar axial resolution compared with the conventional pulse compression method with negligible errors, i.e., ≫36 dB in signal-to-error ratio (SER). These results indicate that the proposed method can maintain the performance of pulse compression of chirp-coded excitation while substantially reducing computational complexity.

  17. Enhancement of Zirconolite Dissolution Due to Water Radiolysis

    SciTech Connect

    Tribet, Magaly; Moncoffre, Nathalie

    2007-07-01

    Zirconolite is a candidate host material for conditioning minor tri- and tetra-valent actinides arising from enhanced nuclear spent fuel reprocessing and partitioning, in the case of disposal of the nuclear waste. Its chemical durability has been studied here under charged particle-induced radiolysis (He{sup 2+} and proton external beams) to identify the possible effects of water radiolysis on the dissolution rates in pure water and to describe the alteration mechanisms. Two experimental geometries have been used in order to evaluate the influence of the following parameters: solid irradiation, water radiolysis. In the first geometry the beam gets through the sample before stopping at the surface/water interface. In the second one the beam stops before the surface/water interface. Results on the elemental releases due to the enhanced dissolution of the zirconolite surface during charged particle-induced irradiation of water are presented. Under radiolysis, an increase of one order of magnitude is observed in the Ti, Zr and Nd elemental releases. No difference in the total elemental releases can be noticed when the solid is also irradiated. (authors)

  18. Leach and radiolysis data for FUETAP concretes containing SRP wastes

    SciTech Connect

    Dole, L.R.; Rogers, G.C.; Morgan, M.T.; Stinton, D.P.; Kessler, J.H.; Robinson, S.M.; Moore, J.G.

    1983-04-01

    This supplement to ORNL/TM-8579 contains experimental results for leach tests and alpha-radiolysis tests made on FUETAP concretes containing Savannah River Plant waste. The results, presented in two sections, consist of both the raw data and calculated values for individual experiments. This information is summarized and analyzed in Sections 5 and 7 of ORNL/TM-8579.

  19. VERSE-Guided Numerical RF Pulse Design: A Fast Method for Peak RF Power Control

    PubMed Central

    Lee, Daeho; Grissom, William A.; Lustig, Michael; Kerr, Adam B.; Stang, Pascal P.; Pauly, John M.

    2013-01-01

    In parallel excitation, the computational speed of numerical radiofrequency (RF) pulse design methods is critical when subject dependencies and system nonidealities need to be incorporated on-the-fly. One important concern with optimization-based methods is high peak RF power exceeding hardware or safety limits. Hence, online controllability of the peak RF power is essential. Variable-rate selective excitation pulse reshaping is ideally suited to this problem due to its simplicity and low computational cost. In this work, we first improve the fidelity of variable-rate selective excitation implementation for discrete-time waveforms through waveform oversampling such that variable-rate selective excitation can be robustly applied to numerically designed RF pulses. Then, a variable-rate selective excitation-guided numerical RF pulse design is suggested as an online RF pulse design framework, aiming to simultaneously control peak RF power and compensate for off-resonance. PMID:22135085

  20. Method and apparatus for electrical cable testing by pulse-arrested spark discharge

    DOEpatents

    Barnum, John R.; Warne, Larry K.; Jorgenson, Roy E.; Schneider, Larry X.

    2005-02-08

    A method for electrical cable testing by Pulse-Arrested Spark Discharge (PASD) uses the cable response to a short-duration high-voltage incident pulse to determine the location of an electrical breakdown that occurs at a defect site in the cable. The apparatus for cable testing by PASD includes a pulser for generating the short-duration high-voltage incident pulse, at least one diagnostic sensor to detect the incident pulse and the breakdown-induced reflected and/or transmitted pulses propagating from the electrical breakdown at the defect site, and a transient recorder to record the cable response. The method and apparatus are particularly useful to determine the location of defect sites in critical but inaccessible electrical cabling systems in aging aircraft, ships, nuclear power plants, and industrial complexes.

  1. Digital pulse deconvolution method for current tails of NaI(Tl) detectors

    NASA Astrophysics Data System (ADS)

    Zeng, Guo-Qiang; Yang, Jian; Yu, Ming-Fu; Zhang, Kai-Qi; Ge, Qing; Ge, Liang-Quan

    2017-01-01

    To overcome the problem of pulse pile-up at high count rates, a digital deconvolution algorithm is used to remove the exponential current tails of NaI(Tl) detectors, so as to obtain a current unit impulse. Then a narrow pulse can be obtained through pulse shaping. The pulse deconvolution technique can thoroughly eliminate the influences of ballistic deficit and improve traditional pulse shaping systems in both pulse throughput and energy resolution. To demonstrate this method, the energy spectrum of a 137Cs radioactive source was measured. When the shaping time constant is 1.5 μs, traditional pulse shaping systems yielded a 6.99% energy resolution and 68 kcps count rate, while the new pulse deconvolution technique, used to improve traditional pulse shaping systems, yielded a 6.37% energy resolution and 102 kcps count rate. Supported by National Natural Science Foundation of China (41474159), Sichuan Youth Science & Technology Foundation (2015JQ0035) and Key Laboratory of Applied Nuclear Techniques in Geosciences Sichuan (gnzds2014006)

  2. A novel acquisition method for nuclear spectra based on pulse area analysis

    NASA Astrophysics Data System (ADS)

    Li, Dong-Cang; Ren, Zhong-Guo; Yang, Lei; Qi, Zhong; Meng, Xiang-Ting; Hu, Bi-Tao

    2015-04-01

    A novel simple method based on pulse area analysis (PAA) is presented for acquisition of nuclear spectra by a digitizer. The PAA method can be used as a substitute for the traditional method of pulse height analysis (PHA). In the PAA method a commercial digitizer was employed to sample and sum in the pulse, and the area of the pulse is proportional to the energy of the detected radiation. The results of simulation and experiment indicate the great advantages of the PAA method, especially as the count rate is high and the shaping time constant is small. When the shaping time constant is 0.5 μs, the energy resolution of PAA is about 66% better than that of PHA. Supported by National Natural Science Foundation of China (11375077, 11027508)

  3. Small-tip-angle spokes pulse design using interleaved greedy and local optimization methods.

    PubMed

    Grissom, William A; Khalighi, Mohammad-Mehdi; Sacolick, Laura I; Rutt, Brian K; Vogel, Mika W

    2012-11-01

    Current spokes pulse design methods can be grouped into methods based either on sparse approximation or on iterative local (gradient descent-based) optimization of the transverse-plane spatial frequency locations visited by the spokes. These two classes of methods have complementary strengths and weaknesses: sparse approximation-based methods perform an efficient search over a large swath of candidate spatial frequency locations but most are incompatible with off-resonance compensation, multifrequency designs, and target phase relaxation, while local methods can accommodate off-resonance and target phase relaxation but are sensitive to initialization and suboptimal local cost function minima. This article introduces a method that interleaves local iterations, which optimize the radiofrequency pulses, target phase patterns, and spatial frequency locations, with a greedy method to choose new locations. Simulations and experiments at 3 and 7 T show that the method consistently produces single- and multifrequency spokes pulses with lower flip angle inhomogeneity compared to current methods.

  4. A method for pressure-pulse suppression in fluid-filled piping

    SciTech Connect

    Shin, Y.W.; Bielick, E.F. ); Wiedermann, A.H. ); Ockert, C.E. )

    1989-01-01

    A simple, nondestructive method to suppress pressure pulses in fluid-filled piping was proposed and theoretically analyzed earlier. In this paper, the proposed method is verified experimentally. The results of experiments performed for the range of parameters of practical importance indicated that the attenuation of pressure pulses was in accordance with the theoretical predictions. This paper describes the experimental setup and the test models of the proposed pulse suppression devices and discusses the experimental results. In particular, the measured attenuation factors are presented and compared with the theoretical predictions. 8 ref., 17 fig., 2 tab.

  5. Note: Novel trigger pulse feed method for mega-volt gas switch

    NASA Astrophysics Data System (ADS)

    Yin, Jiahui; Sun, Fengju; Jiang, Xiaofeng; Wang, Zhiguo; Liang, Tianxue; Jiang, Hongyu; Qiu, Aici

    2017-07-01

    It is difficult to feed the trigger pulse into an electrically triggered mega-volt switch, and the present note presents a novel trigger pulse feed method. The trigger pulse is introduced via a damping resistor, which is mounted between the inner and outer cylindrical electrodes of the pulse transmission line. The mega-volt pulse is damped because the voltage is resistively divided by the resistor and trigger cable arrangement. Both the complex breakdown processes of the switch and its insulation issues are experimentally studied. The function and the beneficial effects of the damping resistor, installed together with an additional inductor, are discussed. Finally, the parameters of these two damping components are set to 500 Ω and 2 μH values for which the switch has been demonstrated to work successfully at over 2.3 MV.

  6. Note: Novel trigger pulse feed method for mega-volt gas switch.

    PubMed

    Yin, Jiahui; Sun, Fengju; Jiang, Xiaofeng; Wang, Zhiguo; Liang, Tianxue; Jiang, Hongyu; Qiu, Aici

    2017-07-01

    It is difficult to feed the trigger pulse into an electrically triggered mega-volt switch, and the present note presents a novel trigger pulse feed method. The trigger pulse is introduced via a damping resistor, which is mounted between the inner and outer cylindrical electrodes of the pulse transmission line. The mega-volt pulse is damped because the voltage is resistively divided by the resistor and trigger cable arrangement. Both the complex breakdown processes of the switch and its insulation issues are experimentally studied. The function and the beneficial effects of the damping resistor, installed together with an additional inductor, are discussed. Finally, the parameters of these two damping components are set to 500 Ω and 2 μH values for which the switch has been demonstrated to work successfully at over 2.3 MV.

  7. Pulsed voltage electrospray ion source and method for preventing analyte electrolysis

    DOEpatents

    Kertesz, Vilmos [Knoxville, TN; Van Berkel, Gary [Clinton, TN

    2011-12-27

    An electrospray ion source and method of operation includes the application of pulsed voltage to prevent electrolysis of analytes with a low electrochemical potential. The electrospray ion source can include an emitter, a counter electrode, and a power supply. The emitter can include a liquid conduit, a primary working electrode having a liquid contacting surface, and a spray tip, where the liquid conduit and the working electrode are in liquid communication. The counter electrode can be proximate to, but separated from, the spray tip. The power system can supply voltage to the working electrode in the form of a pulse wave, where the pulse wave oscillates between at least an energized voltage and a relaxation voltage. The relaxation duration of the relaxation voltage can range from 1 millisecond to 35 milliseconds. The pulse duration of the energized voltage can be less than 1 millisecond and the frequency of the pulse wave can range from 30 to 800 Hz.

  8. Hazardous and Corrosive Gas Production in the Radiolysis of Water/Organic Mixtures in Model TRU Waste

    SciTech Connect

    LaVerne, Jay A.

    2004-12-01

    - from 1,2-DCE and from 1,1-DCE solutions is very significantly higher ({approx} x 3-4) than from deoxygenated solution. Furthermore, the observed yield is both dose and dose rate dependent. The mechanisms for Cl- production in aerated aqueous solutions of 1,2-DCE and of 1,1-DCE are currently under investigation. Rate coefficients for the reaction of eaq- and -OH with chlorinated hydrocarbons. There is considerable disagreement over the rate coefficients for the reaction of the primary radiation-produced reducing and oxidizing radicals from water, eaq- and -OH respectively, with 1,2-DCE and with 1,1-DCE. Electron pulse-radiolysis experiments monitoring the decay of eaq- have been used to measure the rate coefficients: 1,2 DCE eaq- + CH2Cl-CH2Cl ' CH2Cl-CH2- + Cl- k1 = 2.3 x 109 dm3 mole-1 s-1 1,1 DCE eaq- + CH3Cl-CHCl2 ' CH3-CHCl- + Cl- k2 = 3.5 x 109 dm3 mole-1 s-1 while competition kinetic experiments were employed to determine the rate coefficients: 1,2 DCE -OH + CH2Cl-CH2Cl ' CH2Cl-CHCl- + H2O k3 = 1.8 x 108 dm3 mole-1 s-1 1,1 DCE -OH + CH3Cl-CHCl2 ' CH3-CCl2- + H2O k4 = 1.1 x 108 dm3 mole-1 s-1 The values obtained are similar to those measured by Asmus and co-workers, but there is a significant discrepancy from the estimate of Getoff and co-workers for k1. Rate coefficient for the reaction of OH with thiocyanide ion. The rate coefficient for the reaction of the -OH radical with a chlorinated hydrocarbon is obtained by a competition experiment, in which the change in the radiation-induced yield of (SCN)2-- from an aqueous SCN- solution is monitored on the addition of the hydrocarbon. The mechanism for the radiation-induced formation of (SCN)2-- from a SCN- is complex and involves a number of equilibria. Careful electron pulse radiolysis experiments have been performed and analyzed, employing the full, complex reaction mechanism, to re-evaluated the rate coefficient for the fundamental reaction -OH + SCN- ' (HOSCN)-- k5 = 1.4 x 1010 dm3 mole-1 s-1 This reaction is

  9. A method to extract successive velocity pulses governing structural response from long-period ground motion

    NASA Astrophysics Data System (ADS)

    Liu, Shuoyu; Li, Yingmin; Wang, Guojue

    2017-06-01

    A series of relatively long-period velocity pulses appearing in the later part of ground motion, which is the characterization of far-source long-period ground motions in basin ("long-period ground motion" for short), is mainly influenced by focal mechanism, basin effect, and dispersion. It was supposed that the successive low-frequency velocity pulses in long-period ground motion caused the resonance of long-period structures in basin, which are of special concern to designers of super high-rise buildings. The authors proposed a wavelet-based successive frequency-dependent pulse extraction (WSFPE) method to identify and extract these pulses with dominant period of interest from long-period ground motions. The pulses extracted by using two frequently used methods (zero-crossing analysis, empirical mode decomposition) were compared to the pulses extracted by using WSFPE. The results demonstrate that the WSFPE provides higher resolution in time-frequency domain than the other two methods do. The velocity pulses extracted by using WSFPE are responsible for the resonance and maximum response of structure subjected to long-period ground motions. WSFPE can be used to make a better understanding of long-period ground motions and to promote the formation of long-period ground motion model which will help the seismic design of long-period structures built in sedimentary basin.

  10. An efficient motion-resistant method for wearable pulse oximeter.

    PubMed

    Yan, Yong-Sheng; Zhang, Yuan-Ting

    2008-05-01

    Reduction of motion artifact and power saving are crucial in designing a wearable pulse oximeter for long-term telemedicine application. In this paper, a novel algorithm, minimum correlation discrete saturation transform (MCDST) has been developed for the estimation of arterial oxygen saturation (SaO2), based on an optical model derived from photon diffusion analysis. The simulation shows that the new algorithm MCDST is more robust under low SNRs than the clinically verified motion-resistant algorithm discrete saturation transform (DST). Further, the experiment with different severity of motions demonstrates that MCDST has a slightly better performance than DST algorithm. Moreover, MCDST is more computationally efficient than DST because the former uses linear algebra instead of the time-consuming adaptive filter used by latter, which indicates that MCDST can reduce the required power consumption and circuit complexity of the implementation. This is vital for wearable devices, where the physical size and long battery life are crucial.

  11. Production of pulsed atomic oxygen beams via laser vaporization methods

    NASA Technical Reports Server (NTRS)

    Brinza, David E.; Coulter, Daniel R.; Liang, Ranty H.; Gupta, Amitava

    1986-01-01

    The generation of energetic pulsed atomic oxygen beams by laser-driven evaporation of cryogenically frozen ozone/oxygen films and thin indium-tin oxide (ITO) films is reported. Mass spectroscopy is used in the mass and energy characterization of beams from the ozone/oxygen films, and a peak flux of 3 x 10 to the 20th/sq m per sec at 10 eV is found. Analysis of the time-of-flight data suggests that several processes contribute to the formation of the oxygen beam. Results show the absence of metastable states such as the 2p(3)3s(1)(5S) level of atomic oxygen blown-off from the ITO films. The present process has application to the study of the oxygen degradation problem of LEO materials.

  12. Determination of pure neutron radiolysis yields for use in chemical modeling of supercritical water

    NASA Astrophysics Data System (ADS)

    Edwards, Eric J.

    This work has determined pure neutron radical yields at elevated temperature and pressure up to supercritical conditions using a reactor core radiation. The data will be necessary to provides realistic conditions for material corrosion experiments for the supercritical water reactor (SCWR) through water chemistry modeling. The work has been performed at the University of Wisconsin Nuclear Reactor using an apparatus designed to transport supercritical water near the reactor core. Low LET yield data used in the experiment was provided by a similar project at the Notre Dame Radiation Lab. Radicals formed by radiolysis were measured through chemical scavenging reactions. The aqueous electron was measured by two methods, a reaction with N2O to produce molecular nitrogen and a reaction with SF6 to produce fluoride ions. The hydrogen radical was measured through a reaction with ethanol-D6 (CD3CD2OD) to form HD. Molecular hydrogen was measured directly. Gaseous products were measured with a mass spectrometer and ions were measured with an ion selective electrode. Radiation energy deposition was calibrated for neutron and gamma radiation separately with a neutron activation analysis and a radiolysis experiment. Pure neutron yields were calculated by subtracting gamma contribution using the calibrated gamma energy deposition and yield results from work at the Notre Dame Radiation Laboratory. Pure neutron yields have been experimentally determined for aqueous electrons from 25°C to 400°C at 248 bar and for the hydrogen radical from 25°C to 350°C at 248 bar, Isothermal data has been acquired for the aqueous electron at 380°C and 400°C as a function of density. Molecular hydrogen yields were measured as a function of temperature and pressure, although there was evidence that chemical reactions with the walls of the water tubing were creating molecular hydrogen in addition to that formed through radiolysis. Critical hydrogen concentration behavior was investigated but a

  13. Method to precisely measure the phase of few-cycle laser pulses.

    PubMed

    Liao, Qing; Lu, Peixiang; Lan, Pengfei; Yang, Zhenyu; Li, Yunhua

    2008-04-28

    A new method of accurately measuring the carrier-envelope phase (CEP) of few-cycle pulses is presented. The high-energy photo-electron spectrum by a few-cycle pulse is dominated by photoelectrons bursting in very few short time intervals near the maximum of the pulse envelope. For high laser intensities, the positions of interference fringes in the high-energy cutoff region are very sensitive to the CEP, which can be used to measure and stabilize the CEP precisely. The measurement precision of the CEP strongly depends on the laser intensity for the fastest photoelectrons.

  14. Computationally efficient method for Fourier transform of highly chirped pulses for laser and parametric amplifier modeling.

    PubMed

    Andrianov, Alexey; Szabo, Aron; Sergeev, Alexander; Kim, Arkady; Chvykov, Vladimir; Kalashnikov, Mikhail

    2016-11-14

    We developed an improved approach to calculate the Fourier transform of signals with arbitrary large quadratic phase which can be efficiently implemented in numerical simulations utilizing Fast Fourier transform. The proposed algorithm significantly reduces the computational cost of Fourier transform of a highly chirped and stretched pulse by splitting it into two separate transforms of almost transform limited pulses, thereby reducing the required grid size roughly by a factor of the pulse stretching. The application of our improved Fourier transform algorithm in the split-step method for numerical modeling of CPA and OPCPA shows excellent agreement with standard algorithms.

  15. Production of pulsed atomic oxygen beams via laser vaporization methods

    NASA Technical Reports Server (NTRS)

    Brinza, David E.; Coulter, Daniel R.; Liang, Ranty H.; Gupta, Amitava

    1987-01-01

    Energetic pulsed atomic oxygen beams were generated by laser-driven evaporation of cryogenically frozen ozone/oxygen films and thin films of indium-tin oxide (ITO). Mass and energy characterization of beams from the ozone/oxygen films were carried out by mass spectrometry. The peak flux, found to occur at 10 eV, is estimated from this data to be 3 x 10(20) m(-2) s(-1). Analysis of the time-of-flight data indicates a number of processes contribute to the formation of the atomic oxygen beam. The absence of metastable states such as the 2p(3) 3s(1) (5S) level of atomic oxygen blown off from ITO films is supported by the failure to observe emission at 777.3 nm from the 2p(3) 3p(1) (5P sub J) levels. Reactive scattering experiments with polymer film targets for atomic oxygen bombardment are planned using a universal crossed molecular beam apparatus.

  16. Evaluation of the pulse-contour method of determining stroke volume in man.

    NASA Technical Reports Server (NTRS)

    Alderman, E. L.; Branzi, A.; Sanders, W.; Brown, B. W.; Harrison, D. C.

    1972-01-01

    The pulse-contour method for determining stroke volume has been employed as a continuous rapid method of monitoring the cardiovascular status of patients. Twenty-one patients with ischemic heart disease and 21 patients with mitral valve disease were subjected to a variety of hemodynamic interventions. The pulse-contour estimations, using three different formulas derived by Warner, Kouchoukos, and Herd, were compared with indicator-dilution outputs. A comparison of the results of the two methods for determining stroke volume yielded correlation coefficients ranging from 0.59 to 0.84. The better performing Warner formula yielded a coefficient of variation of about 20%. The type of hemodynamic interventions employed did not significantly affect the results using the pulse-contour method. Although the correlation of the pulse-contour and indicator-dilution stroke volumes is high, the coefficient of variation is such that small changes in stroke volume cannot be accurately assessed by the pulse-contour method. However, the simplicity and rapidity of this method compared to determination of cardiac output by Fick or indicator-dilution methods makes it a potentially useful adjunct for monitoring critically ill patients.

  17. Evaluation of the pulse-contour method of determining stroke volume in man.

    NASA Technical Reports Server (NTRS)

    Alderman, E. L.; Branzi, A.; Sanders, W.; Brown, B. W.; Harrison, D. C.

    1972-01-01

    The pulse-contour method for determining stroke volume has been employed as a continuous rapid method of monitoring the cardiovascular status of patients. Twenty-one patients with ischemic heart disease and 21 patients with mitral valve disease were subjected to a variety of hemodynamic interventions. The pulse-contour estimations, using three different formulas derived by Warner, Kouchoukos, and Herd, were compared with indicator-dilution outputs. A comparison of the results of the two methods for determining stroke volume yielded correlation coefficients ranging from 0.59 to 0.84. The better performing Warner formula yielded a coefficient of variation of about 20%. The type of hemodynamic interventions employed did not significantly affect the results using the pulse-contour method. Although the correlation of the pulse-contour and indicator-dilution stroke volumes is high, the coefficient of variation is such that small changes in stroke volume cannot be accurately assessed by the pulse-contour method. However, the simplicity and rapidity of this method compared to determination of cardiac output by Fick or indicator-dilution methods makes it a potentially useful adjunct for monitoring critically ill patients.

  18. Application of digital pulse shaping by least squares method to ultrasonic signals in composites

    NASA Technical Reports Server (NTRS)

    Kishoni, D.

    1985-01-01

    For ultrasonic testing in composites, a signal processing tool is identified that can significantly enhance the sharpness of ultrasonic waveforms and provide clearer pictures of the nature of the material flaw. The technique artificially improves the resolution of the system to discrete events by pulse shaping the measured waveform based on the signal from a reference. The optimum pulse shape operator is determined from a least-squares method in the z-domain.

  19. Radiolysis of actinides and technetium in alkaline media

    SciTech Connect

    Delegard, C.H., Westinghouse Hanford

    1996-07-10

    The {gamma}-radiolysis of aerated alkaline aqueous solutions of Np(V), Np(VI), Pu(VI), Tc(IV), Tc(V), and TC(VII) was studied in the absence of additives and in the presence of CO{sub 3}{sup 2-}, NO{sub 3}{sup -}, NO{sub 2}{sup -}, EDTA, formate, and other organic compounds. The radiolytic reduction of Np(V), Np(VI), Pu(VI), and TC(VII) under different experimental conditions was examined in detail. The addition of EDTA, formate, and alcohols was found to considerably increase the radiation-chemical reduction yields. The formation of the Np(V) peroxo complex was observed in the {gamma}-radiolysis of alkaline aqueous solutions of Np (VI) in the presence of nitrate.

  20. Radiolysis of Resist Polymers. III. Copolymers of Methyl-Alpha-Chloroacrylate and Trihaloethylmethacrylates.

    DTIC Science & Technology

    1983-08-01

    copolymerization reactivity ratios crosslinking scission radiolysis product analysis e 20. ABSTRACT (Continue on reverse side if necessary and identify by block...8217-chloroacrylate (MCA) of a range of composition were synthesized. Radiolysis of copolymers are initiated by Li dissociative electron capture by the...773 TECHNICAL REPORT NO. 3 Radiolysis of Resist Polymers. Ill. Copolymers of Methyl-a-Chloroacrylate and Trihaloethylmethacrylates P. By G.N. Babu, P.H

  1. Radiolysis of Resist Polymers. 2. Poly(haloalkylmethacrylates) and Copolymers with Methylmethacrylate.

    DTIC Science & Technology

    1983-08-01

    AD-Ai32 095 RADIOLYSIS OF RESIST POLYMERS 2OYHLRKLMTRRLTS i/iOPLME-U I S MASSACHUSETTS UNIV AMHERST MATERIALS RESEARCH LAB UNCLASSIFIED G N BABU ET...CATALOG NUMBER 27 4. TITLE (and Subtitle) S. TYPE OF REPORT 6 PERIOD COVERED Radiolysis of Resist Polymers. II. Technical Report Poly...2,3-Sdibromopropyl methacrylate (DBPMA) and copolymers with MMA over a range of composi - tions have been synthesized. Gamma- radiolysis yields for

  2. Silver-halide sensitized gelatin (SHSG) processing method for pulse holograms recorded on VRP plates

    NASA Astrophysics Data System (ADS)

    Evstigneeva, Maria K.; Drozdova, Olga V.; Mikhailov, Viktor N.

    2002-06-01

    One of the most important area of holograph applications is display holography. In case of pulse recording the requirement for vibration stability is easier than compared to CW exposure. At the same time it is widely known that the behavior of sliver-halide holographic materials strongly depends on the exposure duration. In particular the exposure sensitivity drastically decreases under nanosecond pulse duration. One of the effective ways of the diffraction efficiency improvement is SHSG processing method. This processing scheme is based on high modulation of refractive index due to microvoids appearance inside emulsion layer. It should be mentioned that the SHSG method was used earlier only in the cases when the holograms were recorded by use of CW lasers. This work is devoted to the investigation of SHSG method for pulse hologram recording on VRP plates. We used a pulsed YLF:Nd laser with pulse duration of 25 nanoseconds and wavelength of 527 nm. Both transmission and reflection holograms were recorded. The different kinds of bleaching as well as developing solutions were investigated. Our final processing scheme includes the following stages: 1) development in non-tanning solution, 2) rehalogenating bleach, 3) intermediate alcohol drying, 4) uniform second exposure, 5) second development in diluted developer, 6) reverse bleaching, 7) fixing and 8) gradient drying in isopropyl alcohol. Diffraction efficiency of transmission holograms was of about 60 percent and reflection mirror holograms was of about 45 percent. Thus we have demonstrated the SHSG processing scheme for producing effective holograms on VRP plates under pulse exposure.

  3. Formation of stable radicals in the radiolysis of perfluoroalkanes

    SciTech Connect

    Allayarov, S.R.; Demidov, S.V.; Kiryukhin, D.P.; Mikhailov, A.I.; Barkalov, I.M.

    1984-01-01

    The radiolysis of fluorinated aliphatic hydrocarbons by gamma radiation from /sup 60/Co is discussed. Particularly, the formation of stable alkyl radicals is investigated. The kinetics of the formation and accumulation of the alkyl radicals is virtually independent of the molecular weight and viscosity of the original hydrocarbon fraction. The high stability of the radicals is assumed to be caused by the intramolecular steric isolation of the free valence.

  4. Volume Ice Radiolysis in the Outer Solar System

    NASA Astrophysics Data System (ADS)

    Cooper, J. F.; Cooper, P. D.

    2006-05-01

    The primary energy flux of charged particle components of the heliospheric and magnetospheric environments of the solar system is primarily carried by highly penetrating energetic particles. Although laboratory experiments on production of organics and oxidants typically only address effects on very thin surface layers, energy deposition occurs on surfaces of icy bodies of the outer solar system to meters in depth. Time scales for significant radiolytic deposition vary from thousands of years at millimeter depths on Europa to billions of years in the meters-deep regolith of Kuiper Belt Objects. Radioisotope decay (e.g., K-40) also contributes to volume radiolysis as the only energy source at much greater depths. Radiolytic oxygen is a potential resource for life within Europa and a partial source of oxygen for Saturn's magnetosphere and Titan's upper atmosphere. Interactions of very high energy cosmic rays with ices at Titan's surface may provide one of the few sources of oxidants in that organic-rich environment. The red colors of low-inclination classical Kuiper Belt Objects at 40- 50 AU, and Centaur objects originating from this same population, may arise from volume radiolysis of deep ice layers below more refractory radiation crusts eroded away by surface sputtering and micrometeoroid impacts. A variety of techniques are potentially available to measure volume radiolysis products and have been proposed for study as part of the new Space Physics of Life initiative at NASA Goddard Space Flight Center. The technique of Electron Paramagnetic Resonance (EPR) has been used in medical studies to measure oxidant production in irradiated human tissue for cancer treatment. Other potential techniques include optical absorption spectroscopy and standard wet chemical analysis. These and other potential techniques are briefly reviewed for applicability to problems in solar system ice radiolysis and astrobiology.

  5. Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

    NASA Technical Reports Server (NTRS)

    Cassidy, T.; Coll, P.; Raulin, F.; Carlson, R. W.; Hand, K. P.; Johnson, R. E.; Loeffler, M. J.; Baragiola, R. A.

    2010-01-01

    The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O2 and H2 from irradiated H2O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H2O ice, sulfur-containing compounds (such as S02 and S8), carboncontajning compounds (such as CH4), nitrogen-containing compounds (such as NH3 and N2), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N2 and CH4 gases, as appropriate to Titan's upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).

  6. Radiolysis and Hydrolysis of TRUEX-NPH solvent.

    SciTech Connect

    Simonzadeh, N.; Crabtree, A. M.; Trevorrow, L. E.; Vandegrift, G. F.

    1992-07-01

    The TRUEX solvent extraction process separates transuranic (TRU) elements from aqueous nitrate and chloride solutions. During contact with high-level wastes, which may be highly radioactive and highly acidic, the radiolysis and hydrolysis ofTRUEX-NPH solvent can affect the process not only by destroying the extractant CMPO in the solvent, but also by generating products of CMPO destruction, some of which are powerful extractants at low acidities and can prevent the stripping of Am and Pu from solvent that is to be recycled. To provide an experimental basis from which mathematical expressions of these effects could be derived, samples of solvent were degraded by radiolysis and hydrolysis while in contact with acidic aqueous solutions. Following this treatment, the distribution of americium between degraded solvent and aqueous HNO3 was used as a measure of the extent of degradation. Mathematical expressions were derived to represent the distribution coefficient, DAm, as a function of hydrolysis time and/or radiation dose. Assumptions about the dependence of DAm on CMPO concentration were used to derive expressions for the hydrolysis rate for CMPO and also to calculate values of radiation chemical yield for CMPO radiolysis. Also experimentally investigated were changes in acidity of both the aqueous and organic phases as functions of contact time, the effects of a carbonate wash in removing acidic degradation products that function as extractants at low acidities, and changes in compositions of some of the aqueous and organic phases during contact.

  7. Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

    NASA Astrophysics Data System (ADS)

    Cassidy, T.; Coll, P.; Raulin, F.; Carlson, R. W.; Johnson, R. E.; Loeffler, M. J.; Hand, K. P.; Baragiola, R. A.

    2010-06-01

    The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O2 and H2 from irradiated H2O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H2O ice, sulfur-containing compounds (such as SO2 and S8), carbon-containing compounds (such as CH4), nitrogen-containing compounds (such as NH3 and N2), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N2 and CH4 gases, as appropriate to Titan’s upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).

  8. Radiolysis and Photolysis of Icy Satellite Surfaces: Experiments and Theory

    NASA Technical Reports Server (NTRS)

    Cassidy, T.; Coll, P.; Raulin, F.; Carlson, R. W.; Hand, K. P.; Johnson, R. E.; Loeffler, M. J.; Baragiola, R. A.

    2010-01-01

    The transport and exchange of material between bodies in the outer solar system is often facilitated by their exposure to ionizing radiation. With this in mind we review the effects of energetic ions, electrons and UV photons on materials present in the outer solar system. We consider radiolysis, photolysis, and sputtering of low temperature solids. Radiolysis and photolysis are the chemistry that follows the bond breaking and ionization produced by incident radiation, producing, e.g., O2 and H2 from irradiated H2O ice. Sputtering is the ejection of molecules by incident radiation. Both processes are particularly effective on ices in the outer solar system. Materials reviewed include H2O ice, sulfur-containing compounds (such as S02 and S8), carboncontajning compounds (such as CH4), nitrogen-containing compounds (such as NH3 and N2), and mixtures of those compounds. We also review the effects of ionizing radiation on a mixture of N2 and CH4 gases, as appropriate to Titan's upper atmosphere, where radiolysis and photolysis produce complex organic compounds (tholins).

  9. Method and apparatus for pressure pulse arcjet starting

    NASA Technical Reports Server (NTRS)

    Sankovic, John M. (Inventor); Curran, Francis M. (Inventor)

    1996-01-01

    The invention disclosed is directed to a method and apparatus for an arcjet starter. The invention discloses a method of moving an arc from the subsonic region of the thruster to the supersonic region by introducing a pressurized propellant into the casuty of the anode.

  10. Method and Apparatus for Pressure Pulse Arcjet Starting

    NASA Technical Reports Server (NTRS)

    Sankovic, John M. (Inventor); Curran, Francis M. (Inventor)

    1999-01-01

    The invention disclosed is directed to a method and apparatus for an arcjet starter. The invention discloses a method of moving an arc from the subsonic region of the thruster to the supersonic region by introducing a pressurized propellant into the casuty of the anode.

  11. Scintillation event energy measurement via a pulse model based iterative deconvolution method

    NASA Astrophysics Data System (ADS)

    Deng, Zhenzhou; Xie, Qingguo; Duan, Zhiwen; Xiao, Peng

    2013-11-01

    This work focuses on event energy measurement, a crucial task of scintillation detection systems. We modeled the scintillation detector as a linear system and treated the energy measurement as a deconvolution problem. We proposed a pulse model based iterative deconvolution (PMID) method, which can process pileup events without detection and is adaptive for different signal pulse shapes. The proposed method was compared with digital gated integrator (DGI) and digital delay-line clipping (DDLC) using real world experimental data. For singles data, the energy resolution (ER) produced by PMID matched that of DGI. For pileups, the PMID method outperformed both DGI and DDLC in ER and counts recovery. The encouraging results suggest that the PMID method has great potentials in applications like photon-counting systems and pulse height spectrometers, in which multiple-event pileups are common.

  12. Facile time-of-flight methods for characterizing pulsed superfluid helium droplet beams.

    PubMed

    He, Yunteng; Zhang, Jie; Li, Yang; Freund, William M; Kong, Wei

    2015-08-01

    We present two facile time-of-flight (TOF) methods of detecting superfluid helium droplets and droplets with neutral dopants. Without an electron gun and with only a heated filament and pulsed electrodes, the electron impact ionization TOF mass spectrometer can resolve ionized helium clusters such as He2(+) and He4(+), which are signatures of superfluid helium droplets. Without ionizing any helium atoms, multiphoton non-resonant laser ionization of CCl4 doped in superfluid helium droplets at 266 nm generates complex cluster ions of dopant fragments with helium atoms, including (He)(n)C(+), (He)(n)Cl(+), and (He)(n)CCl(+). Using both methods, we have characterized our cryogenic pulsed valve—the Even-Lavie valve. We have observed a primary pulse with larger helium droplets traveling at a slower speed and a rebound pulse with smaller droplets at a faster speed. In addition, the pickup efficiency of dopant is higher for the primary pulse when the nozzle temperature is higher than 13 K, and the total time duration of the doped droplet pulse is only on the order of 20 μs. These results stress the importance of fast and easy characterization of the droplet beam for sensitive measurements such as electron diffraction of doped droplets.

  13. A novel micro-pulse laser active imaging method based on photon counting scheme

    NASA Astrophysics Data System (ADS)

    Liu, Chenghao; Yin, Wenye; Miao, Zhuang; He, Wei-ji; Chen, Qian; Gu, Guo-Hua

    2013-12-01

    We present the use and characterization of a Single Photon Detector (SPD) for active micro-pulse laser imaging. Laser active imaging technology obtains the two dimensional (2D) intensity information of objects by using the active continuous or pulsed laser illumination and an image sensor array. The Maximum range of laser active imaging is limited by the performance of image sensor, whose noise can seriously lower the obtainable SNR and degrade the quality of the reconstructed image. This paper presents a photon counting scheme based micro-pulse laser active imaging method that utilizes the SPD as the receiver and the micro-pulsed laser as the source. In this case, SPD was used to detect the laser echo. By using repeated multi-cycle detection strategies, every detected photon event is treated as an independent measurement of laser echo and thus the intensity information of objects is acquired with the response possibility estimation of laser echo. We chose a Geiger-Mode Avalanche Photodiodes (GM-APD) based approach, extending the methods of micro-pulse laser active imaging. In our implement, the number of TTL pulses output from the GM-APD within the duration of the pixel dwell time was recorder by a LabView pre-programmed instrument and then the laser echo response possibility of GM-APD was established by Full Waveform Analysis algorithm. This approach combined remote imaging with single photon sensitivity and laser active imaging.

  14. Facile time-of-flight methods for characterizing pulsed superfluid helium droplet beams

    SciTech Connect

    He, Yunteng; Zhang, Jie; Li, Yang; Freund, William M.; Kong, Wei

    2015-08-15

    We present two facile time-of-flight (TOF) methods of detecting superfluid helium droplets and droplets with neutral dopants. Without an electron gun and with only a heated filament and pulsed electrodes, the electron impact ionization TOF mass spectrometer can resolve ionized helium clusters such as He{sub 2}{sup +} and He{sub 4}{sup +}, which are signatures of superfluid helium droplets. Without ionizing any helium atoms, multiphoton non-resonant laser ionization of CCl{sub 4} doped in superfluid helium droplets at 266 nm generates complex cluster ions of dopant fragments with helium atoms, including (He){sub n}C{sup +}, (He){sub n}Cl{sup +}, and (He){sub n}CCl{sup +}. Using both methods, we have characterized our cryogenic pulsed valve—the Even-Lavie valve. We have observed a primary pulse with larger helium droplets traveling at a slower speed and a rebound pulse with smaller droplets at a faster speed. In addition, the pickup efficiency of dopant is higher for the primary pulse when the nozzle temperature is higher than 13 K, and the total time duration of the doped droplet pulse is only on the order of 20 μs. These results stress the importance of fast and easy characterization of the droplet beam for sensitive measurements such as electron diffraction of doped droplets.

  15. [A calibrated method for blood pressure measurement based on volume pulse wave].

    PubMed

    Youde, Ding; Qinkai, Deng; Feixue, Liang; Jinseng, Guo

    2010-01-01

    Physiology parameters measurement based on volume pulse wave is suitable for the monitoring blood pressure continuously. This paper described that the systolic blood pressure (SBP) and diastolic blood pressure (DBP) can be calibrated by measuring the pulse propagation time, just on one point of finger tip. The volume pulse wave was acquired by lighting the red and infrared LED alternately, and after signal processing, an accelerated pulse wave was obtained. Then by measuring the pulse wave propagation time between the progressive wave and reflected wave, we can find the relationship of the time and the blood pressure, and establish the related systolic blood pressure measurement equation. At the same time, based on the relationship between alternating current and direct current components in the volume pulse waveforms and through regression analysising, the relevant diastolic blood pressure measurement equation can be established. 33 clinical experimentation cases have been worked by dividing them into two groups: training group (18 cases) and control group (15 cases), by comparing with the measuring results of the OMRON electronic sphygmomanometer. The results indicated that the two methods had good coherence. The measurement described is simple and reliable, and may be served as a new method for noninvasively and continuously measurement of blood pressure.

  16. Facile time-of-flight methods for characterizing pulsed superfluid helium droplet beams

    PubMed Central

    He, Yunteng; Zhang, Jie; Li, Yang; Freund, William M.; Kong, Wei

    2015-01-01

    We present two facile time-of-flight (TOF) methods of detecting superfluid helium droplets and droplets with neutral dopants. Without an electron gun and with only a heated filament and pulsed electrodes, the electron impact ionization TOF mass spectrometer can resolve ionized helium clusters such as He2+ and He4+, which are signatures of superfluid helium droplets. Without ionizing any helium atoms, multiphoton non-resonant laser ionization of CCl4 doped in superfluid helium droplets at 266 nm generates complex cluster ions of dopant fragments with helium atoms, including (He)nC+, (He)nCl+, and (He)nCCl+. Using both methods, we have characterized our cryogenic pulsed valve—the Even-Lavie valve. We have observed a primary pulse with larger helium droplets traveling at a slower speed and a rebound pulse with smaller droplets at a faster speed. In addition, the pickup efficiency of dopant is higher for the primary pulse when the nozzle temperature is higher than 13 K, and the total time duration of the doped droplet pulse is only on the order of 20 μs. These results stress the importance of fast and easy characterization of the droplet beam for sensitive measurements such as electron diffraction of doped droplets. PMID:26329210

  17. Pulse shape discrimination and classification methods for continuous depth of interaction encoding PET detectors

    NASA Astrophysics Data System (ADS)

    Roncali, Emilie; Phipps, Jennifer E.; Marcu, Laura; Cherry, Simon R.

    2012-10-01

    In previous work we demonstrated the potential of positron emission tomography (PET) detectors with depth-of-interaction (DOI) encoding capability based on phosphor-coated crystals. A DOI resolution of 8 mm full-width at half-maximum was obtained for 20 mm long scintillator crystals using a delayed charge integration linear regression method (DCI-LR). Phosphor-coated crystals modify the pulse shape to allow continuous DOI information determination, but the relationship between pulse shape and DOI is complex. We are therefore interested in developing a sensitive and robust method to estimate the DOI. Here, linear discriminant analysis (LDA) was implemented to classify the events based on information extracted from the pulse shape. Pulses were acquired with 2×2×20 mm3 phosphor-coated crystals at five irradiation depths and characterized by their DCI values or Laguerre coefficients. These coefficients were obtained by expanding the pulses on a Laguerre basis set and constituted a unique signature for each pulse. The DOI of individual events was predicted using LDA based on Laguerre coefficients (Laguerre-LDA) or DCI values (DCI-LDA) as discriminant features. Predicted DOIs were compared to true irradiation depths. Laguerre-LDA showed higher sensitivity and accuracy than DCI-LDA and DCI-LR and was also more robust to predict the DOI of pulses with higher statistical noise due to low light levels (interaction depths further from the photodetector face). This indicates that Laguerre-LDA may be more suitable to DOI estimation in smaller crystals where lower collected light levels are expected. This novel approach is promising for calculating DOI using pulse shape discrimination in single-ended readout depth-encoding PET detectors.

  18. Method and Apparatus for Pressure Pulse Arcjet Starting

    NASA Technical Reports Server (NTRS)

    Sandkovic, John M. (Inventor); Curran, Francis M. (Inventor)

    1997-01-01

    The invention disclosed is directed to a model and apparatus for an arcjet starter. The invention discloses a method of moving an arc from the subsonic region of the thruster to the supersonic region by introducing a pressurized propellant into the annular area of the anode.

  19. The method of pulsed x-ray detection with a diode laser

    NASA Astrophysics Data System (ADS)

    Liu, Jun; Ouyang, Xiaoping; Zhang, Zhongbing; Sheng, Liang; Chen, Liang; Tan, Xinjian; Weng, Xiufeng

    2016-12-01

    A new class of pulsed X-ray detection methods by sensing carrier changes in a diode laser cavity has been presented and demonstrated. The proof-of-principle experiments on detecting pulsed X-ray temporal profile have been done through the diode laser with a multiple quantum well active layer. The result shows that our method can achieve the aim of detecting the temporal profile of a pulsed X-ray source. We predict that there is a minimum value for the pre-bias current of the diode laser by analyzing the carrier rate equation, which exists near the threshold current of the diode laser chip in experiments. This behaviour generally agrees with the characterizations of theoretical analysis. The relative sensitivity is estimated at about 3.3 × 10-17 C ṡ cm2. We have analyzed the time scale of about 10 ps response with both rate equation and Monte Carlo methods.

  20. Method and apparatus for pulse width modulation control of an AC induction motor

    DOEpatents

    Geppert, Steven; Slicker, James M.

    1984-01-01

    An inverter is connected between a source of DC power and a three-phase AC induction motor, and a micro-processor-based circuit controls the inverter using pulse width modulation techniques. In the disclosed method of pulse width modulation, both edges of each pulse of a carrier pulse train are equally modulated by a time proportional to sin .THETA., where .THETA. is the angular displacement of the pulse center at the motor stator frequency from a fixed reference point on the carrier waveform. The carrier waveform frequency is a multiple of the motor stator frequency. The modulated pulse train is then applied to each of the motor phase inputs with respective phase shifts of 120.degree. at the stator frequency. Switching control commands of electronic switches in the inverter are stored in a random access memory (RAM) and the locations of the RAM are successively read out in a cyclic manner, each bit of a given RAM location controlling a respective phase input of the motor. The DC power source preferably comprises rechargeable batteries and all but one of the electronic switches in the inverter can be disabled, the remaining electronic switch being part of a "flyback" DC-DC converter circuit for recharging the battery.

  1. Method and apparatus for pulse width modulation control of an AC induction motor

    NASA Technical Reports Server (NTRS)

    Geppert, Steven (Inventor); Slicker, James M. (Inventor)

    1984-01-01

    An inverter is connected between a source of DC power and a three-phase AC induction motor, and a micro-processor-based circuit controls the inverter using pulse width modulation techniques. In the disclosed method of pulse width modulation, both edges of each pulse of a carrier pulse train are equally modulated by a time proportional to sin .THETA., where .THETA. is the angular displacement of the pulse center at the motor stator frequency from a fixed reference point on the carrier waveform. The carrier waveform frequency is a multiple of the motor stator frequency. The modulated pulse train is then applied to each of the motor phase inputs with respective phase shifts of 120.degree. at the stator frequency. Switching control commands of electronic switches in the inverter are stored in a random access memory (RAM) and the locations of the RAM are successively read out in a cyclic manner, each bit of a given RAM location controlling a respective phase input of the motor. The DC power source preferably comprises rechargeable batteries and all but one of the electronic switches in the inverter can be disabled, the remaining electronic switch being part of a flyback DC-DC converter circuit for recharging the battery.

  2. Noninvasive Method for Measuring Local Pulse Wave Velocity by Dual Pulse Wave Doppler: In Vitro and In Vivo Studies

    PubMed Central

    Wang, Zhen; Yang, Yong; Yuan, Li-jun; Liu, Jie; Duan, Yun-you; Cao, Tie-sheng

    2015-01-01

    Objectives To evaluate the validity and reproducibility of a noninvasive dual pulse wave Doppler (DPWD) method, which involves simultaneous recording of flow velocity of two independent sample volumes with a measurable distance, for measuring the local arterial pulse wave velocity (PWV) through in vitro and in vivo studies. Methods The DPWD mode of Hitachi HI Vision Preirus ultrasound system with a 5–13MHz transducer was used. An in vitro model was designed to compare the PWV of a homogeneous rubber tubing with the local PWV of its middle part measured by DPWD method. In the in vivo study, local PWV of 45 hypertensive patients (25 male, 49.8±3.1 years) and 45 matched healthy subjects (25 male, 49.3±3.0 years) were investigated at the left common carotid artery (LCCA) by DPWD method. Results In the in vitro study, the local PWV measured by DPWP method and the PWV of the homogeneous rubber tubing did not show statistical difference (5.16 ± 0.28 m/s vs 5.03 ± 0.15 m/s, p = 0.075). The coefficient of variation (CV) of the intra- and inter- measurements for local PWV were 3.46% and 4.96%, for the PWV of the homogeneous rubber tubing were 0.99% and 1.98%. In the in vivo study, a significantly higher local PWV of LCCA was found in the hypertensive patients as compared to that in healthy subjects (6.29±1.04m/s vs. 5.31±0.72m/s, P = 0.019). The CV of the intra- and inter- measurements in hypertensive patients were 2.22% and 3.94%, in healthy subjects were 2.07% and 4.14%. Conclusions This study demonstrated the feasibility of the noninvasive DPWD method to determine the local PWV, which was accurate and reproducible not only in vitro but also in vivo studies. This noninvasive echocardiographic method may be illuminating to clinical use. PMID:25786124

  3. Determination of diffusion coefficients in polypyrrole thin films using a current pulse relaxation method

    NASA Technical Reports Server (NTRS)

    Penner, Reginald M.; Vandyke, Leon S.; Martin, Charles R.

    1987-01-01

    The current pulse E sub oc relaxation method and its application to the determination of diffusion coefficients in electrochemically synthesized polypyrrole thin films is described. Diffusion coefficients for such films in Et4NBF4 and MeCN are determined for a series of submicron film thicknesses. Measurement of the double-layer capacitance, C sub dl, and the resistance, R sub u, of polypyrrole thin films as a function of potential obtained with the galvanostatic pulse method is reported. Measurements of the electrolyte concentration in reduced polypyrrole films are also presented to aid in the interpretation of the data.

  4. Apparatus and method for recharging a string a avalanche transistors within a pulse generator

    DOEpatents

    Fulkerson, E. Stephen

    2000-01-01

    An apparatus and method for recharging a string of avalanche transistors within a pulse generator is disclosed. A plurality of amplification stages are connected in series. Each stage includes an avalanche transistor and a capacitor. A trigger signal, causes the apparatus to generate a very high voltage pulse of a very brief duration which discharges the capacitors. Charge resistors inject current into the string of avalanche transistors at various points, recharging the capacitors. The method of the present invention includes the steps of supplying current to charge resistors from a power supply; using the charge resistors to charge capacitors connected to a set of serially connected avalanche transistors; triggering the avalanche transistors; generating a high-voltage pulse from the charge stored in the capacitors; and recharging the capacitors through the charge resistors.

  5. Pulsing Depolarization: New Method of In-Vivo Blood Glucometry

    NASA Astrophysics Data System (ADS)

    Romanov, Dmitri; Shvartsman, Leonid; Fine, Ilya

    2002-03-01

    We propose a new system of non-invasive measurements enabling one to monitor in-vivo the glucose content of the blood. The proposed method is based on the transmission oximetry technique [1] and on the model of red blood cell aggregation [2]. We utilize the known birefregence of glucose solutions (in this case, the blood plasma) and the absence of this optical activity on the part of the red cells. Thus, we model the blood as a birefrigent host medium filled with optically non-active inclusions of spheroidal shape, arbitrarily oriented and having one semiaxis growing with time during the cell aggregation. We trace the evolution of initially linearly polarized laser beam in this system, and calculate the ellipticity and the azimuthal angle of the resulting partially depolarized light. The azimuthal angle is obtained as time-independent quantity being a function of the hematocrit, glucose content and thickness of the host medium layer, while the ellipticity depends also on the red cell aggregation, and thus oscillates with the heartbeats. Measurements of both the azimuthal angle and the ellipticity provide us with sufficient data to determine the glucose content of the blood. [1] I. Fine, A. Weinreb, Med. and Biol. Eng. and Comput., 31, 516 (1993). [2] L.D. Shvartsman, I. Fine, SPIE Proc., 4162, 120 (2000).

  6. Pulsed holographic microscopy as a measurement method of dynamic fracture toughness for fast propagating cracks

    NASA Astrophysics Data System (ADS)

    Suzuki, Shinichi; Homma, Hiroomi; Kusaka, Riichiro

    A METHOD OF pulsed holographic microscopy is applied to take instantaneous microscopic photographs of the neighborhoods of crack tips propagating through PMMA or through AISI 4340 steel specimens at a speed of several hundred meters per second. The cracks are in the opening mode. A fast propagating crack is recorded as a hologram at an instant during its propagation. A microscopic photograph of the crack is taken with a conventional microscope to magnify the reconstructed image from the hologram. From the microscopic photograph, crack opening displacement (COD) is measured along the crack in the vicinity of the crack tip. The COD is of the order often to one hundred microns, and in proportion to the square root of the distance from the crack tip. The dynamic fracture toughness KID is obtained using the formula for COD in the singular stress field of a fast propagating crack. Simultaneous KID measurement both through pulsed holographic microscopy and through the caustic method is furthermore carried out with PMMA specimens. The values of KID obtained through pulsed holographic microscopy are in agreement with those through the caustic method. Microcracks accompanied by a main crack are also photographed with the method of pulsed holographic microscopy.

  7. Pulse method of structural and parametric identification of models of heterogeneous catalytic processes

    SciTech Connect

    Kafarov, V.V.; Pisarenko, V.N.; Usacheva, I.I.

    1986-04-01

    A description is given of a pulse method for the investigation of heterogeneous catalytic processes, through which the parameters of a model can be evaluated with high accuracy. An example is given of the application of the procedure to an alloy catalyst.

  8. An ultrasound-based method for determining pulse wave velocity in superficial arteries.

    PubMed

    Rabben, Stein Inge; Stergiopulos, Nikos; Hellevik, Leif Rune; Smiseth, Otto A; Slørdahl, Stig; Urheim, Stig; Angelsen, Bjørn

    2004-10-01

    In this paper, we present a method for estimating local pulse wave velocity (PWV) solely from ultrasound measurements: the area-flow (QA) method. With the QA method, PWV is estimated as the ratio between change in flow and change in cross-sectional area (PWV = dQ/dA) during the reflection-free period of the cardiac cycle. In four anaesthetized dogs and 21 human subjects (age 23-74) we measured the carotid flow and cross-sectional area non-invasively by ultrasound. As a reference method we used the Bramwell-Hill (BH) equation which estimates PWV from pulse pressure and cross-sectional area. Additionally, we therefore measured brachial pulse pressure by oscillometry in the human subjects, and central aortic pulse pressure by micro-manometry in the dogs. As predicted by the pressure dependency of arterial stiffness, the estimated PWV decreased when the aortic pressure was lowered in two of the dogs. For the human subjects, the QA and BH estimates were correlated (R=0.43, p<0.05) and agreed on average (mean difference of -0.14 m/s). The PWV by the BH method increased with age (p<0.01) whereas the PWV by the QA method tended to increase with age (p<0.1). This corresponded to a larger residual variance (residual = deviation of the estimated PWV from the regression line) for the QA method than for the BH method, indicating different precisions for the two methods. This study illustrates that the simple equation PWV = dQ/dA gives estimates correlated to the PWV of the reference method. However, improvements in the basic measurements seem necessary to increase the precision of the method.

  9. Method and circuit for controlling the evolution time interval of a laser output pulse

    NASA Technical Reports Server (NTRS)

    Barnes, Norman P. (Inventor)

    1992-01-01

    The invention is a method and circuit for controlling the evolution time interval of a laser output pulse used for making precise spectral measurements. It comprises the means for pumping a laser medium in a resonator that includes a Q-switch and polarizer that act in combination to control the loss in the resonator. A photodiode senses the resulting fluorescence which is applied to a two level Q-switch and polarizer from high to intermediate to substantially zero loss states to control the evolution time interval of the resulting laser output pulse.

  10. Practical method and device for enhancing pulse contrast ratio for lasers and electron accelerators

    DOEpatents

    Zhang, Shukui; Wilson, Guy

    2014-09-23

    An apparatus and method for enhancing pulse contrast ratios for drive lasers and electron accelerators. The invention comprises a mechanical dual-shutter system wherein the shutters are placed sequentially in series in a laser beam path. Each shutter of the dual shutter system has an individually operated trigger for opening and closing the shutter. As the triggers are operated individually, the delay between opening and closing first shutter and opening and closing the second shutter is variable providing for variable differential time windows and enhancement of pulse contrast ratio.

  11. Split-Step Fourier Method for Laser Pulse Propagation in Particulate Media,

    DTIC Science & Technology

    1981-10-01

    AD-A109 50 5 DEFENCE RESEARCH ESTABLISHMENT VALCARTIER (QUEBEC) F/9 20/6 SPLIT-STEP FOURIER METHO0D FOR LASER PULSE PROPAGATION IN PARTIC--ETCIU...SPLIT-STEP FOURIER METHOD FOR LASER PULSE PROPAGATION IN PARTICULATE MEDIA by W.G. Tam CENTRE DE RECHERCHES POUR LA DEFENSE DEFENCE RESEARCH...la fonction de coh6rence mutuelle est d6termin6e A l1’aide d’une transforma- tion Fourier ’split-step’. Cette approche nous permet d𔄀viter l’utili

  12. Radiolysis and Chemical Weathering on the Galilean Satellites

    NASA Astrophysics Data System (ADS)

    Carlson, R. W.

    2002-12-01

    The Galiliean satellites are bombarded by energetic particles that profoundly affect the surface composition. Reactive sulfur is implanted from the Iogenic plasma, and new chemical species are produced by radiolysis. Characteristic times for radiolytic destruction are very short compared to geological time scales, and the depth of direct radiolytic influence is about 1 mm, comparable to the depth of the optically observed layer. Europa's radiolytic products include hydrogen peroxide and molecular oxygen, as well as a hydrated material that exhibits a strong trailing side enhancement. Carlson, Johnson, and Anderson (Science 286, 97-99, 1999) identified the latter as hydrated sulfuric acid and proposed that it is part of Europa's radiolytic sulfur cycle, wherein elemental sulfur, sulfur dioxide, hydrogen sulfide, and sulfuric acid are in dynamic equilibrium between continuous production and destruction. A dark material that is spatially associated with hydrated sulfuric acid was suggested to be radiolytically produced sulfur allotropes. Sulfur dioxide was also found to be associated with the hydrate (Hendrix et al., Eurojove, 2002) and is present at levels consistent with the abundance of sulfuric acid and measured radiolysis rates (Carlson et al., Icarus 157, 456-463, 2002). Ion implantation can provide the observed amount of total sulfur in just 30,000 years, suggesting that burial by impact gardening may be occurring. The variegated surface color may be due to diapiric heating of the surface, which sublimates water and preferentially concentrates lower vapor pressure sulfurous material. Any endogenic sources of sulfurous material would be rapidly assimilated into the radiolytic sulfur cycle. Ganymede contains O2 in its surface and atmosphere, likely produced from the radiolysis of H2O. Both Ganymede and Callisto show CO2 in their surfaces, and a corresponding CO2 atmosphere has been found on Callisto. The trailing side enhancement of surficial CO2 on Callisto

  13. Multi-Gaussian fitting for pulse waveform using Weighted Least Squares and multi-criteria decision making method.

    PubMed

    Wang, Lu; Xu, Lisheng; Feng, Shuting; Meng, Max Q-H; Wang, Kuanquan

    2013-11-01

    Analysis of pulse waveform is a low cost, non-invasive method for obtaining vital information related to the conditions of the cardiovascular system. In recent years, different Pulse Decomposition Analysis (PDA) methods have been applied to disclose the pathological mechanisms of the pulse waveform. All these methods decompose single-period pulse waveform into a constant number (such as 3, 4 or 5) of individual waves. Furthermore, those methods do not pay much attention to the estimation error of the key points in the pulse waveform. The estimation of human vascular conditions depends on the key points' positions of pulse wave. In this paper, we propose a Multi-Gaussian (MG) model to fit real pulse waveforms using an adaptive number (4 or 5 in our study) of Gaussian waves. The unknown parameters in the MG model are estimated by the Weighted Least Squares (WLS) method and the optimized weight values corresponding to different sampling points are selected by using the Multi-Criteria Decision Making (MCDM) method. Performance of the MG model and the WLS method has been evaluated by fitting 150 real pulse waveforms of five different types. The resulting Normalized Root Mean Square Error (NRMSE) was less than 2.0% and the estimation accuracy for the key points was satisfactory, demonstrating that our proposed method is effective in compressing, synthesizing and analyzing pulse waveforms.

  14. Application of P4 Polyphase codes pulse compression method to air-coupled ultrasonic testing systems.

    PubMed

    Li, Honggang; Zhou, Zhenggan

    2017-07-01

    Air-coupled ultrasonic testing systems are usually restricted by low signal-to-noise ratios (SNR). The use of pulse compression techniques based on P4 Polyphase codes can improve the ultrasound SNR. This type of codes can generate higher Peak Side Lobe (PSL) ratio and lower noise of compressed signal. This paper proposes the use of P4 Polyphase sequences to code ultrasound with a NDT system based on air-coupled piezoelectric transducer. Furthermore, the principle of selecting parameters of P4 Polyphase sequence for obtaining optimal pulse compression effect is also studied. Successful results are presented in molded composite material. A hybrid signal processing method for improvement in SNR up to 12.11dB and in time domain resolution about 35% are achieved when compared with conventional pulse compression technique. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. A new method for the acquisition of arterial pulse wave using self-mixing interferometry

    NASA Astrophysics Data System (ADS)

    Arasanz, A.; Azcona, F. J.; Royo, S.; Jha, A.; Pladellorens, J.

    2014-11-01

    In this paper we present a technique based on self-mixing interferometry as a method for the acquisition and reconstruction of the arterial pulse wave. A modification of the classic fringe counting reconstruction algorithm is proposed to deal with some of the problems caused by biological tissue surface roughness, therefore allowing a reconstruction of the arterial displacement with a resolution of 400 nm. The traits of the arterial pulse wave have been retrieved with high detail, allowing their interpretation by a skilled practitioner. The heart beat measurements show a good agreement when compared to the readings of a commercial pulse-meter, therefore proving the versatility and the viability of the technique for the measurement of other cardiovascular signals.

  16. Method and apparatus for generating high power laser pulses in the two to six micron wavelength range

    DOEpatents

    MacPherson, D.C.; Nelson, L.D.; O`Brien, M.J.

    1996-12-10

    Apparatus performs a method of generating one or more output laser pulses in a range of 2 to 6 microns. When a plurality of the output laser pulses are generated, a first output pulse has any selected wavelength within the range and a second output pulse is temporally closely spaced relative to the first output pulse and has a chosen wavelength differing from the selected wavelength. An oscillator laser cavity is provided with a tunable oscillator rod capable of generating initial laser pulses within a range of from 750 to 1000 nm, and a tuning element is coupled to the rod. A flashlamp is operable to pump the rod. For two pulse operation, the flashlamp has a given duration. A Q-switch provides the initial laser pulses upon operation of the tuning element and the flashlamp. A Raman device coupled to the rod shifts the wavelength of such initial laser pulse into the range of from 2 to 6 microns to form the output laser pulse having a wavelength within the range. For multiple pulses, a controller causes the Q-switch to provide first and second ones of the initial laser pulses, spaced by a time interval less than the given duration. Also, a selector coupled to the tuning element is operable within such duration to successively select the wavelength of the first output pulse and the chosen wavelength of the second initial pulse. The Raman device is responsive to each of the initial light pulses to generate radiation at first and second Stokes wavelengths, each of said the output laser pulses being radiation at the second Stokes wavelength. 30 figs.

  17. Method and apparatus for generating high power laser pulses in the two to six micron wavelength range

    DOEpatents

    MacPherson, David C.; Nelson, Loren D.; O'Brien, Martin J.

    1996-01-01

    Apparatus performs a method of generating one or more output laser pulses in a range of 2 to 6 microns. When a plurality of the output laser pulses are generated, a first output pulse has any selected wavelength within the range and a second output pulse is temporally closely spaced relative to the first output pulse and has a chosen wavelength differing from the selected wavelength. An oscillator laser cavity is provided with a tunable oscillator rod capable of generating initial laser pulses within a range of from 750 to 1000 nm, and a tuning element is coupled to the rod. A flashlamp is operable to pump the rod. For two pulse operation, the flashlamp has a given duration. A Q-switch provides the initial laser pulses upon operation of the tuning element and the flashlamp. A Raman device coupled to the rod shifts the wavelength of such initial laser pulse into the range of from 2 to 6 microns to form the output laser pulse having a wavelength within the range. For multiple pulses, a controller causes the Q-switch to provide first and second ones of the initial laser pulses, spaced by a time interval less than the given duration. Also, a selector coupled to the tuning element is operable within such duration to successively select the wavelength of the first output pulse and the chosen wavelength of the second initial pulse. The Raman device is responsive to each of the initial light pulses to generate radiation at first and second Stokes wavelengths, each of said the output laser pulses being radiation at the second Stokes wavelength.

  18. Coupling the Mixed Potential and Radiolysis Models for Used Fuel Degradation

    SciTech Connect

    Buck, Edgar C.; Jerden, James L.; Ebert, William L.; Wittman, Richard S.

    2013-08-30

    The primary purpose of this report is to describe the strategy for coupling three process level models to produce an integrated Used Fuel Degradation Model (FDM). The FDM, which is based on fundamental chemical and physical principals, provides direct calculation of radionuclide source terms for use in repository performance assessments. The G-value for H2O2 production (Gcond) to be used in the Mixed Potential Model (MPM) (H2O2 is the only radiolytic product presently included but others will be added as appropriate) needs to account for intermediate spur reactions. The effects of these intermediate reactions on [H2O2] are accounted for in the Radiolysis Model (RM). This report details methods for applying RM calculations that encompass the effects of these fast interactions on [H2O2] as the solution composition evolves during successive MPM iterations and then represent the steady-state [H2O2] in terms of an “effective instantaneous or conditional” generation value (Gcond). It is anticipated that the value of Gcond will change slowly as the reaction progresses through several iterations of the MPM as changes in the nature of fuel surface occur. The Gcond values will be calculated with the RM either after several iterations or when concentrations of key reactants reach threshold values determined from previous sensitivity runs. Sensitivity runs with RM indicate significant changes in G-value can occur over narrow composition ranges. The objective of the mixed potential model (MPM) is to calculate the used fuel degradation rates for a wide range of disposal environments to provide the source term radionuclide release rates for generic repository concepts. The fuel degradation rate is calculated for chemical and oxidative dissolution mechanisms using mixed potential theory to account for all relevant redox reactions at the fuel surface, including those involving oxidants produced by solution radiolysis and provided by the radiolysis model (RM). The RM calculates

  19. Portable apparatus with CRT display for nondestructive testing of concrete by the ultrasonic pulse method

    NASA Technical Reports Server (NTRS)

    Manta, G.; Gurau, Y.; Nica, P.; Facacaru, I.

    1974-01-01

    The development of methods for the nondestructive study of concrete structures is discussed. The nondestructive test procedure is based on the method of ultrasonic pulse transmission through the material. The measurements indicate that the elastic properties of concrete or other heterogeneous materials are a function of the rate of ultrasonic propagation. Diagrams of the test equipment are provided. Mathematical models are included to support the theoretical aspects.

  20. Sample preparation method for glass welding by ultrashort laser pulses yields higher seam strength

    SciTech Connect

    Cvecek, K.; Miyamoto, I.; Strauss, J.; Wolf, M.; Frick, T.; Schmidt, M.

    2011-05-01

    Glass welding by ultrashort laser pulses allows joining without the need of an absorber or a preheating and postheating process. However, cracks generated during the welding process substantially impair the joining strength of the welding seams. In this paper a sample preparation method is described that prevents the formation of cracks. The measured joining strength of samples prepared by this method is substantially higher than previously reported values.

  1. Portable apparatus with CRT display for nondestructive testing of concrete by the ultrasonic pulse method

    NASA Technical Reports Server (NTRS)

    Manta, G.; Gurau, Y.; Nica, P.; Facacaru, I.

    1974-01-01

    The development of methods for the nondestructive study of concrete structures is discussed. The nondestructive test procedure is based on the method of ultrasonic pulse transmission through the material. The measurements indicate that the elastic properties of concrete or other heterogeneous materials are a function of the rate of ultrasonic propagation. Diagrams of the test equipment are provided. Mathematical models are included to support the theoretical aspects.

  2. Influence of Nitric Acid on the Helium Ion Radiolysis of Aqueous Butanal Oxime Solutions.

    PubMed

    Costagliola, A; Venault, L; Deroche, A; Vermeulen, J; Duval, F; Blain, G; Vandenborre, J; Fattahi-Vanani, M; Vigier, N

    2017-07-13

    Samples of butanal oxime in aqueous nitric acid solutions have been irradiated with the helium ion ((4)He(2+)) beam of the CEMHTI (Orléans, France) cyclotron. The consumption yield of butanal oxime has been measured by gas chromatography coupled with mass spectrometry. Gaseous products (mainly H2 and N2O) have also been monitored by micro-gas chromatography. Yields of liquid phase products (hydrogen peroxide and nitrous acid) have been determined by colorimetric methods. The influence of nitric acid on the radiation chemical behavior of butanal oxime depends on the nitric acid concentration. For a low concentration (≤0.5 mol L(-1)) butanal oxime is protected by the nitrate ions, which can efficiently scavenge the water radiolysis radicals. For higher concentrations, nitrous acid can accumulate in the medium, therefore leading to a strong increase of the butanal oxime degradation. The associated mechanism is an autocatalytic oxidation of butanal oxime by HNO2.

  3. Caltrop particles synthesized by photochemical reaction induced by X-ray radiolysis.

    PubMed

    Yamaguchi, Akinobu; Fukuoka, Takao; Okada, Iukuo; Ishihara, Mari; Sakurai, Ikuya; Utsumi, Yuichi

    2017-05-01

    X-ray radiolysis of a Cu(CH3COO)2 solution was observed to produce caltrop-shaped particles of cupric oxide (CuO, Cu2O), which were characterized using high-resolution scanning electron microscopy and micro-Raman spectrometry. X-ray irradiation from a synchrotron source drove the room-temperature synthesis of submicrometer- and micrometer-scale cupric oxide caltrop particles from an aqueous Cu(CH3COO)2 solution spiked with ethanol. The size of the caltrop particles depended on the ratio of ethanol in the stock solution and the surface of the substrate. The results indicated that there were several synthetic routes to obtain caltrop particles, each associated with electron donation. The technique of X-ray irradiation enables the rapid synthesis of caltrop cupric oxide particles compared with conventional synthetic methods.

  4. The RMT method for describing many-electron atoms in intense short laser pulses

    NASA Astrophysics Data System (ADS)

    Lysaght, M. A.; Moore, L. R.; Nikolopoulos, L. A. A.; Parker, J. S.; van der Hart, H. W.; Taylor, K. T.

    2012-11-01

    We describe how we have extended the underlying methods of the HELIUM code to describe multi-electron systems exposed to intense short-pulse laser light. We achieve this extension through exploiting the powerful R-matrix division-of-space concept to bring together a numerical method (basis set) most appropriate to the multi-electron finite inner region and a different numerical method (finite difference) most appropriate to the one-electron outer region. In order for the method to exploit massively parallel supercomputers efficiently, we time-propagate the wave function in both regions by employing schemes based on the Arnoldi method, long employed in HELIUM.

  5. A single-probe heat pulse method for estimating sap velocity in trees.

    PubMed

    López-Bernal, Álvaro; Testi, Luca; Villalobos, Francisco J

    2017-10-01

    Available sap flow methods are still far from being simple, cheap and reliable enough to be used beyond very specific research purposes. This study presents and tests a new single-probe heat pulse (SPHP) method for monitoring sap velocity in trees using a single-probe sensor, rather than the multi-probe arrangements used up to now. Based on the fundamental conduction-convection principles of heat transport in sapwood, convective velocity (Vh ) is estimated from the temperature increase in the heater after the application of a heat pulse (ΔT). The method was validated against measurements performed with the compensation heat pulse (CHP) technique in field trees of six different species. To do so, a dedicated three-probe sensor capable of simultaneously applying both methods was produced and used. Experimental measurements in the six species showed an excellent agreement between SPHP and CHP outputs for moderate to high flow rates, confirming the applicability of the method. In relation to other sap flow methods, SPHP presents several significant advantages: it requires low power inputs, it uses technically simpler and potentially cheaper instrumentation, the physical damage to the tree is minimal and artefacts caused by incorrect probe spacing and alignment are removed. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

  6. Direct measurement method of specific impulse for pulse laser ablation micro-propulsion

    NASA Astrophysics Data System (ADS)

    Zhou, Weijing; Jin, Xing; Chang, Hao

    2017-05-01

    Laser ablation micro-propulsion technology is the most promising field in laser propulsion. The specific impulse is the important evaluate indicator of the micro propulsion performance. It represents the impulse generation by consuming unit weight of the working medium. Its accurate measurement can not only help to analyze the mechanism of laser ablation matter, but also help the design of micro laser ablation thruster. This paper presents a measurement method, which can not only obtain the impulse by single pulsed laser ablation the working medium, but also measure the ablation mass, which can directly measure the specific impulse. The method is based on the model of torsion pendulum in vertical direction movement, which is the direction of impulse by pulsed laser ablation and the gravitation direction caused by the loss of the ablation mass, to obtain the corresponding impulse and ablative weight. The paper deduced the measuring principle, pointed out the error and analysed the design principle of the torsion balance, the results show that, according to the torsion angle change due to the impulse by pulsed laser ablation and the mass loss by laser ablation, the maximum angle can be used to calculate the impulse and the stable rotation angle can be used to calculate the loss weight when the torsion period is much greater than four times the width of a single pulse.

  7. Spatial domain method for the design of RF pulses in multicoil parallel excitation.

    PubMed

    Grissom, William; Yip, Chun-yu; Zhang, Zhenghui; Stenger, V Andrew; Fessler, Jeffrey A; Noll, Douglas C

    2006-09-01

    Parallel excitation has been introduced as a means of accelerating multidimensional, spatially-selective excitation using multiple transmit coils, each driven by a unique RF pulse. Previous approaches to RF pulse design in parallel excitation were either formulated in the frequency domain or restricted to echo-planar trajectories, or both. This paper presents an approach that is formulated as a quadratic optimization problem in the spatial domain and allows the use of arbitrary k-space trajectories. Compared to frequency domain approaches, the new design method has some important advantages. It allows for the specification of a region of interest (ROI), which improves excitation accuracy at high speedup factors. It allows for magnetic field inhomogeneity compensation during excitation. Regularization may be used to control integrated and peak pulse power. The effects of Bloch equation nonlinearity on the large-tip-angle excitation error of RF pulses designed with the method are investigated, and the utility of Tikhonov regularization in mitigating this error is demonstrated. Copyright (c) 2006 Wiley-Liss, Inc.

  8. A FBG pulse wave demodulation method based on PCF modal interference filter

    NASA Astrophysics Data System (ADS)

    Zhang, Cheng; Xu, Shan; Shen, Ziqi; Zhao, Junfa; Miao, Changyun; Bai, Hua

    2016-10-01

    Fiber optic sensor embedded in textiles has been a new direction of researching smart wearable technology. Pulse signal which is generated by heart beat contains vast amounts of physio-pathological information about the cardiovascular system. Therefore, the research for textile-based fiber optic sensor which can detect pulse wave has far-reaching effects on early discovery and timely treatment of cardiovascular diseases. A novel wavelength demodulation method based on photonic crystal fiber (PCF) modal interference filter is proposed for the purpose of developing FBG pulse wave sensing system embedded in smart clothing. The mechanism of the PCF modal interference and the principle of wavelength demodulation based on In-line Mach-Zehnder interferometer (In-line MZI) are analyzed in theory. The fabricated PCF modal interferometer has the advantages of good repeatability and low temperature sensitivity of 3.5pm/°C from 25°C to 60°C. The designed demodulation system can achieve linear demodulation in the range of 2nm, with the wavelength resolution of 2.2pm and the wavelength sensitivity of 0.055nm-1. The actual experiments' result indicates that the pulse wave can be well detected by this demodulation method, which is in accordance with the commercial demodulation instrument (SM130) and more sensitive than the traditional piezoelectric pulse sensor. This demodulation method provides important references for the research of smart clothing based on fiber grating sensor embedded in textiles and accelerates the developments of wearable fiber optic sensors technology.

  9. Radiolysis of aqueous adenine (vitamin B4) and 8-hydroxyadenine

    NASA Astrophysics Data System (ADS)

    Hartmann, J.; Quint, R. M.; Getoff, N.

    2007-05-01

    The radiolysis of adenine (vitamin B4) was studied in aqueous solution (pH˜7.4) saturated either with argon (operating radicals: 44% e -aq, 46% OH, 10% H) or with air (46% OH, 54% O 2rad - ) and with N 2O (90% OH, 10% H), respectively. The obtained initial Gi-values are: 0.88, 1.16 and 1.45. As main radiolytic product was determined 8-hydroxyadenine (8-HOA), whose yield depends on the OH concentration in the reacting media. Hence, under the same experimental conditions the Gi-values are in media saturated with argon: 0.1, in air: 0.15 and in N 2O: 0.29. In aerated solution also a mixture of aldehydes as well as of carboxylic acids were formed, but they were not identified. 8-HOA is of some biological interest; therefore, its radiolysis was also investigated under the same conditions. The determined Gi(-8HOA)-values were in airfree solution negligible, in aerated solutions: 3.1 and in the presence of N 2O: 4.0. For explanation of the product formation some probable reaction mechanisms were given.

  10. Radiolysis Model Formulation for Integration with the Mixed Potential Model

    SciTech Connect

    Buck, Edgar C.; Wittman, Richard S.

    2014-07-10

    The U.S. Department of Energy Office of Nuclear Energy (DOE-NE), Office of Fuel Cycle Technology has established the Used Fuel Disposition Campaign (UFDC) to conduct the research and development activities related to storage, transportation, and disposal of used nuclear fuel (UNF) and high-level radioactive waste. Within the UFDC, the components for a general system model of the degradation and subsequent transport of UNF is being developed to analyze the performance of disposal options [Sassani et al., 2012]. Two model components of the near-field part of the problem are the ANL Mixed Potential Model and the PNNL Radiolysis Model. This report is in response to the desire to integrate the two models as outlined in [Buck, E.C, J.L. Jerden, W.L. Ebert, R.S. Wittman, (2013) “Coupling the Mixed Potential and Radiolysis Models for Used Fuel Degradation,” FCRD-UFD-2013-000290, M3FT-PN0806058

  11. Various methods of optimizing control pulses for quantum systems with decoherence

    NASA Astrophysics Data System (ADS)

    Pawela, Łukasz; Sadowski, Przemysław

    2016-05-01

    We design control setting that allows the implementation of an approximation of an unitary operation of a quantum system under decoherence using various quantum system layouts and numerical algorithms. We focus our attention on the possibility of adding ancillary qubits which help to achieve a desired quantum map on the initial system. Furthermore, we use three methods of optimizing the control pulses: genetic optimization, approximate evolution method and approximate gradient method. To model the noise in the system we use the Lindblad equation. We obtain results showing that applying the control pulses to the ancilla allows one to successfully implement unitary operation on a target system in the presence of noise, which is not possible which control field applied to the system qubits.

  12. Differential time domain method improves performance of pulsed laser ranging and three-dimensional imaging.

    PubMed

    Cao, Jie; Hao, Qun; Cheng, Yang; Peng, Yuxin; Zhang, Kaiyu; Mu, Jiaxing; Wang, Peng

    2016-01-10

    A ranging method based on the differential time domain method (DTDM) is proposed in order to improve ranging accuracy and the range of active measurement based on peak discriminator (PD). We develop mathematical models and deduce that zero-crossing sensitivity is an important factor, which affects the ranging error of DTDM. Additionally, zero-crossing sensitivity is determined by delayed time. We carried out relative experiments and obtained the smallest ranging error when delayed time is receiving pulse width. We also compare ranging, three-dimensional (3D) point clouds and depth images based on two methods under same testing conditions. The results show that DTDM is beneficial in improving performance of pulse laser ranging and 3D imaging.

  13. General implementation of the ERETIC method for pulsed field gradient probe heads.

    PubMed

    Ziarelli, Fabio; Viel, Stéphane; Caldarelli, Stefano; Sobieski, Daniel N; Augustine, Matthew P

    2008-10-01

    A capacitive coupling between a secondary radiofrequency (rf) channel and the gradient coil of a standard commercially available high resolution NMR spectrometer and probe head is described and used to introduce a low level exponentially damped rf signal near the frequency of the primary rf channel to serve as an external concentration standard, in analogy to the so-called ERETIC method. The stability of this inexpensive and simple to implement method, here referred to as the Pulse Into the Gradient (PIG) approach, is superb over a 14-h period and both gradient tailored water suppression and one-dimensional imaging applications are provided. Since the low level signal is introduced via the pulsed field gradient coil, the coupling is identical to that for a free induction signal and thus the method proves to be immune (within 5%) to sample ionic strength effects up to the 2M NaCl solutions explored here.

  14. Comparison of parabolic filtration methods for 3D filtered back projection in pulsed EPR imaging

    NASA Astrophysics Data System (ADS)

    Qiao, Zhiwei; Redler, Gage; Epel, Boris; Halpern, Howard J.

    2014-11-01

    Pulse electron paramagnetic resonance imaging (Pulse EPRI) is a robust method for noninvasively measuring local oxygen concentrations in vivo. For 3D tomographic EPRI, the most commonly used reconstruction algorithm is filtered back projection (FBP), in which the parabolic filtration process strongly influences image quality. In this work, we designed and compared 7 parabolic filtration methods to reconstruct both simulated and real phantoms. To evaluate these methods, we designed 3 error criteria and 1 spatial resolution criterion. It was determined that the 2 point derivative filtration method and the two-ramp-filter method have unavoidable negative effects resulting in diminished spatial resolution and increased artifacts respectively. For the noiseless phantom the rectangular-window parabolic filtration method and sinc-window parabolic filtration method were found to be optimal, providing high spatial resolution and small errors. In the presence of noise, the 3 point derivative method and Hamming-window parabolic filtration method resulted in the best compromise between low image noise and high spatial resolution. The 3 point derivative method is faster than Hamming-window parabolic filtration method, so we conclude that the 3 point derivative method is optimal for 3D FBP.

  15. Evaluation of cardiac output by 5 arterial pulse contour techniques using trend interchangeability method

    PubMed Central

    Fischer, Marc-Olivier; Diouf, Momar; de Wilde, Robert B.P.; Dupont, Hervé; Hanouz, Jean-Luc; Lorne, Emmanuel

    2016-01-01

    Abstract Cardiac output measurement with pulse contour analysis is a continuous, mini-invasive, operator-independent, widely used, and cost-effective technique, which could be helpful to assess changes in cardiac output. The 4-quadrant plot and the polar plot have been described to compare the changes between 2 measurements performed under different conditions, and the direction of change by using different methods of measurements. However, the 4-quadrant plot and the polar plot present a number of limitations, with a risk of misinterpretation in routine clinical practice. We describe a new trend interchangeability method designed to objectively define the interchangeability of each change of a variable. Using the repeatability of the reference method, we classified each change as either uninterpretable or interpretable and then as either noninterchangeable, in the gray zone or interchangeable. An interchangeability rate can then be calculated by the number of interchangeable changes divided by the total number of interpretable changes. In this observational study, we used this objective method to assess cardiac output changes with 5 arterial pulse contour techniques (Wesseling's method, LiDCO, PiCCO, Hemac method, and Modelflow) in comparison with bolus thermodilution technique as reference method in 24 cardiac surgery patients. A total of 172 cardiac output variations were available from the 199 data points: 88 (51%) were uninterpretable, according to the first step of the method. The second step of the method, based on the 84 (49%) interpretable variations, showed that only 18 (21%) to 30 (36%) variations were interchangeable regardless of the technique used. None of pulse contour cardiac output technique could be interchangeable with bolus thermodilution to assess changes in cardiac output using the trend interchangeability method in cardiac surgery patients. Future studies may consider using this method to assess interchangeability of changes between different

  16. The RMT method for describing many-electron atoms in intense short laser pulses

    NASA Astrophysics Data System (ADS)

    Lysaght, M. A.; Moore, L. R.; Nikolopoulos, L. A. A.; Parker, J. S.; van der Hart, H. W.; Taylor, K. T.

    2012-11-01

    We describe how we have developed an ab initio R-Matrix incorporating Time (RMT) method to provide an accurate description of the single ionization of a general many-electron atom exposed to short intense laser pulses. The new method implements the "division-of-space" concept central to R-matrix theory and takes over the sophisticated time-propagation algorithms of the HELIUM code. We have tested the accuracy of the new method by calculating multiphoton ionization rates of He and Ne and have found excellent agreement with other highly accurate and well-established methods.

  17. Assay of brines for common radiolysis products

    SciTech Connect

    MacDougall, C.S.

    1981-01-01

    Brines are assayed for four common products of radiolytic reaction. Free chlorine is determined spectrophotometrically after reaction with o-tolidine. The test is specific for chlorine, and quantities of chlorine from 0.1 to 6 ..mu..g in the test aliquot are determined with a precision of about +- 5%. Hydrogen peroxide is reacted with xylenol orange and determined spectrophotometrically with a precision of +- 5% on 2-..mu..g quantities of peroxide. A spectrophotometric method using thiocyanate is employed in the chlorate assay. After subtracting the bias caused by any H/sub 2/O/sub 2/ or Cl/sub 2/, 1-..mu..g quantities of chlorate can be determined with a precision of +- 10%. Perchlorate ion quantities of 1 ppM can be determined directly in brines by ion chromatography with a precision of about +- 15%.

  18. Development of ultrasonic pulse-train Doppler method for velocity profile and flowrate measurement

    NASA Astrophysics Data System (ADS)

    Wada, Sanehiro; Furuichi, Noriyuki; Shimada, Takashi

    2016-11-01

    We present a novel technique for measuring the velocity profile and flowrate in a pipe. This method, named the ultrasonic pulse-train Doppler method (UPTD), has the advantages of expanding the velocity range and setting the smaller measurement volume with low calculation and instrument costs in comparison with the conventional ultrasonic pulse Doppler method. The conventional method has limited measurement of the velocity range due to the Nyquist sampling theorem. In addition, previous reports indicate that a smaller measurement volume increases the accuracy of the measurement. In consideration of the application of the conventional method to actual flow fields, such as industrial facilities and power plants, the issues of velocity range and measurement volume are important. The UPTD algorithm, which exploits two pulses of ultrasound with a short interval and envelope detection, is proposed. Velocity profiles calculated by this algorithm were examined through simulations and excellent agreement was found in all cases. The influence of the signal-to-noise ratio (SNR) on the algorithm was also estimated. The result indicates that UPTD can measure velocity profiles with high accuracy, even under a small SNR. Experimental measurements were conducted and the results were evaluated at the national standard calibration facility of water flowrate in Japan. Every detected signal forms a set of two pulses and the enveloped line can be observed clearly. The results show that UPTD can measure the velocity profiles over the pipe diameter, even if the velocities exceed the measurable velocity range. The measured flowrates were under 0.6% and the standard deviations for all flowrate conditions were within  ±0.38%, which is the uncertainty of the flowrate measurement estimated in the previous report. In conclusion, UPTD provides superior accuracy and expansion of the velocity range.

  19. Development of a standardized method for motion testing in pulse oximeters.

    PubMed

    Shang, Allan B; Kozikowski, Raymond T; Winslow, Andrew W; Weininger, Sandy

    2007-12-01

    Pulse oximeter performance in the presence of motion varies among devices and manufacturers because of variations in hardware, software, testing, and calibration. Compounding these differences is a lack of uniform characterization of motion, and the consequential effects of motion upon the wide range of normal and abnormal human physiology. Traditional motion testing attempts to standardize motion into a reproducible form by using a mechanical jig to produce passive motion of a known amplitude and frequency. This type of motion challenge fails to account for the physiologic changes induced by active movement. We postulate that a more appropriate method for testing the performance of pulse oximeters in the presence of motion is to create a feedback control loop between the device and the test subject, providing a reproducible, actively created, and controlled motion test suitable for standardized testing among manufacturers. It is hoped that relying on a signal as seen from the oximeter's perspective will enable the creation of a sensitive and reproducible test method capable of separating those oximeters that can reject motion artifact from those that cannot. Preliminary results have concentrated on building the tools and clinical protocols needed to evaluate this method. Some basic observations are reported, but insufficient numbers of experienced subjects precludes rigorous conclusions. We have set the stage for a feasibility demonstration using a novel form of testing. With sufficient subjects and proper statistical evaluation, a robust test method for assessing the performance of pulse oximeters in the presence of motion may be at hand.

  20. Compressive strength evaluation of structural lightweight concrete by non-destructive ultrasonic pulse velocity method.

    PubMed

    Bogas, J Alexandre; Gomes, M Glória; Gomes, Augusto

    2013-07-01

    In this paper the compressive strength of a wide range of structural lightweight aggregate concrete mixes is evaluated by the non-destructive ultrasonic pulse velocity method. This study involves about 84 different compositions tested between 3 and 180 days for compressive strengths ranging from about 30 to 80 MPa. The influence of several factors on the relation between the ultrasonic pulse velocity and compressive strength is examined. These factors include the cement type and content, amount of water, type of admixture, initial wetting conditions, type and volume of aggregate and the partial replacement of normal weight coarse and fine aggregates by lightweight aggregates. It is found that lightweight and normal weight concretes are affected differently by mix design parameters. In addition, the prediction of the concrete's compressive strength by means of the non-destructive ultrasonic pulse velocity test is studied. Based on the dependence of the ultrasonic pulse velocity on the density and elasticity of concrete, a simplified expression is proposed to estimate the compressive strength, regardless the type of concrete and its composition. More than 200 results for different types of aggregates and concrete compositions were analyzed and high correlation coefficients were obtained. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Determining the sizes of micropores in activated charcoals by the pulsed NMR method

    NASA Astrophysics Data System (ADS)

    Gogelashvili, G. Sh.; Khozina, E. V.; Vartapetyan, R. Sh.; Ladychuk, D. V.; Grunin, Yu. B.

    2011-07-01

    The pulsed NMR method was used to measure the nuclear spin-spin relaxation of protons of water adsorbed in micropores of activated charcoal (AC) samples with different porous structures. A correlation was found between the spin-spin relaxation time of water protons in AC with completely filled micropores and the volume density of water primary adsorption centers in the AC samples. An equation for approximating obtained dependences is proposed that allows us to determine the volume of micropores in AC.

  2. Magnetic field error measurement of the CEBAF (NIST) wiggler using the pulsed wire method

    SciTech Connect

    Wallace, Stephen; Colson, William; Neil, George; Harwood, Leigh

    1993-07-01

    The National Institute for Science and Technology (NIST) wiggler has been loaded to the Continuous Electron Beam Accelerator Facility (CEBAF). The pulsed wire method [R.W. Warren, Nucl. Instr. and Meth. A272 (1988) 267] has been used to measure the field errors of the entrance wiggler half, and the net path deflection was calculated to be Δx ≈ 5.2 m.

  3. Method and apparatus for improving the quality and efficiency of ultrashort-pulse laser machining

    DOEpatents

    Stuart, Brent C.; Nguyen, Hoang T.; Perry, Michael D.

    2001-01-01

    A method and apparatus for improving the quality and efficiency of machining of materials with laser pulse durations shorter than 100 picoseconds by orienting and maintaining the polarization of the laser light such that the electric field vector is perpendicular relative to the edges of the material being processed. Its use is any machining operation requiring remote delivery and/or high precision with minimal collateral dames.

  4. Development of glucose measurement system based on pulsed laser-induced ultrasonic method

    NASA Astrophysics Data System (ADS)

    Ren, Zhong; Wan, Bin; Liu, Guodong; Xiong, Zhihua

    2016-09-01

    In this study, a kind of glucose measurement system based on pulsed-induced ultrasonic technique was established. In this system, the lateral detection mode was used, the Nd: YAG pumped optical parametric oscillator (OPO) pulsed laser was used as the excitation source, the high sensitivity ultrasonic transducer was used as the signal detector to capture the photoacoustic signals of the glucose. In the experiments, the real-time photoacoustic signals of glucose aqueous solutions with different concentrations were captured by ultrasonic transducer and digital oscilloscope. Moreover, the photoacoustic peak-to-peak values were gotten in the wavelength range from 1300nm to 2300nm. The characteristic absorption wavelengths of glucose were determined via the difference spectral method and second derivative method. In addition, the prediction models of predicting glucose concentrations were established via the multivariable linear regression algorithm and the optimal prediction model of corresponding optimal wavelengths. Results showed that the performance of the glucose system based on the pulsed-induced ultrasonic detection method was feasible. Therefore, the measurement scheme and prediction model have some potential value in the fields of non-invasive monitoring the concentration of the glucose gradient, especially in the food safety and biomedical fields.

  5. Pulse wave detection method based on the bio-impedance of the wrist

    NASA Astrophysics Data System (ADS)

    He, Jianman; Wang, Mengjun; Li, Xiaoxia; Li, Gang; Lin, Ling

    2016-05-01

    The real-time monitoring of pulse rate can evaluate the heart health to some extent, and the measurement of bio-impedance has the potential in wearable health monitoring system. In this paper, an effective method, which contains self-balancing bridge, flexible electrode, and high-speed digital lock-in algorithm (DLIA) with over-sampling, was designed to detect the impedance pulse wave at the wrist. By applying the self-balancing bridge, the basic impedance can be compensated as much as possible, and the low amplitude of impedance variation related to heart pulse can be obtained more easily. And the flexible conductive rubber electrode used in our experiment is human-friendly. Besides, the over-sampling method and high-speed DLIA are used to enhance the effective resolution of the existing data sampled by analog to digital converter. With the high-speed data process and simple circuit above, this proposed method has the potential in wrist-band wearable systems and it can satisfy quests of small volume and low power consumption.

  6. Water Sorption and Gamma Radiolysis Studies for Uranium Oxides

    SciTech Connect

    Icenhour, A.S.

    2002-02-27

    During the development of a standard for the safe, long-term storage of {sup 233}U-containing materials, several areas were identified that needed additional experimental studies. These studies were related to the perceived potential for the radiolytic generation of large pressures or explosive concentrations of gases in storage containers. This report documents the results of studies on the sorption of water by various uranium oxides and on the gamma radiolysis of uranium oxides containing various amounts of sorbed moisture. In all of the experiments, {sup 238}U was used as a surrogate for the {sup 233}U. For the water sorption experiments, uranium oxide samples were prepared and exposed to known levels of humidity to establish the water uptake rate. Subsequently, the amount of water removed was studied by heating samples in a oven at fixed temperatures and by thermogravimetric analysis (TGA)/differential thermal analysis (DTA). It was demonstrated that heating at 650 C adequately removes all moisture from the samples. Uranium-238 oxides were irradiated in a {sup 60}Co source and in the high-gamma-radiation fields provided by spent nuclear fuel elements of the High Flux Isotope Reactor. For hydrated samples of UO{sub 3}, H{sub 2} was the primary gas produced; but the total gas pressure increase reached steady value of about 10 psi. This production appears to be a function of the dose and the amount of water present. Oxygen in the hydrated UO{sub 3} sample atmosphere was typically depleted, and no significant pressure rise was observed. Heat treatment of the UO{sub 3} {center_dot} xH{sub 2}O at 650 C would result in conversion to U{sub 3}O{sub 8} and eliminate the H{sub 2} production. For all of the U{sub 3}O{sub 8} samples loaded in air and irradiated with gamma radiation, a pressure decrease was seen and little, if any, H{sub 2} was produced--even for samples with up to 9 wt % moisture content. Hence, these results demonstrated that the efforts to remove trace

  7. A practical method for determining minimum detectable values in pulse-counting measurements.

    PubMed

    Furukawa, Yoichiro; Iwasaki, Manabu; Tanaka, Akihiro

    2010-01-01

    The purpose of this paper is to propose a statistical method for determining minimum detectable values in a pulse-counting measurements. The output of x-ray, electron and ion-spectroscopy detectors is a series of pulses that vary in their arrival frequency according to a Poisson distribution. The analysis presented here relates this to a Normal distribution, making it consistent with the standards and methodology recommended by IUPAC and in the ISO 11843 series of international standards. The theory and limitations of doing this are presented using two types of approximations: a Simple approximation and a Square Root approximation. The variance, critical values of the response variables, capability of detection criteria and the minimum detectable values are then defined. Finally, the validity of the approximations is checked using experimental data. It is concluded that the methodology is accurate enough for practical use.

  8. Radiolysis of alanine adsorbed in a clay mineral

    SciTech Connect

    Aguilar-Ovando, Ellen Y.; Negron-Mendoza, Alicia

    2013-07-03

    Optical activity in molecules is a chemical characteristic of living beings. In this work, we examine the hypothesis of the influence of different mineral surfaces on the development of a specific chirality in organic molecules when subjected to conditions simulating the primitive Earth during the period of chemical evolution. By using X-ray diffraction techniques and HPLC/ELSD to analyze aqueous suspensions of amino acids adsorbed on minerals irradiated in different doses with a cobalt-60 gamma source, the experiments attempt to prove the hypothesis that some solid surfaces (like clays and meteorite rocks) may have a concentration capacity and protective role against external sources of ionizing radiation (specifically {gamma}-ray) for some organic compounds (like some amino acids) adsorbed on them. Preliminary results show a slight difference in the adsorption and radiolysis of the D-and L-alanine.

  9. The radiolysis of iodine in aqueous solutions containing methane

    NASA Astrophysics Data System (ADS)

    Paquette, Jean; Ford, Beverly L.

    The γ-radiolysis of iodine, iodine, iodate and periodate solutions containing methane has been investigated. Iodoalkanes are produced in these solutions upon irradiation. In the case of unbuffered iodine, iodate and periodate solutions at an initial concentration of 1.0 × 10 -4 mol dm -3, nearly all of the initial iodine is transformed into iodoalkanes after the absorption of a 4 kGy radiation dose. The yield of iodoalkanes is lower for iodine solutions and for iodide solutions buffered at neutral pH. It is concluded that the main reactions leading to the formation of iodoalkanes are CH 3+I 2→CH 3I+I and CH 3+I→CH 3I. In the case of iodate and periodate, these reactions could be preceeded by reactions involving the methyl radical and oxyiodine species: CH 3+IO x→CH 2O+HIO x-1.

  10. Formation of stable radicals in the radiolysis of fluoroorganic compounds

    NASA Astrophysics Data System (ADS)

    Goldanskii, V. I.; Barkalov, I. M.

    The existence of anomally long-living radicals (life time in liquid more than 100 days at 300 K) which arise in the process of radiolysis has been discovered in liquid perfluorocarbons. The ESR spectra analysis has allowed the singling out of two types of radical: (1) the perfluoroalkyl radical in which the unpaired electron stabilization is thought to be connected with the steric isolation of the surrounding perfluoromethyl groups and (2) the perfluoroalkyl radical whose stabilization is connected with the delocalization of the unpaired electron conjugated with the double CC bond. These stable radicals may be employed in the synthesis and modification of fluoropolymers as initiators and regulators, in the dosimetry of reactor irradiation, as well as in medico-biological investigations as spin-labelled compounds.

  11. Robust segmentation methods with an application to aortic pulse wave velocity calculation.

    PubMed

    Babin, Danilo; Devos, Daniel; Pižurica, Aleksandra; Westenberg, Jos; Vansteenkiste, Ewout; Philips, Wilfried

    2014-04-01

    Aortic stiffness has proven to be an important diagnostic and prognostic factor of many cardiovascular diseases, as well as an estimate of overall cardiovascular health. Pulse wave velocity (PWV) represents a good measure of the aortic stiffness, while the aortic distensibility is used as an aortic elasticity index. Obtaining the PWV and the aortic distensibility from magnetic resonance imaging (MRI) data requires diverse segmentation tasks, namely the extraction of the aortic center line and the segmentation of aortic regions, combined with signal processing methods for the analysis of the pulse wave. In our study non-contrasted MRI images of abdomen were used in healthy volunteers (22 data sets) for the sake of non-invasive analysis and contrasted magnetic resonance (MR) images were used for the aortic examination of Marfan syndrome patients (8 data sets). In this research we present a novel robust segmentation technique for the PWV and aortic distensibility calculation as a complete image processing toolbox. We introduce a novel graph-based method for the centerline extraction of a thoraco-abdominal aorta for the length calculation from 3-D MRI data, robust to artifacts and noise. Moreover, we design a new projection-based segmentation method for transverse aortic region delineation in cardiac magnetic resonance (CMR) images which is robust to high presence of artifacts. Finally, we propose a novel method for analysis of velocity curves in order to obtain pulse wave propagation times. In order to validate the proposed method we compare the obtained results with manually determined aortic centerlines and a region segmentation by an expert, while the results of the PWV measurement were compared to a validated software (LUMC, Leiden, the Netherlands). The obtained results show high correctness and effectiveness of our method for the aortic PWV and distensibility calculation.

  12. Common products from gamma-radiolysis and ultraviolet photolysis of metronidazole

    NASA Astrophysics Data System (ADS)

    Moore, Douglas E.; Wilkins, Brian J.

    u.v. Photolysis of metronidazole in aqueous solution at pH 7.0 results in rearrangement through an imino-ketone to an oxadiazole. These compounds were also found following γ-radiolysis of metronidazole, being about 10% of the products. Saturation of the solution with nitrous oxide caused a slight increase in the yield of imino-ketone in radiolysis. Conversely, the imino-ketone was not detected on addition of sodium formate or propan-2-ol to the radiolysis, but an increased yield of other products was observed. It is suggested that formation of the imino-ketone and oxadiazole in both photolysis and radiolysis occurs via processes which do not involve the nitro radical anion as first transient species.

  13. High Resolution Pulse Compression Imaging Using Super Resolution FM-Chirp Correlation Method (SCM)

    NASA Astrophysics Data System (ADS)

    Fujiwara, M.; Okubo, K.; Tagawa, N.

    This study addresses the issue of the super-resolution pulse compression technique (PCT) for ultrasound imaging. Time resolution of multiple ultrasonic echoes using the FM-Chirp PCT is limited by the bandwidth of the sweep-frequency. That is, the resolution depends on the sharpness of auto-correlation function. We propose the Super resolution FM-Chirp correlation Method (SCM) and evaluate its performance. This method is based on the multiple signal classification (MUSIC) algorithm. Our simulations were made for the model assuming multiple signals reflected from some scatterers. We confirmed that SCM detects time delay of complicated reflected signals successfully with high resolution.

  14. Methods and optical fibers that decrease pulse degradation resulting from random chromatic dispersion

    DOEpatents

    Chertkov, Michael; Gabitov, Ildar

    2004-03-02

    The present invention provides methods and optical fibers for periodically pinning an actual (random) accumulated chromatic dispersion of an optical fiber to a predicted accumulated dispersion of the fiber through relatively simple modifications of fiber-optic manufacturing methods or retrofitting of existing fibers. If the pinning occurs with sufficient frequency (at a distance less than or are equal to a correlation scale), pulse degradation resulting from random chromatic dispersion is minimized. Alternatively, pinning may occur quasi-periodically, i.e., the pinning distance is distributed between approximately zero and approximately two to three times the correlation scale.

  15. [Application of three heat pulse technique-based methods to determine the stem sap flow].

    PubMed

    Wang, Sheng; Fan, Jun

    2015-08-01

    It is of critical importance to acquire tree transpiration characters through sap flow methodology to understand tree water physiology, forest ecology and ecosystem water exchange. Tri-probe heat pulse sensors, which are widely utilized in soil thermal parameters and soil evaporation measurement, were applied to implement Salix matsudana sap flow density (Vs) measurements via heat-ratio method (HRM), T-Max method (T-Max) and single-probe heat pulse probe (SHPP) method, and comparative analysis was conducted with additional Grainer's thermal diffusion probes (TDP) measured results. The results showed that, it took about five weeks to reach a stable measurement stage after TPHP installation, Vs measured with three methods in the early stage after installation was 135%-220% higher than Vs in the stable measurement stage, and Vs estimated via HRM, T-Max and SHPP methods were significantly linearly correlated with Vs estimated via TDP method, with R2 of 0.93, 0.73 and 0.91, respectively, and R2 for Vs measured by SHPP and HRM reached 0.94. HRM had relatively higher precision in measuring low rates and reverse sap flow. SHPP method seemed to be very promising to measure sap flow for configuration simplicity and high measuring accuracy, whereas it couldn' t distinguish directions of flow. T-Max method had relatively higher error in sap flow measurement, and it couldn' t measure sap flow below 5 cm3 · cm(-2) · h(-1), thus this method could not be used alone, however it could measure thermal diffusivity for calculating sap flow when other methods were imposed. It was recommended to choose a proper method or a combination of several methods to measure stem sap flow, based on specific research purpose.

  16. Method and apparatus for rapidly growing films on substrates using pulsed supersonic jets

    DOEpatents

    Eres, Diula; Lowndes, Douglas H.

    1992-01-01

    A method and apparatus for the rapid and economical deposition of uniform and high quality films upon a substrate for subsequent use in producing electronic devices, for example. The resultant films are either epitaxial (crystalline) or amorphous depending upon the incidence rate and the temperature and structure of the substrate. The deposition is carried out in a chamber maintained at about 10.sup.-6 Torr. A gaseous source of the material for forming the deposit is injected into the deposition chamber in the form of a pulsed supersonic jet so as to obtain a high incidence rate. The supersonic jet is produced by a pulsed valve between a relatively high presure reservoir, containing the source gaseous molecules, and the deposition chamber; the valve has a small nozzle orifice (e.g., 0.1-1.0 mm diameter). The type of deposit (crystalline amorphous) is then dependent upon the temperature and structure of the substrate. Very high deposition rates are achieved, and the deposit is very smooth and of uniform thickness. Typically the deposition rate is about 100 times that of much more expensive conventional molecular beam methods for deposition, and comparable to certain expensive plasma-assisted CVD methods of the art. The high growth rate of this method results in a reduced contamination of the deposit from other elements in the environment. The method is illustrated by the deposition of epitaxial and amorphour germanium films upon GaAs substrates.

  17. Doppler ultrasound in the measurement of pulse wave velocity: agreement with the Complior method

    PubMed Central

    2011-01-01

    Aortic stiffness is an independent predictor factor for cardiovascular risk. Different methods for determining pulse wave velocity (PWV) are used, among which the most common are mechanical methods such as SphygmoCor or Complior, which require specific devices and are limited by technical difficulty in obtaining measurements. Doppler guided by 2D ultrasound is a good alternative to these methods. We studied 40 patients (29 male, aged 21 to 82 years) comparing the Complior method with Doppler. Agreement of both devices was high (R = 0.91, 0.84-0.95, 95% CI). The reproducibility analysis revealed no intra-nor interobserver differences. Based on these results, we conclude that Doppler ultrasound is a reliable and reproducible alternative to other established methods for the measurement of aortic PWV. PMID:21496271

  18. A method for pulsed scannerless laser imaging using focal plane array

    NASA Astrophysics Data System (ADS)

    Zhang, Zhi-peng; Wang, Ke-yong; Deng, Jia-hao; Hai, Yan

    2011-06-01

    Laser imaging techniques have advantages for EMI (Electro Magnetic Interference) immunity and abundant image information. This contribution describes the research activity on the scannerless laser imaging detection technique using direct detection aimed at laser fuze applications. The technique using a pulsed laser to illuminate the target and a focal plane array can be used as a receiver. The range information is achieved by means of a direct time of light measurement. Information about the reflectivity of the target is gathered by recording the amplitude of the received pulse. In this paper a high-repetition-frequency, narrow pulse semiconductor laser floodlight emitting system is designed; corresponding optics is used to generate the homogenously illuminated FOI (field of illumination). The echo of laser is collected by receiving optical system fed to focal plane array. Some experiments were done with the emitting and receiving systems that had been designed. Experiments show the validity and rationality of this method. The scannerless structure is robust and provides instantaneous snapshot-type imaging. Avoiding any moving mechanical parts, scannerless laser imaging system have distinct characteristics such as small, compact, high frame rate, wide field of view and high reliability. It is an optimal approach to realize laser imaging fuze.

  19. Investigation of a pulsed current annealing method in reusing MOSFET dosimeters for in vivo IMRT dosimetry

    SciTech Connect

    Luo, Guang-Wen; Qi, Zhen-Yu Deng, Xiao-Wu; Rosenfeld, Anatoly

    2014-05-15

    Purpose: To explore the feasibility of pulsed current annealing in reusing metal oxide semiconductor field-effect transistor (MOSFET) dosimeters forin vivo intensity modulated radiation therapy (IMRT) dosimetry. Methods: Several MOSFETs were irradiated atd{sub max} using a 6 MV x-ray beam with 5 V on the gate and annealed with zero bias at room temperature. The percentage recovery of threshold voltage shift during multiple irradiation-annealing cycles was evaluated. Key dosimetry characteristics of the annealed MOSFET such as the dosimeter's sensitivity, reproducibility, dose linearity, and linearity of response within the dynamic range were investigated. The initial results of using the annealed MOSFETs for IMRT dosimetry practice were also presented. Results: More than 95% of threshold voltage shift can be recovered after 24-pulse current continuous annealing in 16 min. The mean sensitivity degradation was found to be 1.28%, ranging from 1.17% to 1.52%, during multiple annealing procedures. Other important characteristics of the annealed MOSFET remained nearly consistent before and after annealing. Our results showed there was no statistically significant difference between the annealed MOSFETs and their control samples in absolute dose measurements for IMRT QA (p = 0.99). The MOSFET measurements agreed with the ion chamber results on an average of 0.16% ± 0.64%. Conclusions: Pulsed current annealing provides a practical option for reusing MOSFETs to extend their operational lifetime. The current annealing circuit can be integrated into the reader, making the annealing procedure fully automatic.

  20. Method and apparatus for fast laser-pulse detection using gaseous plasmas

    DOEpatents

    McLellan, E.J.; Webb, J.A.

    1981-06-18

    The method and device of the instant invention is a detector of pulsed laser radiation which utilizes the electromotive force generated by the plasma formed when such radiation is focused onto a surface. Measurements are made with a 10.6 ..mu..m CO/sub 2/ laser capable of producing peak intensities of 10/sup 13/ W/cm/sup 2/ when directed through a converging lens. Evacuated detector response to such laser intensity if 1 kV signal peak amplitude and subnanosecond risetimes into a 50 ..cap omega.. load. Detector performance is found to be greatly altered with the introduction of a background gas. For example, with one atmosphere of air, the detector produces prompt signals of the order of 1 V with subnanosecond response for pulse trains lasting 100 ns. With argon, krypton, or zenon at pressures of the order of 10 torr, the detector generates trigger pulses of about 250 V amplitude and 0.2 ns risetimes. Such detectors are quite robust when irradiated with high intensity laser radiation and are useful for qualitative laser beam monitoring.

  1. Method and apparatus for fast laser pulse detection using gaseous plasmas

    DOEpatents

    McLellan, Edward J.; Webb, John A.

    1984-01-01

    The method and device of the instant invention is a detector of pulsed laser radiation which utilizes the electromotive force generated by the plasma formed when such radiation is focused onto a surface (1). Measurements are made with a 10.6 .mu.m CO.sub.2 laser capable of producing peak intensities of 10.sup.13 W/cm.sup.2 when directed through a converging lens (2). Evacuated detector response to such laser intensity is 1 kV signal peak amplitude and subnanosecond risetimes into a 50.OMEGA. load (3). Detector performance is found to be greatly altered with the introduction of a background gas (4). For example, with one atmosphere of air, the detector produces prompt signals of the order of 1 V with subnanosecond response for pulse trains lasting 100 ns. With argon, krypton, or zenon at pressures of the order of 10 torr, the detector generates "trigger pulses" of about 250 V amplitude and 0.2 ns risetimes. Such detectors are quite robust when irradiated with high intensity laser radiation and are useful for qualitative laser beam monitoring.

  2. Method and apparatus for measuring the intensity and phase of an ultrashort light pulse

    DOEpatents

    Kane, Daniel J.; Trebino, Rick P.

    1998-01-01

    The pulse shape I(t) and phase evolution x(t) of ultrashort light pulses are obtained using an instantaneously responding nonlinear optical medium to form a signal pulse. A light pulse, such a laser pulse, is split into a gate pulse and a probe pulse, where the gate pulse is delayed relative to the probe pulse. The gate pulse and the probe pulse are combined within an instantaneously responding optical medium to form a signal pulse functionally related to a temporal slice of the gate pulse corresponding to the time delay of the probe pulse. The signal pulse is then input to a wavelength-selective device to output pulse field information comprising intensity vs. frequency for a first value of the time delay. The time delay is varied over a range of values effective to yield an intensity plot of signal intensity vs. wavelength and delay. In one embodiment, the beams are overlapped at an angle so that a selected range of delay times is within the intersection to produce a simultaneous output over the time delays of interest.

  3. Multiple headspace-solid-phase microextraction as a powerful tool for the quantitative determination of volatile radiolysis products in a multilayer food packaging material sterilized with γ-radiation.

    PubMed

    de Oliveira, Cristiane Patrícia; Rodriguez-Lafuente, Angel; Soares, Nilda de Fátima Ferreira; Nerin, Cristina

    2012-06-29

    A method consisting of multiple headspace solid-phase microextraction followed by gas chromatography-mass spectrometry analysis was developed and used to determine the main volatile radiolysis products formed by γ-irradiation of flexible multilayer food packaging samples. The developed method allows the use of solid-phase microextraction in the quantification of compounds from plastic solid samples. A screening of volatiles in the γ-irradiated and non-irradiated films was performed and 29 compounds were identified in the irradiated packaging, 17 of which were absent in the non-irradiated samples. The main volatile radiolysis products identified were: 1,3-di-tert-butylbenzene; 2,6-di-tert-butyl-1,4-benzoquinone; 4-tert-butyl-phenol and the off-odor compounds butanoic acid and valeric acid. These volatile radiolysis compounds were determined with the proposed method and the results are shown and discussed. Solid-liquid extraction and headspace solid-phase microextraction methods were also studied for comparative purposes. The automated solvent-free multiple HSPME technique here presented can be used to quantify the radiolysis compounds in irradiated plastic solid samples in a simple way with the advantages of being free from matrix influence and environmentally friendly. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Density dependence of the yield of hydrated electrons in the low-LET radiolysis of supercritical water at 400 °C: influence of the geminate recombination of subexcitation-energy electrons prior to thermalization.

    PubMed

    Meesungnoen, Jintana; Sanguanmith, Sunuchakan; Jay-Gerin, Jean-Paul

    2013-10-21

    Monte Carlo simulations were used to calculate the yield of hydrated electrons (eaq(-)) in the low-linear energy transfer radiolysis of supercritical water at 400 °C as a function of water density over the range of ~0.15 to 0.6 g cm(-3). Very good agreement was found between our calculations and picosecond pulse radiolysis experimental data at ~60 ps and 1 ns at high density (>0.35 g cm(-3)). At densities lower than ~0.35 g cm(-3), our eaq(-) yields were lower than the experimental data, especially at ~60 ps. However, if we incorporated into the simulations a prompt geminate electron-cation (H2O˙(+)) recombination (prior thermalization of the electron) that decreased as the density decreased, our computed eaq(-) yields at ~60 ps and 1 ns compared fairly well with the experimental data for the entire density range studied.

  5. AFM and pulsed laser ablation methods for Cultural Heritage: application to archeometric analysis of stone artifacts

    NASA Astrophysics Data System (ADS)

    Barberio, M.; Veltri, S.; Stranges, F.; Bonanno, A.; Xu, F.; Antici, P.

    2015-09-01

    In this paper, we introduce the use of the atomic force microscope (AFM) and of the pulsed laser ablation as methods for morphological diagnostic with nanoscale precision of archeological artifacts and corrosive patina removal from stone artifacts. We test our methodology on stone artifacts extracted from the Church of Sotterra (located in Calabria, South Italy). The AFM microscopy was compared with different petrographic, chemical, optical and morphological analysis methods for identifying the textural characteristics, evaluating the state of preservation and formulating some hypotheses about the provenance and composition of the impurity patina located on the artifact surfaces. We demonstrate that with the nanometric precision obtained with AFM microscopy, it is possible to distinguish the different states of preservation, much better than using conventional petrographic methods. The surface's roughness is evaluated from very small artifact's fragments, reducing the coring at micrometric scale with a minimal damage to the artworks. After the diagnosis, we performed restoration tests using the pulsed laser ablation (PLA) method and compared it with the more common micro-sandblasting under dry conditions. We find that the PLA is highly effective for the removal of the surficial patina, with a control of a few hundreds of nanometers in the cleaning of surface, without introducing chemical or morphological damages to the artifacts. Moreover, PLA can be easily implemented in underwater conditions; this has the great advantage that stone and pottery artifacts for marine archeological sites do not need to be removed from the site.

  6. A new method for measurement of pulse wave velocity in arterial wall

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoming; Kinnick, Randall R.; Fatemi, Mostafa; Greenleaf, James F.

    2003-10-01

    Arterial wall stiffness can be associated with various diseases. The stiffness of an artery can be assessed by measurement of the pulse wave velocity (PWV). PWV is directly related to the Youngs modulus by the well-known Moens-Korteweg equation. Usually, PWV is estimated using the foot-to-foot method. However, the foot of the pressure wave is not very clear due to reflected waves. Also, the pressure wave is normally at a low frequency, hence, the time resolution is low. PWV is an average indicator of artery stiffness between the two measuring points, therefore it is not easy to identify local stiffness. We propose producing a very short pulse wave in the arterial wall using ultrasound radiation force and measuring its propagation speed along the artery by laser. The temporal resolution of this method is in the range of microseconds, which allows PWV to be measured accurately over a few millimeters. Experiments were carried out on a silicone tube in gelatin. PWV was measured by two scanning methods: (1) fixed source and scanning detector, (2) scanning source and fixed detector. Results: PWV was measured at 2 mm/40 μs by both methods. The Doppler technique was also tested which is potentially suitable for clinical applications.

  7. Stability and a fast calculation method of travel speed of pulse peak in convergence zone

    NASA Astrophysics Data System (ADS)

    Ren, Yun; Zhang, RenHe; Wang, Jun; Guo, YongGang; Luo, WenYu

    2014-07-01

    A long-range sound propagation experiment was conducted in the West Pacific Ocean in summer 2013. The signals received by a towed array indicate that the travel speed of pulse peak (TSPP) in the convergence zones is stable. Therefore, an equivalent sound speed can be used at all ranges in the convergence zones. A fast calculation method based on the beam-displacement ray-mode (BDRM) theory and convergence zone theory is proposed to calculate this equivalent sound speed. The computation speed of this proposed method is over 1000 times faster than that of the conventional calculation method based on the normal mode theory, with the computation error less than 0.4% compared with the experimental result. Also, the effect of frequency and sound speed profile on the TSPP is studied with the conventional and fast calculation methods, showing that the TSPP is almost independent of the frequency and sound speed profile in the ocean surface layer.

  8. [Determination of polydextrose in food by high performance anion exchange chromatographic method with pulsed amperometric detector].

    PubMed

    Li, Jianwen; Wang, Guodong; Yang, Yuexin

    2008-03-01

    The HPAEC-PAD method for polydextrose determination was developed based on AOAC 2000.11. This method included water extraction, centrifugal ultrafiltration, mulienzyme hydrolysis, and anion exchange chromatography detection. The polydextrose was elated by a gradient program of 0.15 mol/L NaOH and 0.5mol/L sodium acetate in 0.15 mol/L NaOH on a CarboPAC TM PA 1 column, then detected by a gold electrode with pulse amperometric detection mold. The inject volume was 20 microl. The LOD and LOQ of this method were 1.69 microg/g, 5.47 microg/g, respectively. The repeatability and reproducibility were excellent, ranging from 2.10% to 6.62%. The average recovery of polydextrose in various food matrix were 92.4%-104.4%. This method could be used for polydextrose determination in foods.

  9. Pulse-shape discrimination in neutron depth profiling radioanalytical methods. Part II

    NASA Astrophysics Data System (ADS)

    Vacík, J.; Červená, J.; Hnatowicz, V.; Havránek, V.; Hoffmann, J.; Pošta, S.; Fink, D.

    1999-01-01

    Pulse shape discrimination (PSD) is used for the reduction of radiation background in the depth sensitive neutron depth profiling method (NDP) based on the detection of charged particles from the (n, α) and (n, p) nuclear reactions induced by thermal neutrons on some light elements. The experimental NDP-PSD arrangement is described and its performance is demonstrated on the measurement of real samples. Background reduction by several orders of magnitude in the region below 1 MeV leads to a corresponding sensitivity improvement and to an extension of the measurable depth region for some light elements.

  10. Pulse retrieval in frequency-resolved optical gating based on the method of generalized projections

    SciTech Connect

    DeLong, K.W.; Fittinghoff, D.N.; Trebino, R. ); Kohler, B.; Wilson, K. )

    1994-12-15

    We use the algorithmic method of generalized projections (GP's) to retrieve the intensity and phase of an ultrashort laser pulse from the experimental trace in frequency-resolved optical gating (FROG). Using simulations, we show that the use of GP's improves significantly the convergence properties of the algorithm over the basic FROG algorithm. In experimental measurements, the GP-based algorithm achieves significantly lower errors than previous algorithms. The use of GP's also permits the inclusion of an arbitrary material response function in the FROG problem.

  11. Application of the Marquardt least-squares method to the estimation of pulse function parameters

    NASA Astrophysics Data System (ADS)

    Lundengârd, Karl; Rančić, Milica; Javor, Vesna; Silvestrov, Sergei

    2014-12-01

    Application of the Marquardt least-squares method (MLSM) to the estimation of non-linear parameters of functions used for representing various lightning current waveshapes is presented in this paper. Parameters are determined for the Pulse, Heidler's and DEXP function representing the first positive, first and subsequent negative stroke currents as given in IEC 62305-1 Standard Ed.2, and also for some other fast- and slow-decaying lightning current waveshapes. The results prove the ability of the MLSM to be used for the estimation of parameters of the functions important in lightning discharge modeling.

  12. Noncontact single-pulse optical method to measure interfacial properties in intact systems.

    PubMed

    Clark, David C; Kim, Myung K

    2012-12-15

    We introduce a noncontact purely optical approach to measuring the localized surface properties of an interface within a system using a single optical pressure pulse and a time-resolved digital holographic quantitative phase-imaging technique to track the propagating nanometric capillary disturbance. We demonstrate the proposed method's ability to measure the surface energy of deionized water, methanol, and chemical monolayers formed by surfactants with good agreement to published values. The development of this technique boasts immediate application to static and dynamic systems and near-future applications for living biological cell membranes.

  13. Structure and Properties of Nanocrystalline Iron Oxide Powder Prepared by the Method of Pulsed Laser Ablation

    NASA Astrophysics Data System (ADS)

    Svetlichnyi, V. A.; Shabalina, A. V.; Lapin, I. N.

    2017-04-01

    Colloidal solution of iron oxide nanoparticles is synthesized by nanosecond pulsed laser ablation (Nd:YAG laser, 1064 nm, 7 ns, and 180 mJ) of a metallic iron target in water, and nanocrystalline powder is prepared from this solution by vacuum drying. A composition and structure of the material obtained are investigated by methods of electron microscopy, x-ray diffraction, and optical spectroscopy. It is established that oxide particles with average size of about 5 nm and Fe3O4 magnetite structure are mainly formed during ablation. Preliminary investigation of magnetic properties of the prepared nanoparticle powders shows that they can be in ferromagnetic and/or superparamagnetic states.

  14. A method for localized computation of Pulse Wave Velocity in carotid structure.

    PubMed

    Patil, Ravindra B; Krishnamoorthy, P; Sethuraman, Shriram

    2015-01-01

    Pulse Wave Velocity (PWV) promises to be a useful clinical marker for noninvasive diagnosis of atherosclerosis. This work demonstrates the ability to perform localized carotid PWV measurements from the distention waveform derived from the Radio Frequency (RF) ultrasound signal using a carotid phantom setup. The proposed system consists of low cost custom-built ultrasound probe and algorithms for envelope detection, arterial wall identification, echo tracking, distension waveform computation and PWV estimation. The method is proposed on a phantom data acquired using custom-built prototype non-imaging probe. The proposed approach is non-image based and can be seamlessly integrated into existing clinical ultrasound scanners.

  15. A Heuristic Fast Method to Solve the Nonlinear Schroedinger Equation in Fiber Bragg Gratings with Arbitrary Shape Input Pulse

    SciTech Connect

    Emami, F.; Hatami, M.; Keshavarz, A. R.; Jafari, A. H.

    2009-08-13

    Using a combination of Runge-Kutta and Jacobi iterative method, we could solve the nonlinear Schroedinger equation describing the pulse propagation in FBGs. By decomposing the electric field to forward and backward components in fiber Bragg grating and utilizing the Fourier series analysis technique, the boundary value problem of a set of coupled equations governing the pulse propagation in FBG changes to an initial condition coupled equations which can be solved by simple Runge-Kutta method.

  16. Long pulse generation technology of solid-state laser adopting a new real time multi-discharge method

    NASA Astrophysics Data System (ADS)

    Hong, Jung-Hwan; Song, Kum-Young; Chung, Hyun-Ju; Jung, Jong-Han; Kim, Whi-Young; Kang, Uk; Kim, Hee-Je

    2002-04-01

    In this study, a solid-state laser system adopting a new real time multi-discharge method in which three flashlamps are turned on consecutively was designed and fabricated to examine the pulse width and the pulse shape of the laser beams depending upon the changes in the lamp turn-on time. That is, this study shows a technology that makes it possible to make various pulse shapes by turning on three flashlamps consecutively on a real-time basis with the aid of a program integrated circuit one-chip microprocessor. With this technique, the lamp turn-on delay time can be varied more diversely from 0 to 10 ms and the real-time control is possible with an external keyboard, enabling various pulse shapes. In addition, longer pulses can be more widely used for industrial processing and many medical purposes.

  17. X-ray pulse preserving single-shot optical cross-correlation method for improved experimental temporal resolution

    SciTech Connect

    Beye, M.; Krupin, O.; Hays, G.; Jong, S. de; Lee, S.; Coffee, R.; Holmes, M. R.; Fry, A. R.; White, W. E.; Bostedt, C.; Schlotter, W. F.; Reid, A. H.; Rupp, D.; Lee, W.-S.; Scherz, A. O.; Chuang, Y.-D.; Cryan, J. P.; Glownia, J. M.; Foehlisch, A.; Durr, H. A.

    2012-03-19

    We measured the relative arrival time between an optical pulse and a soft x-ray pulse from a free-electron laser. This femtosecond cross-correlation measurement was achieved by observing the change in optical reflectivity induced through the absorption of a fraction of the x-ray pulse. The main x-ray pulse energy remained available for an independent pump-probe experiment where the sample may be opaque to soft x-rays. The method was employed to correct the two-pulse delay data from a canonical pump-probe experiment and demonstrate 130 {+-} 20 fs (FWHM) temporal resolution. We further analyze possible timing jitter sources and point to future improvements.

  18. Calculation of photon pulse height distribution using deterministic and Monte Carlo methods

    NASA Astrophysics Data System (ADS)

    Akhavan, Azadeh; Vosoughi, Naser

    2015-12-01

    Radiation transport techniques which are used in radiation detection systems comprise one of two categories namely probabilistic and deterministic. However, probabilistic methods are typically used in pulse height distribution simulation by recreating the behavior of each individual particle, the deterministic approach, which approximates the macroscopic behavior of particles by solution of Boltzmann transport equation, is being developed because of its potential advantages in computational efficiency for complex radiation detection problems. In current work linear transport equation is solved using two methods including collided components of the scalar flux algorithm which is applied by iterating on the scattering source and ANISN deterministic computer code. This approach is presented in one dimension with anisotropic scattering orders up to P8 and angular quadrature orders up to S16. Also, multi-group gamma cross-section library required for this numerical transport simulation is generated in a discrete appropriate form. Finally, photon pulse height distributions are indirectly calculated by deterministic methods that approvingly compare with those from Monte Carlo based codes namely MCNPX and FLUKA.

  19. Pulsed arrays: A new method of flaw detection by generating a frequency dependent angle of propagation

    NASA Astrophysics Data System (ADS)

    Hill, S. J.; Dixon, S. M.

    2012-05-01

    A new method of using an array of generation sources, pulsed simultaneously to generate a wavefront with a frequency dependant angle of propagation, has been developed. If pulsed arrays are used to generate a wave with a frequency dependent angle of propagation, the angle at which the wave was launched can be identified by measuring the frequency of the detected wave. In an isotropic material this means that it is possible use a second transducer to locate the position of the scatterer, whereas with a conventional single element generator method, it can only be located onto an ellipse. In addition to an increased scan speed, the resolution of detection should also be improved. A theoretical framework is put forward to explain how the wavefront is created from the superposition of the waves from the individual elements, and how the frequency varies along the wavefront. Finite element models and experimental measurements were also carried out, and both agreed with the analytic model. This method will have applications within NDE, but could also extend to sonar and radar techniques.

  20. Method and apparatus for enhancing surface absorption and emissivity in optical pulsed infrared nondestructive evaluation

    NASA Astrophysics Data System (ADS)

    Duan, Yuxia; Zhang, Cunlin; Jin, Wanping; Wu, Naiming

    2009-07-01

    In the application of optical pulsed infrared NDE, the visible light absorption and IR emissivity of the detected object must be considered. One of the simple methods is spraying paint on the highly reflective and low IR emissivity surface before testing. However, for some materials such as with pore space in the surface or easily to be corrupted have to be pretreated by other method and apparatus. Two kinds of apparatus for surface pretreating are designed according to the dimension of the detected object and the testing conditions. One apparatus is independent of the former detecting system, and the other is an improvement of the former system. The basic principle of the two apparatus is covering a flexible membrane of high light absorption and IR emissivity on the specimen surface by vacuum pumping. The paper also present the applications of the method, including the detection of the metal mesh material and the honeycomb structures with aluminum coating. The experimental results show that the technique of covering thin film by vacuum pump is effective for enhancing surface absorption and emissivity; moreover, it does not pollute or damage the sample. The application of the technique has practical significance, because it extends the scope of the application of the optical pulsed thermography nondestructive evaluation.

  1. Pulsed Dilution Method for the Recovery of Aggregated Mouse TNF-α

    PubMed Central

    Mahmoodi, Merat; Ghodsi, Maryam; Moghadam, Malihe; Sankian, Mojtaba

    2017-01-01

    Background: The expression of mouse tumor necrosis factor alpha (TNF-α) in Escherichia coli is a favorable way to get high yield of protein; however, the formation of cytoplasmic inclusion bodies, which is the consequence of insoluble accumulated proteins, is a major obstacle in this system. To overcome this obstacle, we used a pulsed dilution method to convert the product to its native conformation Methods: Reducing agent and guanidine hydrochloride were used to solubilize inclusion bodies formed after TNF-(α) expression. Then, the refolding procedure was performed by pulsed dilution of the denatured protein into a refolding buffer. The properly-folded protein was purified by metal affinity chromatography. Results: SDS-PAGE showed a 19.9 kDa band related to the mature TNF-(α) protein. The protein was recognized by anti-mouse TNF-(α) on western blots. The final concentration of the purified recombinant TNF-(α) was 62.5 µg/mL Conclusions: Our study demonstrates the efficiency of this method to produce a high yield of folded mature TNF- (α). PMID:28367471

  2. Analysis of capacity fading effect on Lithium Cobalt cells caused by pulse current technique in fast charging methods

    NASA Astrophysics Data System (ADS)

    Hafiz, S.; Arianto, S.; Yunaningsih, R. Y.; Majid, N.; Prihandoko, B.

    2017-04-01

    Charging a battery in a short time is important for portable devices. Many techniques have been developed to find out the proper method for fast charging. One of those techniques that has been patented in several fast charging methods is pulse current technique. This technique implements pulse current with adjusting pulse wide and voltage threshold in a certain values. In this paper, the capacity fading effects caused by the current pulse in lithium cobalt cells were investigated. The experiment was done by applying pulse current at high-level SOC to charge four cylindrical lithium cobalt cells. The Capacity of each cell was checked every 50 charge-discharge cycles. The experiment result shows that the changing capacity in each cell forms patterns alike. As if there was a slight increament on their capacities at first checking but rapidly decreasing at the next check. Then, their capacities continue to decrease slowly but the more often the charge-discharge cycling, the battery lifetime decreased. This research has provided analysis of pulse current effect on lithium cobalt capacity fading that should be noted as a reference in applying current pulse for fast charging methods.

  3. On study fine atmospheric structure by using of the method of decomposition of infrasonic signals from pulsed sources

    NASA Astrophysics Data System (ADS)

    Kulichkov, Sergey; Chunchuzov, Igor; Demin, Dmitry

    2016-04-01

    The proposed method are based on the decomposition of infrasonic signals from pulse sources. In this method, the recorded infrasonic signal is modeled by the sequence of single acoustic pulse having the form of a U and N waves. Each pulse U and N wave corresponds to the reflection of sound from atmospheric inhomogeneities at different altitudes in the atmosphere. By determining time intervals between such pulses U and N waves it is possible to determine vertical gradients of the effective sound speed at the different altitudes in the atmosphere. The method to determine the vertical profiles of the vertical gradients of effective sound velocity in the atmosphere by using data from infrasound monitoring are proposed. The obtained data are corresponds to the theory of the fine structure in the upper atmosphere.

  4. Calibration of pulsed electroacoustic method considering electrode-dielectric interface status and porosity

    NASA Astrophysics Data System (ADS)

    Huang, Meng; Zhou, Yuanxiang; Chen, Weijiang; Lu, Licheng; Jin, Fubao; Huang, Jianwen

    2014-10-01

    Pulsed electroacoustic (PEA) method is widely used, but measurement conditions not always agree with the underlying PEA assumptions. This necessitates space charge recovery; however, existing research only addresses the attenuation and dispersion in lossy media. The effects of electrode-dielectric interface contact status and porosity on the accuracy of space charge distribution are discussed in the present article. It is shown that the presence of nonlinear interface and porosity can introduce severe error. However, because the properties of acoustic propagation of waves (which are generated from charge on the electrode and in the bulk) are different, the conventional recovery algorithm is no longer suitable for calibrating the charge density. To obtain accurate space charge profiles, it is necessary to eliminate these effects. A method has been proposed which is based on the original measurement process. The validity of the proposed method was tested by reasonable post-recovery electric field distributions.

  5. Protonmotive stoichiometry of rat liver cytochrome c oxidase: determination by a new rate/pulse method.

    PubMed

    Moody, A J; Mitchell, R; West, I C; Mitchell, P

    1987-11-19

    The stoichoimetry of vectorial H+ ejection coupled to electron flow through the cytochrome c oxidase (EC 1.9.3.1) of rat liver mitochondria was determined by a new rate/pulse method. This is a modification of the oxygen-pulse method. Electron flow through the oxidase is initiated by adding oxygen to suspensions of anaerobic mitochondria at a known and constant rate. Cytochrome c oxidase was examined directly or in combination with cytochrome c reductase (ubiquinol:ferricytochrome c oxidoreductase). In both cases the----H0+/2e- ratio was found to be constant during the time-course of oxygen reduction, and thus independent of delta pH. The stoichiometries observed were consistent with mechanistic stoichiometries of 2 and 6 for cytochrome c oxidase alone and cytochrome c oxidase together with cytochrome c reductase, respectively. The stoichiometry of cytochrome c reductase alone was also examined, by using ferricyanide in place of oxygen. The results obtained were consistent with the accepted mechanistic stoichiometry of 4 for this enzyme.

  6. Pulse-fitting - A novel method for the evaluation of pulse measurements, demonstrated for the low frequency behavior of lithium-ion cells

    NASA Astrophysics Data System (ADS)

    Schmidt, Jan Philipp; Ivers-Tiffée, Ellen

    2016-05-01

    The impedance of a commercial lithium ion cell (2 Ah) is evaluated over a wide frequency range of 10-5 Hz < f < 102 Hz using a new approach. The so-called pulse-fitting method (PFM) derives the cell impedance from time domain measurements, which are transferred into frequency data by a using a newly developed evaluation algorithm in combination with the distribution of relaxation times (DRT). The time constants of the individual polarization processes taking place during charging/discharging were analyzed at 20 different state-of-charge levels at 23 °C in a wide frequency range spanning from 10-5 Hz < f < 102 Hz. The pulse-fitting method seems to be especially useful for monitoring the change of individual polarization losses in the course of time, as self-discharge effects can be sorted out.

  7. Conditions for critical effects in the mass action kinetics equations for water radiolysis.

    PubMed

    Wittman, Richard S; Buck, Edgar C; Mausolf, Edward J; McNamara, Bruce K; Smith, Frances N; Soderquist, Chuck Z

    2014-12-26

    We report on a subtle global feature of the mass action kinetics equations for water radiolysis that results in predictions of a critical behavior in H2O2 and associated radical concentrations. While radiolysis kinetics have been studied extensively in the past, it is only in recent years that high-speed computing has allowed the rapid exploration of the solution over widely varying dose and compositional conditions. We explore the radiolytic production of H2O2 under various externally fixed conditions of molecular H2 and O2 that have been regarded as problematic in the literature-specifically, "jumps" in predicted concentrations, and inconsistencies between predictions and experiments have been reported for α radiolysis. We computationally map-out a critical concentration behavior for α radiolysis kinetics using a comprehensive set of reactions. We then show that all features of interest are accurately reproduced with 15 reactions. An analytical solution for steady-state concentrations of the 15 reactions reveals regions in [H2] and [O2] where the H2O2 concentration is not unique-both stable and unstable concentrations exist. The boundary of this region can be characterized analytically as a function of G-values and rate constants independent of dose rate. Physically, the boundary can be understood as separating a region where a steady-state H2O2 concentration exists from one where it does not exist without a direct decomposition reaction. We show that this behavior is consistent with reported α radiolysis data and that no such behavior should occur for γ radiolysis. We suggest experiments that could verify or discredit a critical concentration behavior for α radiolysis and could place more restrictive ranges on G-values from derived relationships between them.

  8. Conditions for critical effects in the mass action kinetics equations for water radiolysis

    SciTech Connect

    Wittman, Richard S.; Buck, Edgar C.; Mausolf, Edward J.; McNamara, Bruce K.; Smith, Frances N.; Soderquist, Chuck Z.

    2014-11-25

    We report on a subtle global feature of the mass action kinetics equations for water radiolysis that results in predictions of a critical behavior in H2O2 and associated radical concentrations. While radiolysis kinetics has been studied extensively in the past, it is only in recent years that high speed computing has allowed the rapid exploration of the solution over widely varying dose and compositional conditions. We explore the radiolytic production of H2O2 under various externally fixed conditions of molecular H2 and O2 that have been regarded as problematic in the literature – specifically, “jumps” in predicted concentrations, and inconsistencies between predictions and experiments have been reported for alpha radiolysis. We computationally map-out a critical concentration behavior for alpha radiolysis kinetics using a comprehensive set of reactions. We then show that all features of interest are accurately reproduced with 15 reactions. An analytical solution for steady-state concentrations of the 15 reactions reveals regions in [H2] and [O2] where the H2O2 concentration is not unique – both stable and unstable concentrations exist. The boundary of this region can be characterized analytically as a function of G-values and rate constants independent of dose rate. Physically, the boundary can be understood as separating a region where a steady-state H2O2 concentration exists, from one where it does not exist without a direct decomposition reaction. We show that this behavior is consistent with reported alpha radiolysis data and that no such behavior should occur for gamma radiolysis. We suggest experiments that could verify or discredit a critical concentration behavior for alpha radiolysis and could place more restrictive ranges on G-values from derived relationships between them.

  9. Conditions for critical effects in the mass action kinetics equations for water radiolysis

    SciTech Connect

    Wittman, Richard S.; Buck, Edgar C.; Mausolf, Edward J.; McNamara, Bruce K.; Smith, Frances N.; Soderquist, Chuck Z.

    2014-12-26

    We report on a subtle global feature of the mass action kinetics equations for water radiolysis that results in predictions of a critical behavior in H2O2 and associated radical concentrations. While radiolysis kinetics has been studied extensively in the past, it is only in recent years that high speed computing has allowed the rapid exploration of the solution over widely varying dose and compositional conditions. We explore the radiolytic production of H2O2 under various externally fixed conditions of molecular H2 and O2 that have been regarded as problematic in the literature – specifically, “jumps” in predicted concentrations, and inconsistencies between predictions and experiments have been reported for alpha radiolysis. We computationally map-out a critical concentration behavior for alpha radiolysis kinetics using a comprehensive set of reactions. We then show that all features of interest are accurately reproduced with 15 reactions. An analytical solution for steady-state concentrations of the 15 reactions reveals regions in [H2] and [O2] where the H2O2 concentration is not unique – both stable and unstable concentrations exist. The boundary of this region can be characterized analytically as a function of G-values and rate constants independent of dose rate. Physically, the boundary can be understood as separating a region where a steady-state H2O2 concentration exists, from one where it does not exist without a direct decomposition reaction. We show that this behavior is consistent with reported alpha radiolysis data and that no such behavior should occur for gamma radiolysis. We suggest experiments that could verify or discredit a critical concentration behavior for alpha radiolysis and could place more restrictive ranges on G-values from derived relationships between them.

  10. A method for the formation of Pt metal nanoparticle arrays using nanosecond pulsed laser dewetting

    SciTech Connect

    Owusu-Ansah, Ebenezer; Horwood, Corie A.; Birss, Viola I.; Shi, Yujun J.; El-Sayed, Hany A.

    2015-05-18

    Nanosecond pulsed laser dewetting of Pt thin films, deposited on a dimpled Ta (DT) surface, has been studied here in order to form ordered Pt nanoparticle (NP) arrays. The DT substrate was fabricated via a simple electrochemical anodization process in a highly concentrated H{sub 2}SO{sub 4} and HF solution. Pt thin films (3–5 nm) were sputter coated on DT and then dewetted under vacuum to generate NPs using a 355 nm laser radiation (6–9 ns, 10 Hz). The threshold laser fluence to fully dewet a 3.5 nm thick Pt film was determined to be 300 mJ/cm{sup 2}. Our experiments have shown that shorter irradiation times (≤60 s) produce smaller nanoparticles with more uniform sizes, while longer times (>60 s) give large nanoparticles with wider size distributions. The optimum laser irradiation time of 1 s (10 pulses) has led to the formation of highly ordered Pt nanoparticle arrays with an average nanoparticle size of 26 ± 3 nm with no substrate deformation. At the optimum condition of 1 s and 500 mJ/cm{sup 2}, as many as 85% of the dewetted NPs were found neatly in the well-defined dimples. This work has demonstrated that pulsed laser dewetting of Pt thin films on a pre-patterned dimpled substrate is an efficient and powerful technique to produce highly ordered Pt nanoparticle arrays. This method can thus be used to produce arrays of other high-melting-point metal nanoparticles for a range of applications, including electrocatalysis, functionalized nanomaterials, and analytical purposes.

  11. A method for the formation of Pt metal nanoparticle arrays using nanosecond pulsed laser dewetting

    NASA Astrophysics Data System (ADS)

    Owusu-Ansah, Ebenezer; Horwood, Corie A.; El-Sayed, Hany A.; Birss, Viola I.; Shi, Yujun J.

    2015-05-01

    Nanosecond pulsed laser dewetting of Pt thin films, deposited on a dimpled Ta (DT) surface, has been studied here in order to form ordered Pt nanoparticle (NP) arrays. The DT substrate was fabricated via a simple electrochemical anodization process in a highly concentrated H2SO4 and HF solution. Pt thin films (3-5 nm) were sputter coated on DT and then dewetted under vacuum to generate NPs using a 355 nm laser radiation (6-9 ns, 10 Hz). The threshold laser fluence to fully dewet a 3.5 nm thick Pt film was determined to be 300 mJ/cm2. Our experiments have shown that shorter irradiation times (≤60 s) produce smaller nanoparticles with more uniform sizes, while longer times (>60 s) give large nanoparticles with wider size distributions. The optimum laser irradiation time of 1 s (10 pulses) has led to the formation of highly ordered Pt nanoparticle arrays with an average nanoparticle size of 26 ± 3 nm with no substrate deformation. At the optimum condition of 1 s and 500 mJ/cm2, as many as 85% of the dewetted NPs were found neatly in the well-defined dimples. This work has demonstrated that pulsed laser dewetting of Pt thin films on a pre-patterned dimpled substrate is an efficient and powerful technique to produce highly ordered Pt nanoparticle arrays. This method can thus be used to produce arrays of other high-melting-point metal nanoparticles for a range of applications, including electrocatalysis, functionalized nanomaterials, and analytical purposes.

  12. Method of synchronization measurement via spatial-spectral interference in coherent combination of multi-channel ultra-short pulses

    NASA Astrophysics Data System (ADS)

    Li, Z. L.; Zuo, Y. L.; Wu, Z. H.; Wang, X.; Mu, J.; Yu, H. Y.; Zhao, D.; Zhu, Q. H.; Su, J. Q.; Zhou, K. N.; Zhou, S.; Feng, X.; Zhang, S.; Liu, H. Z.

    2017-08-01

    Spatial-spectral interference fringes contain information on the time delay between pulses. By extracting the slope of the equiphase line in the spatial-spectral interference fringes, a large range and high-precision detection of the time delay is realized. Theoretical analysis is given. An experiment demonstrates the fundamental process for obtaining the time delay between two femtosecond pulses. In the current experiment the measurement range is from 0.4 fs to hundreds of fs. This method was first proposed for synchronization measurement of coherent combination of ultra-short pulses in a multi-channel system. The method can be applied at large scales in an ultra-short pulse laser facility.

  13. A new oscillometric method for pulse wave analysis: comparison with a common tonometric method

    PubMed Central

    Wassertheurer, S; Kropf, J; Weber, T; van der Giet, M; Baulmann, J; Ammer, M; Hametner, B; Mayer, C C; Eber, B; Magometschnigg, D

    2010-01-01

    In the European Society of Cardiology–European Society of Hypertension guidelines of the year 2007, the consequences of arterial stiffness and wave reflection on cardiovascular mortality have a major role. But the investigators claimed the poor availability of devices/methods providing easy and widely suitable measuring of arterial wall stiffness or their surrogates like augmentation index (AIx) or aortic systolic blood pressure (aSBP). The aim of this study was the validation of a novel method determining AIx and aSBP based on an oscillometric method using a common cuff (ARCSolver) against a validated tonometric system (SphygmoCor). aSBP and AIx measured with the SphygmoCor and ARCSolver method were compared for 302 subjects. The mean age was 56 years with an s.d. of 20 years. At least two iterations were performed in each session. This resulted in 749 measurements. For aSBP the mean difference was −0.1 mm Hg with an s.d. of 3.1 mm Hg. The mean difference for AIx was 1.2% with an s.d. of 7.9%. There was no significant difference in reproducibility of AIx for both methods. The variation estimate of inter- and intraobserver measurements was 6.3% for ARCSolver and 7.5% for SphygmoCor. The ARCSolver method is a novel method determining AIx and aSBP based on an oscillometric system with a cuff. The results agree with common accepted tonometric measurements. Its application is easy and for widespread use. PMID:20237499

  14. A method for reproducibly preparing synthetic nanopores for resistive-pulse biosensors.

    PubMed

    Wharton, John E; Jin, Pu; Sexton, Lindsay T; Horne, Lloyd P; Sherrill, Stefanie A; Mino, Warren K; Martin, Charles R

    2007-08-01

    There is increasing interest in using nanopores in synthetic membranes as resistive-pulse sensors for biomedical analytes. Analytes detected with prototype artificial-nanopore biosensors include drugs, DNA, proteins, and viruses. This field is, however, currently in its infancy. A key question that must be addressed in order for such sensors to progress from an interesting laboratory experiment to practical devices is: Can the artificial-nanopore sensing element be reproducibly prepared? We have been evaluating sensors that employ a conically shaped nanopore prepared by the track-etch method as the sensor element. We describe here a new two-step pore-etching procedure that allows for good reproducibility in nanopore fabrication. In addition, we describe a simple mathematical model that allows us to predict the characteristics of the pore produced given the experimental parameters of the two-step etch. This method and model constitute important steps toward developing practical, real-world, artificial-nanopore biosensors.

  15. Fabrication of Nanocomposite Thermoelectric Materials by a Pulsed Laser Deposition Method

    NASA Astrophysics Data System (ADS)

    Matsubara, Masato; Azuma, Hirozumi; Asahi, Ryoji

    2011-05-01

    We applied a pulsed laser deposition (PLD) technique to fabricate nanocomposite half-Heusler thermoelectrics by employing two different methods: a dry process and a wet process. First, we tried to obtain nanosized thermoelectric particles by using PLD in a liquid solvent. Nanosized (<100 nm) spherical and crystalline half-Heusler particles containing Ti, Zr, Hf, Ni, and Sn elements were obtained by this method, showing good controllability of stoichiometry. The key is to select a solvent that prevents oxidation. Second, the dry PLD process was employed to coat the thermoelectric powder with metal oxides. To this end, we developed a PLD coating apparatus. After sintering the coated powder using the spark plasma sintering (SPS) technique, we confirmed that a nanosized layer of the metal oxides was uniformly formed at the grain boundaries of the half-Heusler matrix. With these two examples, the capability of the PLD techniques to fabricate well-controlled nanocomposite thermoelectric materials is demonstrated.

  16. Vitroceramic interface deposited on titanium substrate by pulsed laser deposition method.

    PubMed

    Voicu, Georgeta; Miu, Dana; Dogaru, Ionut; Jinga, Sorin Ion; Busuioc, Cristina

    2016-08-30

    Pulsed laser deposition (PLD) method was used to obtain biovitroceramic thin film coatings on titanium substrates. The composition of the targets was selected from SiO2-CaO-P2O5-(CaF2) systems and the corresponding masses were prepared using the sol-gel method. The depositions were performed in oxygen atmosphere (100mTorr), while the substrates were heated at 400°C. The PLD deposited films were analysed through different experimental techniques: X-ray diffraction, scanning (SEM, EDX) and transmission (HRTEM, SAED) electron microscopy and infra-red spectroscopy coupled with optical microscopy. They were also biologically tested by in vitro cell culture and the contact angle was determined. The bioevaluation results indicate a high biocompatibilty of the obtained materials, demonstrating their potential use for biomedical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Methods on handling missing rainfall data with Neyman-Scott rectangular pulse modeling

    NASA Astrophysics Data System (ADS)

    Yendra, Rado; Jemain, Abdul Aziz; Zahari, Marina; Wan Zin, Wan Zawiah

    2013-04-01

    Rainfall data from rain-gauge stations suffers the risk of being missing due to factors such as human negligence, faulty equipment and disasters. In this paper, complete monthly rainfall data from 1985 to 1992 in Payakangsar station is used as the base data to determine the appropriate method for handling missing data. A portion of this complete data is then omitted at random by as much as 5%, 10% and 15% of the total number of data. Three methods of missing data replacement are considered that is, replacement of the missing data with zero (NR), single imputation (SI) and multiple imputation (MI) methods. The Neyman-Scott Rectangular Pulse (NSRP) rainfall stochastic model is then fitted to the resulting data from these three methods. Data from the month of October and November are selected for further analysis as these two months represent the months with highest rainfall amount received. To assess the performance of these three methods, a goodness-of-fit test based on the mean absolute error is applied. Results from the goodness-of-fit test indicate that NR method is the best for each case of missing data in the month of October, and also for the 5% case in November. On the other hand, method of imputation with 4 stages (MI) is superior for cases of 10% and 15% in November.

  18. Method for producing H.sub.2 using a rotating drum reactor with a pulse jet heat source

    DOEpatents

    Paulson, Leland E.

    1990-01-01

    A method of producing hydrogen by an endothermic steam-carbon reaction using a rotating drum reactor and a pulse jet combustor. The pulse jet combustor uses coal dust as a fuel to provide reaction temperatures of 1300.degree. to 1400.degree. F. Low-rank coal, water, limestone and catalyst are fed into the drum reactor where they are heated, tumbled and reacted. Part of the reaction product from the rotating drum reactor is hydrogen which can be utilized in suitable devices.

  19. Track effects in the radiolysis of aromatic liquids

    NASA Astrophysics Data System (ADS)

    LaVerne, Jay A.; Baidak, Aliaksandr

    2012-09-01

    The chemical effects induced by the track structure of heavy ions have been exploited to show that H2 production in the radiolysis of simple aromatic liquids (benzene, pyridine, toluene and aniline) is primarily due to second order processes. Similar dependences of H2 yields on the linear energy transfer, LET, for each of these compounds suggest a common mechanism for H2 formation. Furthermore, the yields of H2 are significant at very high LET and they approach that found with aliphatic compounds. Yields of "dimers" (biphenyl, bibenzyl, dipyridyl, and diphenylamine for benzene, toluene, pyridine, and aniline, respectively) have different dependences on LET reflecting the variety of pathways leading to their production. Bibenzyl formation in toluene exhibits a complex dependence on LET suggesting several competing pathways for its production whereas biphenyl formation in benzene is nearly independent of LET suggesting a unimolecular process. Dipyridyl, and diphenylamine yields in pyridine and aniline, respectively, decrease with increasing LET, which indicates that their precursor is being depleted.

  20. Radiolysis gases from nitric acid solutions containing HSA and HAN

    SciTech Connect

    Smith, J.R.

    1995-12-31

    The concentration of hydrogen (H{sub 2}) in the radiolytically produced off-gas from 2.76-4.25M HNO{sub 3} solutions is greatly reduced by dilution in the presence of HSA (sulfamic acid) and HAN (hydroxylamine nitrate). This dilution continues at a constant rate until the HSA and HAN are exhausted. The generation rate, G(H{sub 2}), was not affected by these two compounds giving a value of 0.201 mol/100 eV for 2.77M NO{sub 3}{sup -}. The other radiolysis gases produced are O{sub 2}, N{sub 2}, and N{sub 2}O, the later two due to reduction of nitrous acid by HSA and HAN respectively. At high nitrate concentrations, >2.8M, and in the presence of HAN the total off-gas production rate is greatly reduced. This may be due to reaction of nitrate and HAN to produce oxygen reactive compounds such as HNO which can react with dissolved O{sub 2} to regenerate nitrate directly, by-passing nitrous acid. The initial reduction in the off-gas rate is lost after destruction of the HAN.

  1. Nanoclusters Synthesized by Synchrotron Radiolysis in Concert with Wet Chemistry

    PubMed Central

    Oyanagi, Hiroyuki; Orimoto, Yuuichi; Hayakawa, Kuniko; Hatada, Keisuke; Sun, Zhihu; Zhang, Ling; Yamashita, Kenichi; Nakamura, Hiroyuki; Uehara, Masato; Fukano, Atsuyuki; Maeda, Hideaki

    2014-01-01

    Wet chemical reduction of metal ions, a common strategy for synthesizing metal nanoparticles, strongly depends on the electric potential of the metal, and its applications to late transition metal clusters have been limited to special cases. Here, we describe copper nanoclusters grown by synchrotron radiolysis in concert with wet chemistry. The local structure of copper aggregates grown by reducing Cu(II) pentanedionate using synchrotron x-ray beam was studied in situ by x-ray absorption spectroscopy. A detailed analysis of the XANES and EXAFS spectra, compared with DFT calculations and full-potential non-muffin-tin multiple scattering calculations, identified the nanocluster as Cu13 with icosahedral symmetry. The novel “charged” nanoclusters tightly bound to electron-donating amido molecules, which formed as a result of photo-induced deprotonation of ligand amines, were stabilized by irradiation. Monodispersive deposition of nanoclusters was enabled by controlling the type and density of “monomers”, in remarkable contrast to the conventional growth of metallic nanoparticles. PMID:25425181

  2. Nanoclusters synthesized by synchrotron radiolysis in concert with wet chemistry.

    PubMed

    Oyanagi, Hiroyuki; Orimoto, Yuuichi; Hayakawa, Kuniko; Hatada, Keisuke; Sun, Zhihu; Zhang, Ling; Yamashita, Kenichi; Nakamura, Hiroyuki; Uehara, Masato; Fukano, Atsuyuki; Maeda, Hideaki

    2014-11-26

    Wet chemical reduction of metal ions, a common strategy for synthesizing metal nanoparticles, strongly depends on the electric potential of the metal, and its applications to late transition metal clusters have been limited to special cases. Here, we describe copper nanoclusters grown by synchrotron radiolysis in concert with wet chemistry. The local structure of copper aggregates grown by reducing Cu(II) pentanedionate using synchrotron x-ray beam was studied in situ by x-ray absorption spectroscopy. A detailed analysis of the XANES and EXAFS spectra, compared with DFT calculations and full-potential non-muffin-tin multiple scattering calculations, identified the nanocluster as Cu13 with icosahedral symmetry. The novel "charged" nanoclusters tightly bound to electron-donating amido molecules, which formed as a result of photo-induced deprotonation of ligand amines, were stabilized by irradiation. Monodispersive deposition of nanoclusters was enabled by controlling the type and density of "monomers", in remarkable contrast to the conventional growth of metallic nanoparticles.

  3. Improvement of the dissolution rate of nitrendipine using a new pulse combustion drying method.

    PubMed

    Wang, Liang; Cui, Fu-De; Sunada, Hisakazu

    2007-08-01

    Solid dispersions (SDs) of nitrendipine (NTD), a poorly water-soluble drug, were prepared with the Hypulcon pulse combustion dryer system, and the physicochemical properties of particles were investigated and compared with those of particles prepared with a spray dryer. The SD particles prepared with Hypulcon using Aerosil and Tween 80 as carriers showed improved properties over those prepared with a conventional spray dryer, such as smaller particle size, tighter particle size distribution, and no agglomeration. Powder X-ray diffraction and differential scanning calorimetry evaluation showed that the drug in the NTD-Aerosil SD prepared with 5% (v/v) Tween 80 solution was dispersed in an amorphous state. Fourier transformation IR spectroscopy indicated the presence of hydrogen bonds between NTD and Aerosil. Aerosil had greater ability to improve the dissolution of NTD than Sylysia and other polymers. The highest drug supersaturation concentration was maintained continuously during the dissolution test of the NTD-Aerosil SD prepared with 5% (v/v) Tween 80 solution using Hypulcon. The good hydrophilicity and dispersibility of Aerosil, solubilization of Tween 80, and actions of shock waves and ultrasonic waves might account for the amorphization of NTD and improved dissolution rate of SDs. Pulse combustion drying with low drying costs and high thermal efficiency is a promising method for the preparation of SD particles with improved properties without using organic solvent.

  4. A novel defect depth measurement method based on Nonlinear System Identification for pulsed thermographic inspection

    NASA Astrophysics Data System (ADS)

    Zhao, Yifan; Mehnen, Jörn; Sirikham, Adisorn; Roy, Rajkumar

    2017-02-01

    This paper introduces a new method to improve the reliability and confidence level of defect depth measurement based on pulsed thermographic inspection by addressing the over-fitting problem. Different with existing methods using a fixed model structure for all pixels, the proposed method adaptively detects the optimal model structure for each pixel thus targeting to achieve better model fitting while using less model terms. Results from numerical simulations and real experiments suggest that (a) the new method is able to measure defect depth more accurately without a pre-set model structure (error is usually within 1 % when SNR>32 dB) in comparison with existing methods, (b) the number of model terms should be 8 for signals with SNR∈ [ 30 dB , 40 dB ] , 8-10 for SNR>40 dB and 5-8 for SNR<30 dB, and (c) a data length with at least 100 data points and 2-3 times of the characteristic time usually produces the best results.

  5. A two-dose-rate method for general recombination correction for liquid ionization chambers in pulsed beams

    NASA Astrophysics Data System (ADS)

    Tölli, Heikki; Sjögren, Rickard; Wendelsten, Mikael

    2010-08-01

    The correction for general recombination losses in liquid ionization chambers (LICs) is more complex than that in air-filled ionization chambers. The reason for this is that the saturation charge in LICs, i.e. the charge that escapes initial recombination, depends on the applied voltage. This paper presents a method, based on measurements at two different dose rates in a pulsed beam, for general recombination correction in LICs. The Boag theory for pulsed beams is used and the collection efficiency is determined by numerical methods which are equivalent to the two-voltage method used in dosimetry with air-filled ionization chambers. The method has been tested in experiments in water in a 20 MeV electron beam using two LICs filled with isooctane and tetramethylsilane. The dose per pulse in the electron beam was varied between 0.1 mGy/pulse and 8 mGy/pulse. The relative standard deviations of the collection efficiencies determined with the two-dose-rate method ranged between 0.1% and 1.5%. The dose-rate variations of the general recombination corrected charge measured with the LICs are in excellent agreement with the corresponding values obtained with an air-filled plane parallel ionization chamber.

  6. Amplifiable DNA from Gram-negative and Gram-positive bacteria by a low strength pulsed electric field method

    PubMed Central

    Vitzthum, Frank; Geiger, Georg; Bisswanger, Hans; Elkine, Bentsian; Brunner, Herwig; Bernhagen, Jürgen

    2000-01-01

    An efficient electric field-based procedure for cell disruption and DNA isolation is described. Isoosmotic suspensions of Gram-negative and Gram-positive bacteria were treated with pulsed electric fields of <60 V/cm. Pulses had an exponential decay waveform with a time constant of 3.4 µs. DNA yield was linearly dependent on time or pulse number, with several thousand pulses needed. Electrochemical side-effects and electrophoresis were minimal. The lysates contained non-fragmented DNA which was readily amplifiable by PCR. As the method was not limited to samples of high specific resistance, it should be applicable to physiological fluids and be useful for genomic and DNA diagnostic applications. PMID:10734214

  7. A new method for compensation of the effect of charging transformer's leakage inductance on PFN voltage regulation in Klystron pulse modulators

    NASA Astrophysics Data System (ADS)

    Patel, Akhil; Kale, Umesh; Shrivastava, Purushottam

    2017-04-01

    The Line type modulators have been widely used to generate high voltage rectangular pulses to power the klystron for high power RF generation. In Line type modulator, the Pulse Forming Network (PFN) which is a cascade combination of lumped capacitors and inductors is used to store the electrical energy. The charged PFN is then discharged into a klystron by firing a high voltage Thyratron switch. This discharge generates a high voltage rectangular pulse across the klystron electrodes. The amplitude and phase of Klystron's RF output is governed by the high voltage pulse amplitude. The undesired RF amplitude and phase stability issues arises at the klystron's output due to inter-pulse and during the pulse amplitude variations. To reduce inter-pulse voltage variations, the PFN is required to be charged at the same voltage after every discharge cycle. At present, the combination of widely used resonant charging and deQing method is used to regulate the pulse to pulse PFN voltage variations but the charging transformer's leakage inductance puts an upper bound on the regulation achievable by this method. Here we have developed few insights of the deQing process and devised a new compensation method to compensate this undesired effect of charging transformer's leakage inductance on the pulse to pulse PFN voltage stability. This compensation is accomplished by the controlled partial discharging of the split PFN capacitor using a low voltage MOSFET switch. Theoretically, very high values of pulse to pulse voltage stability may be achieved using this method. This method may be used in deQing based existing modulators or in new modulators, to increase the pulse to pulse voltage stability, without having a very tight bound on charging transformer's leakage inductance. Given a stable charging power supply, this method may be used to further enhance the inter-pulse voltage stability of modulators which employ the direct charging, after replacing the direct charging with the

  8. Chemical aspects of radiosensitization. Reaction of sensitizers with radicals produced in the radiolysis of aqueous solutions of nucleic acid components.

    PubMed Central

    Asmus, K. D.; Deeble, D. J.; Garner, A.; Ali, K. M.; Scholes, G.

    1978-01-01

    The effects of oxidants (sensitizers) in the radiolysis of aqueous solutions of pyrimidine and purine bases have been investigated. Their influence on the nature of the permanent radiolysis products and on the kinetics of disappearance of transient intermediates is reported. Particular attention has been paid to the chemical fates of carbocationic intermediates which can be produced from radical-sensitizer interaction. PMID:277256

  9. Method for continuous control of composition and doping of pulsed laser deposited films by pressure control

    DOEpatents

    Lowndes, Douglas H.; McCamy, James W.

    1996-01-01

    A method for growing a deposit upon a substrate of semiconductor material involves the utilization of pulsed laser deposition techniques within a low-pressure gas environment. The substrate and a target of a first material are positioned within a deposition chamber and a low-pressure gas atmosphere is developed within the chamber. The substrate is then heated, and the target is irradiated, so that atoms of the target material are ablated from the remainder of the target, while atoms of the gas simultaneously are adsorbed on the substrate/film surface. The ablated atoms build up upon the substrate, together with the adsorbed gas atoms to form the thin-film deposit on the substrate. By controlling the pressure of the gas of the chamber atmosphere, the composition of the formed deposit can be controlled, and films of continuously variable composition or doping can be grown from a single target of fixed composition.

  10. Method for continuous control of composition and doping of pulsed laser deposited films

    DOEpatents

    Lowndes, Douglas H.; McCamy, James W.

    1995-01-01

    A method for growing a deposit upon a substrate of semiconductor material involves the utilization of pulsed laser deposition techniques within a low-pressure gas environment. The substrate and a target of a first material are positioned within a deposition chamber and a low-pressure gas atmosphere is developed within the chamber. The substrate is then heated, and the target is irradiated, so that atoms of the target material are ablated from the remainder of the target, while atoms of the gas simultaneously are adsorbed on the substrate/film surface. The ablated atoms build up upon the substrate, together with the adsorbed gas atoms to form the thin-film deposit on the substrate. By controlling the pressure of the gas of the chamber atmosphere, the composition of the formed deposit can be controlled, and films of continuously variable composition or doping can be grown from a single target of fixed composition.

  11. Method and apparatus for the control of fluid dynamic mixing in pulse combustors

    DOEpatents

    Bramlette, T. Tazwell; Keller, Jay O.

    1992-06-02

    In a method and apparatus for controlling total ignition delay time in a pulse combustor, and thus controlling the mixing characteristics of the combustion reactants and the combustion products in the combustor, the total ignition delay time is controlled by adjusting the inlet geometry of the inlet to the combustion chamber. The inlet geometry may be fixed or variable for controlling the mixing characteristics. A feedback loop may be employed to sense actual combustion characteristics, and, in response to the sensed combustion characteristics, the inlet geometry may be varied to obtain the total ignition delay time necessary to achieve the desired combustion characteristics. Various embodiments relate to the varying of the mass flow rate of reactants while holding the radius/velocity ratio constant.

  12. Apparatus and method for pulsed laser deposition of materials on wires and pipes

    NASA Technical Reports Server (NTRS)

    Fernandez, Felix E. (Inventor)

    2003-01-01

    Methods and apparatuses are disclosed which allow uniform coatings to be applied by pulsed laser deposition (PLD) on inner and outer surfaces of cylindrical objects, such as rods, pipes, tubes, and wires. The use of PLD makes this technique particularly suitable for complex multicomponent materials, such as superconducting ceramics. Rigid objects of any length, i.e., pipes up to a few meters, and with diameters from less than 1 centimeter to over 10 centimeters can be coated using this technique. Further, deposition is effected simultaneously onto an annular region of the pipe wall. This particular arrangement simplifies the apparatus, reduces film uniformity control difficulties, and can result in faster operation cycles. In addition, flexible wires of any length can be continuously coated using the disclosed invention.

  13. Short-pulsed laser transport in two-dimensional scattering media by natural element method.

    PubMed

    Zhang, Yong; Yi, Hong-Liang; Xie, Ming; Tan, He-Ping

    2014-04-01

    The natural element method (NEM) is extended to solve transient radiative transfer (TRT) in two-dimensional semitransparent media subjected to a collimated short laser irradiation. The least-squares (LS) weighted residuals approach is employed to spatially discretize the transient radiative heat transfer equation. First, for the case of the refractive index matched boundary, LSNEM solutions to TRT are validated by comparison with results reported in the literature. Effects of the incident angle on time-resolved signals of transmittance and reflectance are investigated. Afterward, the accuracy of this algorithm for the case of the refractive index mismatched boundary is studied. Finally, the LSNEM is extended to study the TRT in a two-dimensional semitransparent medium with refractive index discontinuity irradiated by the short pulse laser. The effects of scattering albedo, optical thickness, scattering phase function, and refractive index on transmittance and reflectance signals are investigated. Several interesting trends on the time-resolved signals are observed and analyzed.

  14. Pulse-Echo Ultrasonic Imaging Method for Eliminating Sample Thickness Variation Effects

    NASA Technical Reports Server (NTRS)

    Roth, Don J. (Inventor)

    1997-01-01

    A pulse-echo, immersion method for ultrasonic evaluation of a material which accounts for and eliminates nonlevelness in the equipment set-up and sample thickness variation effects employs a single transducer and automatic scanning and digital imaging to obtain an image of a property of the material, such as pore fraction. The nonlevelness and thickness variation effects are accounted for by pre-scan adjustments of the time window to insure that the echoes received at each scan point are gated in the center of the window. This information is input into the scan file so that, during the automatic scanning for the material evaluation, each received echo is centered in its time window. A cross-correlation function calculates the velocity at each scan point, which is then proportionalized to a color or grey scale and displayed on a video screen.

  15. Pulse-echo ultrasonic imaging method for eliminating sample thickness variation effects

    NASA Technical Reports Server (NTRS)

    Roth, Don J. (Inventor)

    1995-01-01

    A pulse-echo, immersion method for ultrasonic evaluation of a material is discussed. It accounts for and eliminates nonlevelness in the equipment set-up and sample thickness variation effects employs a single transducer, automatic scanning and digital imaging to obtain an image of a property of the material, such as pore fraction. The nonlevelness and thickness variation effects are accounted for by pre-scan adjusments of the time window to insure that the echoes received at each scan point are gated in the center of the window. This information is input into the scan file so that, during the automatic scanning for the material evaluation, each received echo is centered in its time window. A cross-correlation function calculates the velocity at each scan point, which is then proportionalized to a color or grey scale and displayed on a video screen.

  16. Method and apparatus for the control of fluid dynamic mixing in pulse combustors

    DOEpatents

    Bramlette, T.T.; Keller, J.O.

    1992-06-02

    In a method and apparatus for controlling total ignition delay time in a pulse combustor, and thus controlling the mixing characteristics of the combustion reactants and the combustion products in the combustor, the total ignition delay time is controlled by adjusting the inlet geometry of the inlet to the combustion chamber. The inlet geometry may be fixed or variable for controlling the mixing characteristics. A feedback loop may be employed to sense actual combustion characteristics, and, in response to the sensed combustion characteristics, the inlet geometry may be varied to obtain the total ignition delay time necessary to achieve the desired combustion characteristics. Various embodiments relate to the varying of the mass flow rate of reactants while holding the radius/velocity ratio constant. 10 figs.

  17. A novel pulsed STED microscopy method using FastFLIM and the phasor plots

    NASA Astrophysics Data System (ADS)

    Sun, Yuansheng; Tortarolo, Giorgio; Teng, Kai-Wen; Ishitsuka, Yuji; Coskun, Ulas C.; Liao, Shih-Chu Jeff; Diaspro, Alberto; Vicidomini, Giuseppe; Selvin, Paul R.; Barbieri, Beniamino

    2017-02-01

    Stimulated emission depletion (STED) microscopy is a powerful super-resolution microscopy technique that enables observation of macromolecular complexes and sub-cellular structures with spatial resolution below the diffraction limit. The spatial resolution of STED is limited by power of the depletion laser at the specimen plane. Higher depletion laser power will improve resolution, but at the cost of increased photo-bleaching, photo-toxicity, and anti-stoke emission background. This degrades the signal-to-noise ratio, and can significantly limit STED applications in living specimens. Here, we present an efficient multi-color STED microscopy method based on the digital frequency domain fluorescence lifetime imaging (FastFLIM) and the phasor plots. Our approach utilizes a combination of pulsed excitation and pulsed depletion lasers to record the time-resolved photons by FastFLIM. We demonstrate that the resolution is improved without increasing the depletion laser power by digital separation of the depleted species from the partially depleted species based on their different decay kinetics. We show the utility of this novel STED method applied in both fixed and live cellular samples, and also show its application to fluorescence lifetime correlation spectroscopy (FLCS) measurements. By combining fluorophores with different fluorescence lifetimes, we simultaneously record two-color STED images of cells labeled with Atto655 and Alexa647 in a single scan by using a single pair of excitation and depletion lasers. This novel approach shortens the data acquisition time while minimizing the photo-toxicity caused when using two separate depletion lasers.

  18. Phenylalanine isotope pulse method to measure effect of sepsis on protein breakdown and membrane transport in the pig.

    PubMed

    Ten Have, Gabriella A M; Engelen, Mariëlle P K J; Wolfe, Robert R; Deutz, Nicolaas E P

    2017-06-01

    The primed-continuous (PC) phenylalanine (Phe) stable isotope infusion methodology is often used as a proxy for measuring whole body protein breakdown (WbPB) in sepsis. It is unclear if WbPB data obtained by an easy-to-use single IV Phe isotope pulse administration (PULSE) are comparable to those by PC. Compartmental modeling with PULSE could provide us more insight in WbPB in sepsis. Therefore, in the present study, we compared PULSE with PC as proxy for WbPB in an instrumented pig model with Pseudomonas aeruginosa-induced severe sepsis (Healthy: n = 9; Sepsis: n = 13). Seventeen hours after sepsis induction, we compared the Wb rate of appearance (WbRa) of Phe obtained by PC (L-[ring-(13)C6]Phe) and PULSE (L-[(15)N]Phe) in arterial plasma using LC-MS/MS and (non)compartmental modeling. PULSE-WbRa was highly correlated with PC-WbRa (r = 0.732, P < 0.0001) and WbPB (r = 0.897, P < 0.0001) independent of the septic state. PULSE-WbRa was 1.6 times higher than PC-WbRa (P < 0.001). Compartmental and noncompartmental PULSE modeling provide comparable WbRa values, although compartmental modeling was more sensitive. WbPB was elevated in sepsis (Healthy: 3,378 ± 103; Sepsis: 4,333 ± 160 nmol·kg BW(-1)·min(-1), P = 0.0002). With PULSE, sepsis was characterized by an increase of the metabolic shunting (Healthy: 3,021 ± 347; Sepsis: 4,233 ± 344 nmol·kg BW(-1)·min(-1), P = 0.026). Membrane transport capacity was the same. Both PC and PULSE methods are able to assess changes in WbRa of plasma Phe reflecting WbPB changes with high sensitivity, independent of the (patho)physiological state. The easy-to-use (non)compartmental PULSE reflects better the real WbPB than PC. With PULSE compartmental analysis, we conclude that the membrane transport capacity for amino acids is not compromised in severe sepsis. Copyright © 2017 the American Physiological Society.

  19. An ultrasound automated method for non-invasive assessment of carotid artery pulse wave velocity.

    PubMed

    Zardi, Enrico Maria; Di Geso, Luca; Afeltra, Antonella; Zardi, Domenico Maria; Giorgi, Chiara; Salaffi, Fausto; Carotti, Marina; Gutierrez, Marwin; Filippucci, Emilio; Grassi, Walter

    2017-09-02

    To validate the clinical applicability and feasibility of an automated ultrasound (US) method in measuring the arterial stiffness of patients with chronic inflammatory rheumatic diseases, comparing automated measurements performed by a rheumatologist without experience in vascular sonography with those obtained by a sonographer experienced in vascular US, using a standardized manual method.Twenty subjects affected by different chronic inflammatory rheumatic disorders were consecutively recruited. For each patient, the arterial stiffness of both common carotids was manually calculated. Subsequently, the measure of the pulse wave velocity (PWV) was obtained using an US device called Radio Frequency - Quality Arterial Stiffness (RF-QAS), provided by the same US system (ie, My Lab 70 XVG, Esaote SpA, Genoa, Italy) equipped with a 4-13 MHz linear probe. The reliability comparison between the two US methods was calculated using the intraclass correlation coefficient (ICC). ICC between the values obtained with the two methods for calculating the arterial stiffness resulted 0.789. A significant positive correlation between the two methods was also established with Pearson's (r=0.62, p<0.0001) and Spearman's analysis (r=0.66, p=0.001). A significant performance comparison was seen using Bland-Altman plot. The acquisition of the arterial stiffness parameter with the automated method required about 2 min for each patient. Clinical applicability of this US automated method to assess PWV at common carotid level by a rheumatologist is reliable and feasible in comparison with a conventional manual method. © American Federation for Medical Research (unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

  20. Nature of the products of photolysis and radiolysis of CBr/sub 4/ at 77 K

    SciTech Connect

    Kholmanskii, A.S.

    1988-07-01

    Photolysis and /gamma/-radiolysis of CBr/sub 4/ in different matrices at 77 K in the presence of electron donors were studied spectrophotometrically. The identity of the absorption spectra of the products of photolysis and radiolysis of CBr/sub 4/ and CCl/sub 4/ obtained in the same conditions was demonstrated. It was shown that photolysis and radiolysis of CBr/sub 4/ in the presence of electron donors in any matrices result in the formation of a product with an absorption band at 470-500 nm. The band was assigned to the absorption spectrum of the CBr/sub 3//sup +/ cation in the (CBr/sub 3//sup +//parallel/Br/sup /minus//) ion pair. The most probable mechanism of its formation was proposed.

  1. Comparison of the soluble products from radiolysis and photolysis of CS2

    NASA Astrophysics Data System (ADS)

    Cataldo, F.; Heymann, D.

    2001-05-01

    Soluble products from the radiolysis of CS2 with gamma variable rays from 60Co, include elemental sulfur and CmSn compounds. These compounds were essentially the same as those that had already been reported for the UV photolysis of CS2. The amount of sulfur formed was proportional to the irradiation dose. The radiolysis also formed a dark colored, insoluble polymer in amounts proportional to the irradiation dose. The soluble CmSn molecules found in this work were most likely due to `aborted polymerization'. Radiolysis and photolysis of CS2 may contribute important C-S compounds for the cosmochemistry of circumstellar and interstellar media as well as of comets and atmospheres of the giant planets.

  2. Determination of bosentan in pharmaceutical preparations by linear sweep, square wave and differential pulse voltammetry methods.

    PubMed

    Atila, Alptug; Yilmaz, Bilal

    2015-01-01

    In this study, simple, fast and reliable cyclic voltammetry (CV), linear sweep voltammetry (LSV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV) methods were developed and validated for determination of bosentan in pharmaceutical preparations. The proposed methods were based on electrochemical oxidation of bosentan at platinum electrode in acetonitrile solution containing 0.1 M TBACIO4. The well-defined oxidation peak was observed at 1.21 V. The calibration curves were linear for bosentan at the concentration range of 5-40 µg/mL for LSV and 5-35 µg/mL for SWV and DPV methods, respectively. Intra- and inter-day precision values for bosentan were less than 4.92, and accuracy (relative error) was better than 6.29%. The mean recovery of bosentan was 100.7% for pharmaceutical preparations. No interference was found from two tablet excipients at the selected assay conditions. Developed methods in this study are accurate, precise and can be easily applied to Tracleer and Diamond tablets as pharmaceutical preparation.

  3. Applicability of the polynomial chaos expansion method for personalization of a cardiovascular pulse wave propagation model.

    PubMed

    Huberts, W; Donders, W P; Delhaas, T; van de Vosse, F N

    2014-12-01

    Patient-specific modeling requires model personalization, which can be achieved in an efficient manner by parameter fixing and parameter prioritization. An efficient variance-based method is using generalized polynomial chaos expansion (gPCE), but it has not been applied in the context of model personalization, nor has it ever been compared with standard variance-based methods for models with many parameters. In this work, we apply the gPCE method to a previously reported pulse wave propagation model and compare the conclusions for model personalization with that of a reference analysis performed with Saltelli's efficient Monte Carlo method. We furthermore differentiate two approaches for obtaining the expansion coefficients: one based on spectral projection (gPCE-P) and one based on least squares regression (gPCE-R). It was found that in general the gPCE yields similar conclusions as the reference analysis but at much lower cost, as long as the polynomial metamodel does not contain unnecessary high order terms. Furthermore, the gPCE-R approach generally yielded better results than gPCE-P. The weak performance of the gPCE-P can be attributed to the assessment of the expansion coefficients using the Smolyak algorithm, which might be hampered by the high number of model parameters and/or by possible non-smoothness in the output space.

  4. Determination of Bosentan in Pharmaceutical Preparations by Linear Sweep, Square Wave and Differential Pulse Voltammetry Methods

    PubMed Central

    Atila, Alptug; Yilmaz, Bilal

    2015-01-01

    In this study, simple, fast and reliable cyclic voltammetry (CV), linear sweep voltammetry (LSV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV) methods were developed and validated for determination of bosentan in pharmaceutical preparations. The proposed methods were based on electrochemical oxidation of bosentan at platinum electrode in acetonitrile solution containing 0.1 M TBACIO4. The well-defined oxidation peak was observed at 1.21 V. The calibration curves were linear for bosentan at the concentration range of 5-40 µg/mL for LSV and 5-35 µg/mL for SWV and DPV methods, respectively. Intra- and inter-day precision values for bosentan were less than 4.92, and accuracy (relative error) was better than 6.29%. The mean recovery of bosentan was 100.7% for pharmaceutical preparations. No interference was found from two tablet excipients at the selected assay conditions. Developed methods in this study are accurate, precise and can be easily applied to Tracleer and Diamond tablets as pharmaceutical preparation. PMID:25901151

  5. Cross modulation method of transformation of the spatial coherence of pulsed laser radiation in a nonlinear medium

    SciTech Connect

    Kitsak, M A; Kitsak, A I

    2008-04-30

    The cross modulation method of transformation of the spatial coherence of low-power pulsed laser radiation in a nonlinear medium is proposed. The method is realised experimentally in a multimode optical fibre. The estimates of the degree of spatial coherence of radiation subjected to the phase cross modulation demonstrated the high efficiency of this radiation decorrelation mechanism. (control of laser radiation parameters)

  6. Feeding a subsurface biosphere: radiolysis and abiogenic energy sources

    NASA Astrophysics Data System (ADS)

    Onstott, T.

    Noble gas analyses of ground water collected from the deep, fractured, basaltic andesite and quartzite Archean strata in South Africa suggest subsurface residence times ranging from tens to hundreds of millions of years. Hydraulically isolated compartments of highly saline water contain hundreds of μM concentrations of gas comprised primarily of C1-4 hydrocarbons, H2 and He, with minor Ar and N .2 Carbon and hydrogen isotopic analyses of the hydrocarbons suggest an abiogenic origin com atible with surface catalysed reductive assimilation (i.e. Fischer-Tropschp synthesis). H2 and He data suggest that the H2 is generated by subsurface radiolysis of water. One sample of a saline, isolated water/gas pocket agrees exactly with that predicted by radioactive decay of U, Th, K in the host rock and indicates a subsurface H2 production rate of 0.1 to 1 nM/yr. Other samples yielded less H2 than predicted and require a sink for this H2 . Possible sinks include microbial H2 oxidation and abiotic formation of hydrocarbons at rates slightly less than the H2 production rate. Highly diffusive H2 is essential for life in deep subsurface environments where only trace amounts of organic carbon exist. Lithoautotrophic microbes can acquire energy from the redox reactions involving H2 with other electron acceptors (Fe3 +, SO4 2 - or CO2 ), to synthesis organic carbon and can be fully independent of solar-driven photosynthesis. The microbial abundance in many of these ground water samples, however, is below our detection limit (<5000 cells/ml). This contrasts with shallow sedimentary aquifers where H2 levels of tens of nM are regulated by the coexistence of autotrophs/lithotrophs and heterotrophs for maximum efficiency of H2 utilization. The excessive H2 found in deep crustal environments implies that these microbial ecosystems are electron-acceptor and or substrate limited. The oxidants generated by water radiolysis interact with the reduced solid phases in the rock matrix, e.g. pyrite

  7. The radiation chemistry of CMPO: Part 2. Alpha radiolysis

    SciTech Connect

    Bruce J. Mincher; Stephen P. Mezyk; Gary S. Groenewold; Christian Ekberg; Gunnar Skarnemark; Jay A. LaVerne; Mikael Nilsson; Jeremy Pearson; Nicholas C. Schmitt; Richard D. Tillotson; Lonnie G. Olson; Gracy Elias

    2014-01-01

    Octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in dodecane was subjected to a-irradiation using a He-ion beam, 244 Cm isotopic a-rays, and He and Li ions created by the n,a reaction of 10B in a nuclear reactor. Post-irradiation samples were analyzed for the radiolytically-induced decrease in CMPO concentration, the appearance of degradation products, and their Am solvent extraction distribution ratios. The –G CMPO-value for the radiolytic degradation of CMPO was found to be very low compared to values previously reported for ?-irradiation. Additionally, isotopic irradiation to absorbed a-doses as high as 600 kGy in aerated solution had no effect on Am solvent extraction or stripping. The main CMPO radiolysis products identified in He-ion beam irradiated samples by ESI-MS include amides, an acidic amide, and amines produced by bond rupture on either side of the CMPO carbonyl group. Deaerated samples irradiated using the reactor in the absence of an aqueous phase, or with a dilute nitric acid aqueous phase showed small but measurable decreases in CMPO concentration with increasing absorbed doses. Higher concentrations of nitric acid resulted in lower decomposition rates for the CMPO. The radio-protection by dissolved oxygen and nitric acid previously found for ?-irradiated CMPO also occurs for a-irradiation. This suggests that similar free-radical mechanisms operate in the high-LET system, but with lower degradation yields due to the lower overall radical concentrations produced.

  8. Detection of volatile impurities in turbine oils by the heat-pulse testing method

    NASA Astrophysics Data System (ADS)

    Skripov, P. V.; Demin, V. A.; Shangin, V. V.; Starostin, A. A.

    2016-07-01

    The research is aimed at development and implementation of methods and devices to control critical sections of the oil system of the power equipment that operates in the real time mode. The task was to develop a method for rapid detection of volatile impurities in turbine oils. The approach to the study is based on quantitative assessment of the short-term thermal stability of the substance that is formally associated with the content of the volatile impurity. The approach was selected on the basis of the results of search experiments taking into consideration the formulation of requirements for the method and the device, viz., (1) the method should reliably determine the moisture content in the range of 10-150 g of the impurity per ton of oil and (2) the device is to be applicable "in situ." For this purpose, a variant of the method of the controlled pulse heating of a wire probe, a resistance thermometer, has been developed. The advantages of the method are its speed, sensitivity to small contents of volatile impurities regardless of the nature of the impurity, and smallness of methodologically contributed perturbation. The heating conditions of the probe most sensitive to the appearance of moisture— including its trace amounts—in the system, has been defined. The duration of the measurement is on the order of milliseconds; the heat flux density through the surface of the probe reaches 1 MW/m2. The essence of the method consists in measuring, in the characteristic time interval, the temperature of the thermal instability onset associated with the content of the volatile impurity. The approach proposed by the authors is aimed at increasing the lifetime of the oil and preventing unpredictable failures of the operating equipment.

  9. A real-time receive method of wideband radar based on subband pulse compression

    NASA Astrophysics Data System (ADS)

    Li, Ming; Fu, Wei; Zhang, Peng; Wu, Yan

    2011-10-01

    The data rate with high capacity and speed of wideband signal makes its real-time processing limited by hardware and software. In this paper, wideband signal is made pulse compression based on subband pulse compression system. It is used uniform complex modulation to generate analysis filter bank and synthesis filter bank, then signals are processed in each subband. The processed results of simulated and measured datas indicate, that the parallel means of subband pulse compression raises the operation speed and improves real-time processing performance of the system, selecting proper subband number according to the data quantity when the result closed to that of directed pulse compression.

  10. A new cross-detection method for improved energy-resolving photon counting under pulse pile-up

    NASA Astrophysics Data System (ADS)

    Lee, Daehee; Lim, Kyung Taek; Park, Kyungjin; Lee, Changyeop; Cho, Gyuseong

    2017-09-01

    In recent, photon counting detectors (PCDs) have been replacing the energy-integrating detectors in many medical imaging applications due to the formers' high resolution, low noise, and high efficiency. Under a high flux X-ray exposure, however, a superimposition of pulses, i.e., pulse pile-up, frequently occurs due to the finite output pulse width, causing distortions in the energy spectrum as a consequence. Therefore, pulse pile-up is considered as a major constraint in using PCDs for high flux X-ray applications. In this study, a new photon counting method is proposed to minimize degradations in PCD performance due to pulse pile-up. The proposed circuit was incorporated into a pixel with a size of 200 × 200 μm2. It was fabricated by using a 1-poly 6-metal 0 . 18 μm complementary metal-oxide-semiconductor (CMOS) process and had a power consumption of 7 . 8 μW / pixel. From the result, it was shown that the maximum count rate of the proposed circuit was increased by a factor of 4.7 when compared to that of the conventional circuit at the same pulse width of 700 ns. This implies that the energy spectrum obtained by the proposed circuit is 4.7 times more resistant to distortions than the conventional energy-resolving circuit does under higher X-ray fluxes.

  11. Poly(arylsulfone imide) as E-beam resist: synthesis and radiolysis. Technical report

    SciTech Connect

    Chien, J.C.; Cheng, Z.S.

    1989-01-01

    Aromatic diamines containing -SO/sub 2/-and-S- moieties were used to prepare soluble polyimides with ditrifluoromethyl methane bis(phthalic anhydride) (F-series polyimides) and polyamic acid with pyromellitic dianhydride (P-series). Gamma radiolysis gave G(S) values for scission between 1 to 2 with no crosslinking. Significant weight loss occurred with radiolysis is attributable to efficient -SO/sub 2/-bond scission for the R-series polyimides, as well as imidization in the cases of P-series polyamic acids.

  12. A new method for evaluating the degeneration of articular cartilage using pulse-echo ultrasound.

    PubMed

    Sun, Anyu; Bai, Xiaolong; Ju, Bing-Feng

    2015-03-01

    This paper presents a novel nondestructive ultrasonic technique for measuring the sound speed and acoustic impedance of articular cartilage using the pulsed Vz,t technique. Vz,t data include a series of pulsed ultrasonic echoes collected using different distances between the ultrasonic transducer and the specimen. The 2D Fourier transform is applied to the Vz,t data to reconstruct the 2D reflection spectrum Rθ,ω. To obtain the reflection coefficient of articular cartilage, the Vz,t data from a reference specimen with a well-known reflection coefficient are obtained to eliminate the dependence on the general system transfer function. The ultrasound-derived aggregate modulus (Ha) is computed based on the measured reflection coefficient and the sound speed. In the experiment, 32 cartilage-bone samples were prepared from bovine articular cartilage, and 16 samples were digested using 0.25% trypsin solution. The sound speed and Ha of these cartilage samples were evaluated before and after degeneration. The magnitude of the sound speed decreased with trypsin digestion (from 1663 ± 5.6 m/s to 1613 ± 5.3 m/s). Moreover, the Young's modulus in the corresponding degenerative state was measured and was correlated with the ultrasound-derived aggregate modulus. The ultrasound-derived aggregate modulus was determined to be highly correlated with the Young's modulus (n = 16, r>0.895, p<0.003, Pearson correlation test for each measurement). The results demonstrate the effectiveness of using the proposed method to assess the changes in sound speed and the ultrasound-derived aggregate modulus of cartilage after degeneration.

  13. A harmonic pulse testing method for leakage detection in deep subsurface storage formations

    NASA Astrophysics Data System (ADS)

    Sun, Alexander Y.; Lu, Jiemin; Hovorka, Susan

    2015-06-01

    Detection of leakage in deep geologic storage formations (e.g., carbon sequestration sites) is a challenging problem. This study investigates an easy-to-implement frequency domain leakage detection technology based on harmonic pulse testing (HPT). Unlike conventional constant-rate pressure interference tests, HPT stimulates a reservoir using periodic injection rates. The fundamental principle underlying HPT-based leakage detection is that leakage modifies a storage system's frequency response function, thus providing clues of system malfunction. During operations, routine HPTs can be conducted at multiple pulsing frequencies to obtain experimental frequency response functions, using which the possible time-lapse changes are examined. In this work, a set of analytical frequency response solutions is derived for predicting system responses with and without leaks for single-phase flow systems. Sensitivity studies show that HPT can effectively reveal the presence of leaks. A search procedure is then prescribed for locating the actual leaks using amplitude and phase information obtained from HPT, and the resulting optimization problem is solved using the genetic algorithm. For multiphase flows, the applicability of HPT-based leakage detection procedure is exemplified numerically using a carbon sequestration problem. Results show that the detection procedure is applicable if the average reservoir conditions in the testing zone stay relatively constant during the tests, which is a working assumption under many other interpretation methods for pressure interference tests. HPT is a cost-effective tool that only requires periodic modification of the nominal injection rate. Thus it can be incorporated into existing monitoring plans with little additional investment.

  14. A new method for evaluating the degeneration of articular cartilage using pulse-echo ultrasound

    NASA Astrophysics Data System (ADS)

    Sun, Anyu; Bai, Xiaolong; Ju, Bing-Feng

    2015-03-01

    This paper presents a novel nondestructive ultrasonic technique for measuring the sound speed and acoustic impedance of articular cartilage using the pulsed V(z,t) technique. V(z,t) data include a series of pulsed ultrasonic echoes collected using different distances between the ultrasonic transducer and the specimen. The 2D Fourier transform is applied to the V(z,t) data to reconstruct the 2D reflection spectrum R(θ,ω). To obtain the reflection coefficient of articular cartilage, the V(z,t) data from a reference specimen with a well-known reflection coefficient are obtained to eliminate the dependence on the general system transfer function. The ultrasound-derived aggregate modulus (Ha) is computed based on the measured reflection coefficient and the sound speed. In the experiment, 32 cartilage-bone samples were prepared from bovine articular cartilage, and 16 samples were digested using 0.25% trypsin solution. The sound speed and Ha of these cartilage samples were evaluated before and after degeneration. The magnitude of the sound speed decreased with trypsin digestion (from 1663 ± 5.6 m/s to 1613 ± 5.3 m/s). Moreover, the Young's modulus in the corresponding degenerative state was measured and was correlated with the ultrasound-derived aggregate modulus. The ultrasound-derived aggregate modulus was determined to be highly correlated with the Young's modulus (n = 16, r>0.895, p<0.003, Pearson correlation test for each measurement). The results demonstrate the effectiveness of using the proposed method to assess the changes in sound speed and the ultrasound-derived aggregate modulus of cartilage after degeneration.

  15. Transport critical current of MgB2 wires: pulsed current of varying rate compared to direct current method

    NASA Astrophysics Data System (ADS)

    See, K. W.; Xu, X.; Horvat, J.; Cook, C. D.; Dou, S. X.

    2011-10-01

    The measurement of transport critical current (Ic) for MgB2 wires and tapes has been investigated with two different techniques, the conventional four-probe arrangement with direct current (DC) power source, and a tailored triangle pulse at different rates of current change. The DC method has been widely used and practiced by various groups, but suffers from inevitable heating effects when high currents are used at low magnetic fields. The pulsed current method has no heating effects, but the critical current can depend on the rate of the current change (dI/dt) in the pulse. Our pulsed current measurements with varying dI/dt show that the same values of Ic are obtained as with the DC method, but without the artifacts of heating. Our method is particularly useful at low field regions which are often inaccessible by DC methods. We also performed a finite element method (FEM) analysis to obtain the time dependent heat distribution in MgB2 due to the electric potential produced at the current contacts to the superconducting sample and its gradient around the contacts. This gradient is defined as the current transfer length (CTL) of the samples and leads to Joule heating of the wire near the contacts. The FEM results provide further evidence of the limitation of the DC method in obtaining high transport critical current.

  16. Pressurized liquid extraction as a sample preparation method for the analysis of isoflavones in pulses.

    PubMed

    Delgado-Zamarreño, María Milagros; Pérez-Martín, Lara; Bustamante-Rangel, Myriam; Carabias-Martínez, Rita

    2012-08-01

    In this work, we describe a rapid and simple analytical method that exploits pressurized liquid extraction (PLE) and liquid chromatography with diode array detection for the determination of isoflavones in samples of Spanish pulses. Confirmation of the analytes present was performed using ion-trap mass spectrometry. To optimize the PLE extraction, variables such as the dispersing agent, type of solvent and sample amount, and the experimental parameters, such as temperature and the number of extraction cycles, were studied. Separation was carried out using a reverse-phase C18 with polar endcapping as the stationary phase and acetonitrile/water with 0.2 % of formic acid, under a gradient regime, as the mobile phase. Optimal extraction of formononetin and biochanin-A from chickpeas with PLE was achieved using Hydromatrix as a dispersant agent, methanol/water (50:50), a temperature of 90 °C, and three cycles. The same optimal conditions-except methanol/water (75:25)-for solvent extraction were obtained for the extraction of daidzin, genistin, and formononetin from lentils. Recoveries ranged from 97 to 110 %, and standard deviations lower than 20 % were obtained. The contents obtained for daidzin in lentils using the proposed method were not significantly different from those obtained using another official method of analysis.

  17. A New Wavelet Denoising Method for Experimental Time-Domain Signals: Pulsed Dipolar Electron Spin Resonance.

    PubMed

    Srivastava, Madhur; Georgieva, Elka R; Freed, Jack H

    2017-03-30

    We adapt a new wavelet-transform-based method of denoising experimental signals to pulse-dipolar electron-spin resonance spectroscopy (PDS). We show that signal averaging times of the time-domain signals can be reduced by as much as 2 orders of magnitude, while retaining the fidelity of the underlying signals, in comparison with noiseless reference signals. We have achieved excellent signal recovery when the initial noisy signal has an SNR ≳ 3. This approach is robust and is expected to be applicable to other time-domain spectroscopies. In PDS, these time-domain signals representing the dipolar interaction between two electron spin labels are converted into their distance distribution functions P(r), usually by regularization methods such as Tikhonov regularization. The significant improvements achieved by using denoised signals for this regularization are described. We show that they yield P(r)'s with more accurate detail and yield clearer separations of respective distances, which is especially important when the P(r)'s are complex. Also, longer distance P(r)'s, requiring longer dipolar evolution times, become accessible after denoising. In comparison to standard wavelet denoising approaches, it is clearly shown that the new method (WavPDS) is superior.

  18. Advanced neutron imaging methods with a potential to benefit from pulsed sources

    NASA Astrophysics Data System (ADS)

    Strobl, M.; Kardjilov, N.; Hilger, A.; Penumadu, D.; Manke, I.

    2011-09-01

    During the last decade neutron imaging has seen significant improvements in instrumentation, detection and spatial resolution. Additionally, a variety of new applications and methods have been explored. As a consequence of an outstanding development nowadays various techniques of neutron imaging go far beyond a two- and three-dimensional mapping of the attenuation coefficients for a broad range of samples. Neutron imaging has become sensitive to neutron scattering in the small angle scattering range as well as with respect to Bragg scattering. Corresponding methods potentially provide spatially resolved and volumetric data revealing microstructural inhomogeneities, texture variations, crystalline phase distributions and even strains in bulk samples. Other techniques allow for the detection of refractive index distribution through phase sensitive measurements and the utilization of polarized neutrons enables radiographic and tomographic investigations of magnetic fields and properties as well as electrical currents within massive samples. All these advanced methods utilize or depend on wavelength dependent signals, and are hence suited to profit significantly from pulsed neutron sources as will be discussed.

  19. Improvement of the identification of multiwall carbon nanotubes carpet thermal conductivity by pulsed photothermal method

    SciTech Connect

    Amin-Chalhoub, E.; Wattieaux, G.; Semmar, N.; Gaillard, M.; Petit, A.; Leborgne, C.

    2012-11-01

    Thermal properties in multiwall carbon nanotubes carpets and micro-devices are investigated using a nanosecond photothermal method. Gradually, the identification model and experimental protocol are performed to increase the method accuracy for the thermal conductivity determination. In the experimental protocol, a nanosecond UV monopulse laser beam is used to heat the surface of a multilayer (600 nm of Ti/20 {mu}m of carbon nanotube carpet) sample. In the 1D identification model with two layers and a thermal contact resistance, the effect of the laser excitation temporal shape is taken into account. In this study, this first approach allows to improve the accuracy of apparent thermal conductivity measurements of multiwall carbon nanotubes carpet. The carbon nanotubes carpet apparent thermal conductivity value went from being to 180 {+-} 5 W Multiplication-Sign m{sup -1} Multiplication-Sign K{sup -1}. In the second approach, two laser beams are coupled in order to increase the interaction time duration from 27 ns to 60 ns. It becomes possible to probe different depths in the carpet. The obtained value (180 W Multiplication-Sign m{sup -1} Multiplication-Sign K{sup -1}) confirms the pulsed photothermal method consistency for porous samples. Finally, assuming that the carbon nanotubes are parallel and without any defects, the equivalent intrinsic thermal conductivity of a single carbon nanotube is estimated to be around 3600 W Multiplication-Sign m{sup -1} Multiplication-Sign K{sup -1}.

  20. CONTROLLING THE CHARACTERISTICS OF LASER LIGHT: Possibility of generating femtosecond laser pulses by a deflection method

    NASA Astrophysics Data System (ADS)

    Isaakyan, A. R.; Kolchin, K. V.; Makshantsev, B. I.

    1993-05-01

    The transmission of a laser beam through a multiple-prism traveling-wave deflector is examined theoretically. Femtosecond laser pulses can be generated through the use of such a deflector. Possibilities for using a deflector to measure the shape of pulses with a femtosecond time resolution are discussed.

  1. Improvement of the method to estimate the relative reaction rate constants of hydroxyl radical with polyphenols using ESR spin trap: X-ray irradiation of water with a flowing system.

    PubMed

    Nakagawa, Seiko

    2017-09-05

    UV-photolysis of hydrogen peroxide is a useful technique to produce hydroxyl radical. However, it is not an appropriate method to estimate the reactivity of polyphenols with hydroxyl radicals because many of the polyphenol derivatives also absorb the UV-light to generate hydroxyl radicals. In this study, X-ray irradiation of water with a flowing system was applied to estimate the reactivity of hydroxyl radicals with polyphenols using electron spin resonance (ESR) spin trap. The obtained relative reaction rates reasonably agreed with previous data by pulse radiolysis. This method will be a useful technique to estimate the reactivity of antioxidants including polyphenols with hydroxyl radicals.

  2. HPLC method validation for Digitalis and its analogue by pulsed amperometric detection.

    PubMed

    Kwon, Ha-Jeong; Sim, Hee-Jung; Lee, Sa-im; Lee, Yong-Moon; Park, Yong-Duk; Hong, Seon-Pyo

    2011-01-05

    We developed a highly sensitive and selective reversed-phase HPLC-pulsed amperometric detection (RP-HPLC-PAD) method for cardiac glycoside detection. Eight cardiac glycosides were completely separated within 45 min on a reversed-phase column using a water-acetonitrile gradient, and were detected using a PAD under NaOH alkaline conditions. The detection (S/N=3) and quantification (S/N=10) limits for the cardiac glycosides were 0.1-0.3 and 0.3-0.8 ng, respectively. The linear regression coefficient was 0.9962-0.9998 for concentrations of 1-25 μg/mL. Cardiac glycosides in the Digitalis purpurea leaf displayed intra- and inter-day precisions (RSDs) of <9.30% and average recoveries of 98.63-99.94%. The contents of gitoxin, digitonin, and digitoxin in the D. purpurea were 0.197, 0.11, and 0.379 mg/g for leaf dried at 60 °C, 0.058, 0.11, and 0.090 mg/g for leaf dried at ambient temperature, and N.D. (not detected), and 18.379 mg/g, N.D. for seed, respectively. We conclude that our method shows good precision and accuracy.

  3. Four methods of evaluation of facial erythema and pigment treated with intense pulsed light or cream.

    PubMed

    Hassan, Havva; Lowe, Nicholas J; Barlow, Richard; Harris, David

    2012-08-01

    To evaluate methods of evaluation of patients with mild to moderate facial pigmentation or erythema and compare clinical and photographic grading with instrumental evaluation. Of the 24 female subjects treated, 12 were treated with intense pulsed light (IPL) and 12 were treated with daily cream program. Evaluations before and at 16 weeks consisted of: 1. Clinical examination and severity grading by a dermatologist without knowledge of treatment given. 2. Standardised photographs were evaluated by two other dermatologists without knowledge of treatment given. 3. A computer controlled photographic skin analysis systems was used to grade severity of erythema and pigmentation. 4. Subjects were asked to assess their response at the end of a 16-week period, that is, subject self-evaluation. On clinical evaluation of IPL subjects, 12 showed improvement. Of the cream subjects, 11 showed improvement. There was correlation between dermatologist facial examination and the instrumental method. Overall the different assessments showed a slightly greater trend for improvement with IPL treatments for erythema and pigmentation, but no statistical differences were found between the treatments using Student's t-test and Anova analysis of comparative improvement.

  4. A method for determining transverse permeability of tight reservoir cores by radial pressure pulse decay measurement

    NASA Astrophysics Data System (ADS)

    Yang, Zehao; Dong, Mingzhe; Zhang, Shaojie; Gong, Houjian; Li, Yajun; Long, Feifei

    2016-10-01

    A transverse pressure pulse decay (TPPD) method is presented to measure transverse permeability of tight reservoir cores in a cell with finite volume. Given appropriate assumptions, a mathematical model based on the specially designed experiment is formulated, and its general solution is proposed. Early-time and late-time techniques are further presented for convenient postprocessing applications of experimental data. Meanwhile, sensitivity analysis of TPPD method is given. It is found that a good TPPD experimental principle can be obtained by adjusting test gas, experimental pressure, dimension of core sample, and volume ratio (λ). The volume ratio error (λerror) analysis reveals the following: (1) a larger λerror results in increased transverse permeability error (kerror); (2) the volume ratio (λ) is better not very close to 0.754; (3) when λ is equal to or greater than 1, the kerror resulting from λerror is monotonic decreasing as the volume ratio increases. In practice, λ is usually equal to or greater than 1 due to the very small pore volume of a tight core. But this does not mean that the volume ratio should be as large as possible. The reason for this is that a pressure transducer with higher resolution is needed to record pressure change. That means experimental apparatus is much more costly. And such a TPPD experiment requires a much longer time to attain the late-time straight line behavior. The best choice is to find an optimal balance point among experimental cost, time, and accuracy.

  5. Lattice Boltzmann method for short-pulsed laser transport in a multi-layered medium

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Yi, Hong-Liang; Tan, He-Ping

    2015-04-01

    We construct a lattice Boltzmann method (LBM) for transient radiative transfer in one-dimensional multi-layered medium with distinct refractive index in each layer. The left boundary is irradiated normally by a short-pulsed laser. The Fresnel interfaces conditions, which incorporate reflection and refraction, are used at the boundaries and the interfaces. Based on the Fresnel's law and Snell's law, the interfacial intensity formulas are introduced. The collimated and diffuse intensities are treated individually. At a transient time step, the collimated component is first solved by LBM and then embedded into the transient radiative transfer equation as a source term. To keep the consistency of the directions in all the layers, angular interpolation of the intensities at the interfaces is adopted. The transient radiative transfer in a two-layer medium is first investigated, and the time-resolved results are validated by comparing with those by the Monte Carlo method (MCM). Of particular interest, the angular intensities along the slab at different times are presented to illustrate a variety of interesting phenomena, and the discontinuous nature of the intensity at the interfaces is discussed. The effects of various parameters on the time-resolved signals are examined.

  6. Fixed and pulsed gradient diffusion methods in low-field core analysis.

    PubMed

    Leu, Gabriela; Fordham, Edmund J; Hürlimann, Martin D; Frulla, Phil

    2005-02-01

    We review diffusion-weighted relaxation protocols for two-dimensional diffusion/relaxation time (D, T(2)) distributions and their application to fluid-saturated sedimentary rocks at low fields typical of oil-well logging tools (< or = 2 MHz for 1H). Fixed field gradient (FFG) protocols may be implemented in logging tools and in the laboratory; there, pulsed field gradient (PFG) protocols are also available. In either category, direct or stimulated echoes may be used for the diffusion evolution periods. We compare the results of several variant FFG and PFG protocols obtained on liquids and two contrasting sedimentary rocks. For liquids and rocks of negligible internal gradients (g(int)), results are comparable, as expected, for all the studied protocols. For rocks of strong g(int), protocol-dependent artifacts are seen in the joint (D, T2) distributions, consistent with the effects of the internal fields. For laboratory petrophysics, the PFG methods offer several advantages: (a) significantly improved signal-to-noise ratio and acquisition times for repetitions over many samples; (b) freedom from heteronuclear contamination when fluorinated liquids are used in core holders; and (c) a palette of variants--one comparable with the FFG--for the study of rocks of significant g(int). Given suitable hardware, both PFG and FFG methods can be implemented in the same bench-top apparatus, providing a versatile test bed for application in a petrophysical laboratory.

  7. Investigation of molecular mechanisms in photodynamic action and radiobiology with nanosecond flash photolysis and pulse radiolysis

    NASA Astrophysics Data System (ADS)

    Grossweiner, L. I.

    1981-06-01

    A formula was proposed for predicting enzyme inactivation quantum yields. The predictions were in good agreement with measurements on six important enzymes at 254 nm and 280 nm. Kinetics models were developed and tested for important stages in the photosensitization of DNA to near ultraviolet radiation by furocoumarin compounds currently used for PUVA therapy (psoralen plus UV-A) of psoriasis and other human skin diseases. Experiments on photobinding of psoralen (Ps) and 8-methoxypsoralen (8-MOP) to calf thymus DNA were consistent with the assumption that equilibrium dark complexing of the furocoumarin to the DNA is a precondition for the formation of covalent monoadducts and crosslinks. Singlet oxygen generation by furocoumarins has been investigated with liposomes and human erythrocytes (rbc). Results were obtained with 3-carbethoxypsoralen (3-CPs), and experimental alternate interacts with liposome and rbc membranes in the dark.

  8. Radiation induced primary processes of aqueous 8-methoxy-psoralen. A pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Solar, S.; Quint, R.

    The spectroscopic characteristics as well as the formation and decay kinetics of the 8-MOP radical cation (8-MOP .+), radical anion (8-MOP .-), H-adduct (8-MOP.H) and OH-adduct (8-MOP.OH) are presented.

  9. Breast mass segmentation in digital mammography based on pulse coupled neural network and level set method

    NASA Astrophysics Data System (ADS)

    Xie, Weiying; Ma, Yide; Li, Yunsong

    2015-05-01

    A novel approach to mammographic image segmentation, termed as PCNN-based level set algorithm, is presented in this paper. Just as its name implies, a method based on pulse coupled neural network (PCNN) in conjunction with the variational level set method for medical image segmentation. To date, little work has been done on detecting the initial zero level set contours based on PCNN algorithm for latterly level set evolution. When all the pixels of the input image are fired by PCNN, the small pixel value will be a much more refined segmentation. In mammographic image, the breast tumor presents big pixel value. Additionally, the mammographic image with predominantly dark region, so that we firstly obtain the negative of mammographic image with predominantly dark region except the breast tumor before all the pixels of an input image are fired by PCNN. Therefore, in here, PCNN algorithm is employed to achieve mammary-specific, initial mass contour detection. After that, the initial contours are all extracted. We define the extracted contours as the initial zero level set contours for automatic mass segmentation by variational level set in mammographic image analysis. What's more, a new proposed algorithm improves external energy of variational level set method in terms of mammographic images in low contrast. In accordance with the gray scale of mass region in mammographic image is higher than the region surrounded, so the Laplace operator is used to modify external energy, which could make the bright spot becoming much brighter than the surrounded pixels in the image. A preliminary evaluation of the proposed method performs on a known public database namely MIAS, rather than synthetic images. The experimental results demonstrate that our proposed approach can potentially obtain better masses detection results in terms of sensitivity and specificity. Ultimately, this algorithm could lead to increase both sensitivity and specificity of the physicians' interpretation of

  10. Method specificity of non-invasive blood pressure measurement: oscillometry and finger pulse pressure vs acoustic methods.

    PubMed Central

    De Mey, C; Schroeter, V; Butzer, R; Roll, S; Belz, G G

    1995-01-01

    1. The agreement of blood pressure measurements by stethoscope auscultation (SBPa, DBPa-IV and DBPa-V), oscillometry (Dinamap; SBPo, and DBPo) and digital photoplethysmography (Finapres; SBPf, and DBPf) with the graphical analysis of the analogue microphone signals of vascular wall motion sound (SBPg and DBPg) was evaluated in eight healthy subjects in the presence of responses to the intravenous infusion of 1 microgram min-1 isoprenaline. 2. In general, there was good agreement between the SBP/DBP-measurements based on auscultatory Korotkoff-I- and IV-criteria and the reference method; the average method difference in estimating the isoprenaline responses for SBPa-SBPg was: -1.1, 95% CI: -5.4 to 3.1 mm Hg with a within-subject between-method repeatability coefficient (REP) of 11.6 mm Hg and for DBPa-IV-DBPg: 3.5, 95% CI: -0.5 to 6.5 mm Hg, REP: 11.5 mm Hg. The ausculatation of Korotkoff-V substantially overestimated the isoprenaline induced reduction of DBP: method difference DBPa-V-DBPg: -11.3, 95% CI: -17.8 to -4.7 mm Hg, REP: 31.8 mm Hg. 3. Oscillometry yielded good approximations for the SBP response to isoprenaline (average method difference SBPo-SBPg: -2.9, 95% CI: -9.0 to 3.3 mm Hg, REP: 17.6 mm Hg) but was poorly sensitive with regard to the DBP responses: method difference DBPo-DBPg: 6.5, 95% CI: -1.3 to 14.3 mm Hg, REP: 25.7 mm Hg. 4. Whilst the finger pulse pressure agreed well with regard to DBP (method difference for the DBP responses to isoprenaline: DBPf-DBPg: 1.8, 95% CI: -5.1 to 8.6 mm Hg, REP: 18.5 mm Hg) it was rather unsatisfactory with regard to SBP (method difference SBPf-SBPg: -14.1, 95% CI: -28.2 to -0.1 mm Hg, REP: 49.9 mm Hg).(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8554929

  11. Phase retrieval and time-frequency methods in the measurement of ultrashort laser pulses

    SciTech Connect

    DeLong, K.W.; Fittinghoff, D.N.; Ladera, C.L.; Trebino, R.

    1995-02-01

    Recently several techniques have become available to measure the time- (or frequency-) dependent intensity and phase of ultrashort laser pulses. One of these, Frequency-Resolved Optical Gating (FROG), is rigorous and has achieved single-laser-shot operation. FROG combines the concepts of time-frequency analysis in the form of spectrogram generation (in order to create a two-dimensional problem), and uses a phase-retrieval-based algorithm to invert the experimental data to yield the intensity and phase of the laboratory laser pulse. In FROG it is easy to generate a spectrogram of the unknown signal, and inversion of the spectrogram to recover the signal is the main goal. Because the temporal width of a femtosecond laser pulse is much shorter than anything achievable by electronics, FROG uses the pulse to measure itself. In FROG, the laser pulse is split into two replicas of itself by a partially reflecting beamsplitter, and the two replicas interact with each other in a medium with an instantaneous nonlinear-optical response. This interaction generates a signal field that is then frequency-resolved using a spectrometer. The spectrum of the signal field is measured for all relevant values of the temporal delay between the two pulses. Here, the authors employ FROG and FROG related techniques to measure the time-dependent intensity and phase of an ultrashort laser pulse.

  12. Non-contact thrust stand calibration method for repetitively pulsed electric thrusters.

    PubMed

    Wong, Andrea R; Toftul, Alexandra; Polzin, Kurt A; Pearson, J Boise

    2012-02-01

    A thrust stand calibration technique for use in testing repetitively pulsed electric thrusters for in-space propulsion has been developed and tested using a modified hanging pendulum thrust stand. In the implementation of this technique, current pulses are applied to a solenoid to produce a pulsed magnetic field that acts against a permanent magnet mounted to the thrust stand pendulum arm. The force on the magnet is applied in this non-contact manner, with the entire pulsed force transferred to the pendulum arm through a piezoelectric force transducer to provide a time-accurate force measurement. Modeling of the pendulum arm dynamics reveals that after an initial transient in thrust stand motion the quasi-steady average deflection of the thrust stand arm away from the unforced or "zero" position can be related to the average applied force through a simple linear Hooke's law relationship. Modeling demonstrates that this technique is universally applicable except when the pulsing period is increased to the point where it approaches the period of natural thrust stand motion. Calibration data were obtained using a modified hanging pendulum thrust stand previously used for steady-state thrust measurements. Data were obtained for varying impulse bit at constant pulse frequency and for varying pulse frequency. The two data sets exhibit excellent quantitative agreement with each other. The overall error on the linear regression fit used to determine the calibration coefficient was roughly 1%.

  13. Non-contact thrust stand calibration method for repetitively pulsed electric thrusters

    NASA Astrophysics Data System (ADS)

    Wong, Andrea R.; Toftul, Alexandra; Polzin, Kurt A.; Pearson, J. Boise

    2012-02-01

    A thrust stand calibration technique for use in testing repetitively pulsed electric thrusters for in-space propulsion has been developed and tested using a modified hanging pendulum thrust stand. In the implementation of this technique, current pulses are applied to a solenoid to produce a pulsed magnetic field that acts against a permanent magnet mounted to the thrust stand pendulum arm. The force on the magnet is applied in this non-contact manner, with the entire pulsed force transferred to the pendulum arm through a piezoelectric force transducer to provide a time-accurate force measurement. Modeling of the pendulum arm dynamics reveals that after an initial transient in thrust stand motion the quasi-steady average deflection of the thrust stand arm away from the unforced or "zero" position can be related to the average applied force through a simple linear Hooke's law relationship. Modeling demonstrates that this technique is universally applicable except when the pulsing period is increased to the point where it approaches the period of natural thrust stand motion. Calibration data were obtained using a modified hanging pendulum thrust stand previously used for steady-state thrust measurements. Data were obtained for varying impulse bit at constant pulse frequency and for varying pulse frequency. The two data sets exhibit excellent quantitative agreement with each other. The overall error on the linear regression fit used to determine the calibration coefficient was roughly 1%.

  14. Methods of Optimal Control of Laser-Plasma Instabilities Using Spike Trains of Uneven Duration and Delay (STUD Pulses)

    NASA Astrophysics Data System (ADS)

    Afeyan, Bedros

    2013-10-01

    We have recently introduced and extensively studied a new adaptive method of LPI control. It promises to extend the effectiveness of laser as inertial fusion drivers by allowing active control of stimulated Raman and Brillouin scattering and crossed beam energy transfer. It breaks multi-nanosecond pulses into a series of picosecond (ps) time scale spikes with comparable gaps in between. The height and width of each spike as well as their separations are optimization parameters. In addition, the spatial speckle patterns are changed after a number of successive spikes as needed (from every spike to never). The combination of these parameters allows the taming of parametric instabilities to conform to any desired reduced reflectivity profile, within the bounds of the performance limitations of the lasers. Instead of pulse shaping on hydrodynamical time scales, far faster (from 1 ps to 10 ps) modulations of the laser profile will be needed to implement the STUD pulse program for full LPI control. We will show theoretical and computational evidence for the effectiveness of the STUD pulse program to control LPI. The physics of why STUD pulses work and how optimization can be implemented efficiently using statistical nonlinear optical models and techniques will be explained. We will also discuss a novel diagnostic system employing STUD pulses that will allow the boosted measurement of velocity distribution function slopes on a ps time scale in the small crossing volume of a pump and a probe beam. Various regimes from weak to strong coupling and weak to strong damping will be treated. Novel pulse modulation schemes and diagnostic tools based on time-lenses used in both microscope and telescope modes will be suggested for the execution of the STUD pule program. Work Supported by the DOE NNSA-OFES Joint Program on HEDLP and DOE OFES SBIR Phase I Grants.

  15. Application of the Hartmann method in the investigation of the profile of wavefronts of high-power pulsed lasers

    SciTech Connect

    L`vov, L.V.; Merkulov, S.G.; Ozerov, M.A.

    1994-11-01

    The Hartmann method was used in an investigation of the wavefront profile of the infrared radiation emitted by high-power pulsed lasers. The wavefront profiles were studied for the iodine lasers used in the ISKRA-4 and ISKRA-5 facilities. 5 refs., 3 figs.

  16. Method and apparatus for fine tuning an orifice pulse tube refrigerator

    DOEpatents

    Swift, Gregory W.; Wollan, John J.

    2003-12-23

    An orifice pulse tube refrigerator uses flow resistance, compliance, and inertance components connected to a pulse tube for establishing a phase relationship between oscillating pressure and oscillating velocity in the pulse tube. A temperature regulating system heats or cools a working gas in at least one of the flow resistance and inertance components. A temperature control system is connected to the temperature regulating system for controlling the temperature of the working gas in the at least one of the flow resistance and inertance components and maintains a control temperature that is indicative of a desired temporal phase relationship.

  17. Method of production H/sub 2/ using a rotating drum reactor with a pulse jet heat source

    DOEpatents

    Paulson, L.E.

    1988-05-13

    A method of producing hydrogen by an endothermic steam-carbon reaction using a rotating drum reactor and a pulse jet combustor. The pulse jet combustor uses coal dust as a fuel to provide reaction temperatures of 1300/degree/ to 1400/degree/F. Low-rank coal, water, limestone and catalyst are fed into the drum reactor where they are heated, tumbled and reacted. Part of the reaction product from the rotating drum reactor is hydrogen which can be utilized in suitable devices. 1 fig.

  18. Method of generating a mega-ampere current pulse to accelerate a liner by a magnetic field

    NASA Astrophysics Data System (ADS)

    Duday, P. V.; Zimenkov, A. A.; Ivanov, V. A.; Kraev, A. I.; Pak, S. V.; Skobelev, A. N.; Fevralev, A. Yu.

    2015-01-01

    This paper describes a method and device for generating a mega-ampere quasi-trapezoidal current pulse of given amplitude and duration in a liner load. The experimental device consisting of a current source based on a helical explosive magnetic generator (HEMG) produced a current pulse in the liner load with an amplitude of ≈ 10 MA and controlled duration and current rise and decay times. The use of this source to accelerate cylindrical liners allows the study of the mechanisms of material damage in converging geometry, in which new damage effects may occur due to the multidimensional nature of the loading conditions.

  19. [Calculation and analysis of arc temperature field of pulsed TIG welding based on Fowler-Milne method].

    PubMed

    Xiao, Xiao; Hua, Xue-Ming; Wu, Yi-Xiong; Li, Fang

    2012-09-01

    Pulsed TIG welding is widely used in industry due to its superior properties, and the measurement of arc temperature is important to analysis of welding process. The relationship between particle densities of Ar and temperature was calculated based on the theory of spectrum, the relationship between emission coefficient of spectra line at 794.8 nm and temperature was calculated, arc image of spectra line at 794.8 nm was captured by high speed camera, and both the Abel inversion and Fowler-Milne method were used to calculate the temperature distribution of pulsed TIG welding.

  20. Gamma-Radiolysis of Cysteine-Cysteamine Disulfide in Aqueous Solution,

    DTIC Science & Technology

    Gamma-radiolysis of a mixed disulfide, cysteine- cysteamine disulfide, in unbuffered aqueous solution (0.3 mM) was investigated in the presence and...absence of oxygen. The principal products were the thiols (cysteine and cysteamine ), the corresponding sulfinic and sulfonic acids, the symmetrical

  1. Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions.

    PubMed

    Horne, Gregory P; Donoclift, Thomas A; Sims, Howard E; Orr, Robin M; Pimblott, Simon M

    2016-11-17

    A multiscale modeling approach has been developed for the extended time scale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages: radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modeling. The first three components model the physical and chemical evolution of an isolated radiation chemical track and provide radiolysis yields, within the extremely low dose isolated track paradigm, as the input parameters for a bulk deterministic chemistry model. This approach to radiation chemical modeling has been tested by comparison with the experimentally observed yield of nitrite from the gamma radiolysis of sodium nitrate solutions. This is a complex radiation chemical system which is strongly dependent on secondary reaction processes. The concentration of nitrite is not just dependent upon the evolution of radiation track chemistry and the scavenging of the hydrated electron and its precursors but also on the subsequent reactions of the products of these scavenging reactions with other water radiolysis products. Without the inclusion of intratrack chemistry, the deterministic component of the multiscale model is unable to correctly predict experimental data, highlighting the importance of intratrack radiation chemistry in the chemical evolution of the irradiated system.

  2. Radical ions and excited states in radiolysis. Optically detected time resolved EPR

    SciTech Connect

    Trifunac, A.D.; Smith, J.P.

    1981-01-01

    Excited-state production and radical-ion recombination kinetics in pulse-irradiated solutions of aromatic solutes in cyclohexane are studied by a new method of optical detection of time-resolved electron paramagnetic resonance (EPR) spectra. 7 figures.

  3. New pulsed EPR methods and their application to characterize mitochondrial complex I.

    PubMed

    Maly, Thorsten; Zwicker, Klaus; Cernescu, Adrian; Brandt, Ulrich; Prisner, Thomas F

    2009-06-01

    Electron Paramagnetic Resonance (EPR) spectroscopy is the method of choice to study paramagnetic cofactors that often play an important role as active centers in electron transfer processes in biological systems. However, in many cases more than one paramagnetic species is contributing to the observed EPR spectrum, making the analysis of individual contributions difficult and in some cases impossible. With time-domain techniques it is possible to exploit differences in the relaxation behavior of different paramagnetic species to distinguish between them and separate their individual spectral contribution. Here we give an overview of the use of pulsed EPR spectroscopy to study the iron-sulfur clusters of NADH:ubiquinone oxidoreductase (complex I). While FeS cluster N1 can be studied individually at a temperature of 30 K, this is not possible for FeS cluster N2 due to its severe spectral overlap with cluster N1. In this case Relaxation Filtered Hyperfine (REFINE) spectroscopy can be used to separate the overlapping spectra based on differences in their relaxation behavior.

  4. Are rivers just big streams? A pulse method to quantify nitrogen demand in a large river.

    PubMed

    Tank, Jennifer L; Rosi-Marshall, Emma J; Baker, Michelle A; Hall, Robert O

    2008-10-01

    Given recent focus on large rivers as conduits for excess nutrients to coastal zones, their role in processing and retaining nutrients has been overlooked and understudied. Empirical measurements of nutrient uptake in large rivers are lacking, despite a substantial body of knowledge on nutrient transport and removal in smaller streams. Researchers interested in nutrient transport by rivers (discharge >10000 L/s) are left to extrapolate riverine nutrient demand using a modeling framework or a mass balance approach. To begin to fill this knowledge gap, we present data using a pulse method to measure inorganic nitrogen. (N) transport and removal in the Upper Snake River, Wyoming, USA (seventh order, discharge 12000 L/s). We found that the Upper Snake had surprisingly high biotic demand relative to smaller streams in the same river network for both ammonium (NH4+) and nitrate (NO3-). Placed in the context of a meta-analysis of previously published nutrient uptake studies, these data suggest that large rivers may have similar biotic demand for N as smaller tributaries. We also found that demand for different forms of inorganic N (NH4+ vs. NO3-) scaled differently with stream size. Data from rivers like the Upper Snake and larger are essential for effective water quality management at the scale of river networks. Empirical measurements of solute dynamics in large rivers are needed to understand the role of whole river networks (as opposed to stream reaches) in patterns of nutrient export at regional and continental scales.

  5. Tribological performance of Cu-Ni alloy nanoparticles synthesized using a pulsed-wire evaporation method

    NASA Astrophysics Data System (ADS)

    Oh, Jeongseok; Rhee, Changkyu

    2008-08-01

    Cu-Ni alloy nanoparticles were produced using a pulsed-wire evaporation method in Ar gas. The synthesized Cu-Ni alloy nanoparticles had an average size of 150 nm, were spherical in shape and agglomerated. We investigated the tribological propeties of dispersion-stabilized Cu-Ni alloy nanoparticles when used as a solid lubricant in oil at ambient temperature. The sedimentation behavior of Cu-Ni alloy nanoparticles in oil was examined using Turbiscan LAb. The particles were clearly quantified using delta backscattering profiles and peak thickness kinetics as functions of time. The rubbing surfaces were characterized after a friction test using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). We found that dispersed Cu-Ni nanoparticles as a solid lubricant in oil had superior dispersion stability properties for over 48 h. Dispersed Cu nanoparticles in oil showed a low friction coefficient and good wear rate compared to oil only. Dispersed Cu-Ni alloy nanoparticles had superior friction reduction and antiwear properties compared to Cu nanoparticles, and these effects increased with the Ni content in the alloy. However, non-dispersed Cu-Ni alloy nanoparticles had poor antiwear properties. Dispersion-stabilized Cu-Ni alloy nanoparticles in oil enhanced the rolling effect of spherical nanoparticles between rubbing surfaces during friction processes.

  6. Designing Pulse Laser Surface Modification of H13 Steel Using Response Surface Method

    NASA Astrophysics Data System (ADS)

    Aqida, S. N.; Brabazon, D.; Naher, S.

    2011-01-01

    This paper presents a design of experiment (DOE) for laser surface modification process of AISI H13 tool steel in achieving the maximum hardness and minimum surface roughness at a range of modified layer depth. A Rofin DC-015 diffusion-cooled CO2 slab laser was used to process AISI H13 tool steel samples. Samples of 10 mm diameter were sectioned to 100 mm length in order to process a predefined circumferential area. The parameters selected for examination were laser peak power, overlap percentage and pulse repetition frequency (PRF). The response surface method with Box-Behnken design approach in Design Expert 7 software was used to design the H13 laser surface modification process. Metallographic study and image analysis were done to measure the modified layer depth. The modified surface roughness was measured using two-dimensional surface profilometer. The correlation of the three laser processing parameters and the modified surface properties was specified by plotting three-dimensional graph. The hardness properties were tested at 981 mN force. From metallographic study, the laser modified surface depth was between 37 μm and 150 μm. The average surface roughness recorded from the 2D profilometry was at a minimum value of 1.8 μm. The maximum hardness achieved was between 728 and 905 HV0.1. These findings are significant to modern development of hard coatings for wear resistant applications.

  7. Determination of lithium sulphur batteries internal resistance by the pulsed method during galvanostatic cycling

    NASA Astrophysics Data System (ADS)

    Kolosnitsyn, V. S.; Kuzmina, E. V.; Mochalov, S. E.

    2014-04-01

    The pulsed method of measuring impedance is described. The cell is galvanostatically stimulated by a bipolar current signal of square shape. The cell response is registered by sampling U+[i], U-[i] with selected period Δt. The impedance spectra are calculated by direct Fourier transform. The internal resistance of the lithium sulphur cell is characteristically minimum in the calculated impedance diagrams in the frequency range of 0.035-5 Hz. It is shown that the lithium sulphur cells have maximum internal resistance at the transient between high and low voltage plateaus of charge and discharge curves. The internal resistance increases significantly during the initial stages of cycling because of the formation of passivation layers at the electrodes. It was found that the internal resistance of the lithium sulphur cell in the same charge state is governed by the way in which it is achieved. This is explained by differences in molar volumes of products generated in the sulphur electrode by electrochemical reaction during charging and discharging.

  8. A noncontacting method for measuring sheet grammage and thickness using acoustic pulse techniques

    NASA Astrophysics Data System (ADS)

    Vuohelainen, Reijo Antero

    A new way to use an acoustic pulse transmission method to measure the basis weight and the thickness of paper and other thin materials was developed. The apparatus consisted of a sound source, a microphone, a digital oscilloscope, and a microcomputer. A short acoustic tone burst is transmitted through the sample and the transmission loss is defined as the ratio of the receiver voltage amplitude measured with the sample present to the voltage amplitude measured without the sample. This attenuation is a function of the basis weight of the sample and of the frequency used in the measurement. Different types of paper and plastic foils were measured with good accuracy. The measurement frequencies vary from 5 kHz to 40 kHz depending on the sample parameters. With the optimum frequency for the specific sample the accuracy is about +/-1% and the resolution is 0.5% of the grammage of the sample. This system can be used to measure both transparent and opaque foils, which makes it useful for many industrial and laboratory applications.

  9. Designing Pulse Laser Surface Modification of H13 Steel Using Response Surface Method

    SciTech Connect

    Aqida, S. N.; Brabazon, D.; Naher, S.

    2011-01-17

    This paper presents a design of experiment (DOE) for laser surface modification process of AISI H13 tool steel in achieving the maximum hardness and minimum surface roughness at a range of modified layer depth. A Rofin DC-015 diffusion-cooled CO{sub 2} slab laser was used to process AISI H13 tool steel samples. Samples of 10 mm diameter were sectioned to 100 mm length in order to process a predefined circumferential area. The parameters selected for examination were laser peak power, overlap percentage and pulse repetition frequency (PRF). The response surface method with Box-Behnken design approach in Design Expert 7 software was used to design the H13 laser surface modification process. Metallographic study and image analysis were done to measure the modified layer depth. The modified surface roughness was measured using two-dimensional surface profilometer. The correlation of the three laser processing parameters and the modified surface properties was specified by plotting three-dimensional graph. The hardness properties were tested at 981 mN force. From metallographic study, the laser modified surface depth was between 37 {mu}m and 150 {mu}m. The average surface roughness recorded from the 2D profilometry was at a minimum value of 1.8 {mu}m. The maximum hardness achieved was between 728 and 905 HV{sub 0.1}. These findings are significant to modern development of hard coatings for wear resistant applications.

  10. Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report, [March 1992--March 1993

    SciTech Connect

    Neta, P.

    1993-04-01

    Electron transfer and other reactions of various short-lived intermediates have been studied by pulse radiolysis and laser flash photolysis. Highlights of results during the past year are summarized under two main sections: Metalloporphyrin electron transfer and associated reactions, and solvent effects on reactions of inorganic radicals and organic peroxyl radicals.

  11. Cargo and Container X-Ray Inspection with Intra-Pulse Multi-Energy Method for Material Discrimination

    NASA Astrophysics Data System (ADS)

    Saverskiy, Aleksandr Y.; Dinca, Dan-Cristian; Rommel, J. Martin

    The Intra-Pulse Multi-Energy (IPME) method of material discrimination mitigates main disadvantages of the traditional "interlaced" approach: ambiguity caused by sampling different regions of cargo and reduction of effective scanning speed. A novel concept of creating multi-energy probing pulses using a standing-wave structure allows maintaining a constant energy spectrum while changing the time duration of each sub-pulse and thus enables adaptive cargo inspection. Depending on the cargo density, the dose delivered to the inspected object is optimized for best material discrimination, maximum material penetration, or lowest dose to cargo. A model based on Monte-Carlo simulation and experimental reference points were developed for the optimization of inspection conditions.

  12. A dealiasing method for use with ultrasonic pulsed Doppler in measuring velocity profiles and flow rates in pipes

    NASA Astrophysics Data System (ADS)

    Murakawa, Hideki; Muramatsu, Ei; Sugimoto, Katsumi; Takenaka, Nobuyuki; Furuichi, Noriyuki

    2015-08-01

    The ultrasonic pulsed Doppler method (UDM) is a powerful tool for measuring velocity profiles in a pipe. However, the maximum detectable velocity is limited by the Nyquist sampling theorem. Furthermore, the maximum detectable velocity (also called Nyquist velocity), vmax, and the maximum measurable length are related and cannot be increased at the same time. If the velocity is greater than vmax, velocity aliasing occurs. Hence, the higher velocity that occurs with a larger pipe diameter, i.e. under higher flow rate conditions, cannot be measured with the conventional UDM. To overcome these limitations, dual-pulse repetition frequency (dual PRF) and feedback methods were employed in this study to measure velocity profiles in a pipe. The velocity distributions obtained with the feedback method were found to be more accurate than those obtained with the dual PRF method. However, misdetection of the Nyquist folding number using the feedback method was found to increase with the flow velocity. A feedback method with a moving average is proposed to improve the measurement accuracy. The method can accurately measure the velocity distributions at a velocity five times greater than the maximum velocity that can be measured with the conventional UDM. The measurement volume was found to be among the important parameters that must be considered in assessing the traceability of the reflector during the pulse emission interval. Hence, a larger measurement volume is required to measure higher velocities using the dual PRF method. Integrating velocity distributions measured using the feedback method with a moving average makes it possible to accurately determine flow rates six times greater than those that can be determined using the conventional pulsed Doppler method.

  13. Method and means for generating a synchronizing pulse from a repetitive wave of varying frequency

    DOEpatents

    DeVolpi, Alexander; Pecina, Ronald J.; Travis, Dale J.

    1976-01-01

    An event that occurs repetitively at continuously changing frequencies can be used to generate a triggering pulse which is used to synchronize or control. The triggering pulse is generated at a predetermined percentage of the period of the repetitive waveform without regard to frequency. Counts are accumulated in two counters, the first counting during the "on" fraction of the period, and the second counting during the "off" fraction. The counts accumulated during each cycle are compared. On equality the trigger pulse is generated. Count input rates to each counter are determined by the ratio of the on-off fractions of the event waveform and the desired phase relationship. This invention is of particular utility in providing a trigger or synchronizing pulse during the open period of the shutter of a high-speed framing camera during its acceleration as well as its period of substantially constant speed.

  14. Solid cartridge for a pulse weld forming electrode and method of joining tubular members

    DOEpatents

    Bonnen, John Joseph Francis; Golovashchenko, Sergey Fedorovich; Mamutov, Alexander; Maison, Lloyd Douglas; Dawson, Scott Alwyn; deVries, James

    2016-02-23

    A cartridge assembly is disclosed for a pulse welding a first tube supported on a mandrel to a second tube. An outer tool is assembled over the second tube and a stored charge is discharged in the cartridge assembly. The cartridge comprises an annular conductor and a solid casing enveloping the conductor. The stored charge is electrically connected to the conductor and discharged through the conductor to compress the second tube and pulse weld the second tube to the first tube.

  15. Determination of intrinsic mobility of a bilayer oxide thin-film transistor by pulsed I-V method.

    PubMed

    Woo, Hyunsuk; Kim, Taeho; Hur, Jihyun; Jeon, Sanghun

    2017-04-28

    Amorphous oxide semiconductor thin-film transistors (TFT) have been considered as outstanding switch devices owing to their high mobility. However, because of their amorphous channel material with a certain level of density of states, a fast transient charging effect in an oxide TFT occurs, leading to an underestimation of the mobility value. In this paper, the effects of the fast charging of high-performance bilayer oxide semiconductor TFTs on mobility are examined in order to determine an accurate mobility extraction method. In addition, an approach based on a pulse I D -V G measurement method is proposed to determine the intrinsic mobility value. Even with the short pulse I D -V G measurement, a certain level of fast transient charge trapping cannot be avoided as long as the charge-trap start time is shorter than the pulse rising time. Using a pulse-amplitude-dependent threshold voltage characterization method, we estimated a correction factor for the apparent mobility, thus allowing us to determine the intrinsic mobility.

  16. Optimized pulses for Raman excitation through the continuum: Verification using the multiconfigurational time-dependent Hartree-Fock method

    NASA Astrophysics Data System (ADS)

    Greenman, Loren; Whaley, K. Birgitta; Haxton, Daniel J.; McCurdy, C. William

    2017-07-01

    We have verified a mechanism for Raman excitation of atoms through continuum levels previously obtained by quantum optimal control using the multiconfigurational time-dependent Hartree-Fock (MCTDHF) method. For the optimal control, which requires running multiple propagations to determine the optimal pulse sequence, we used the computationally inexpensive time-dependent configuration interaction singles (TDCIS) method. TDCIS captures all of the necessary correlation of the desired processes but assumes that ionization pathways reached via double excitations are not present. MCTDHF includes these pathways and all multiparticle correlations in a set of time-dependent orbitals. The mechanism that was determined to be optimal in the Raman excitation of the Ne 1 s22 s22 p53 p1 valence state via the metastable 1 s22 s12 p63 p1 resonance state involves a sequential resonance-valence excitation. First, a long pump pulse excites the core-hole state, and then a shorter Stokes pulse transfers the population to the valence state. This process represents the first step in a multidimensional x-ray spectroscopy scheme that will provide a local probe of valence electronic correlations. Although at the optimal pulse intensities at the TDCIS level of theory the MCTDHF method predicts multiple ionization or excitation ionization of the atom, at slightly lower intensities (reduced by a factor of about 4) the TDCIS mechanism is shown to hold qualitatively. Quantitatively, the MCTDHF populations are reduced from the TDCIS calculations by a factor of 4.

  17. Oxidation of UO 2 fuel by the products of gamma radiolysis of water

    NASA Astrophysics Data System (ADS)

    Sunder, S.; Shoesmith, D. W.; Christensen, H.; Miller, N. H.

    1992-08-01

    The kinetics of UO 2 fuel oxidation by the products of gamma radiolysis of water were studied as a function of absorbed dose rate. The oxidation of UO 2 during radiolysis was monitored by recording the corrosion potential of a UO 2 electrode as a function of time. Changes in the surface of UO 2 were determined using cathodic-stripping voltammetry (CSV) and X-ray photoelectron spectroscopy (XPS). The effects of specific radicals on UO 2 oxidation were determined by adding suitable scavengers to the solution to maximize the yield of a particular radical. The radical species formed during radiolysis of water are much more effective in causing UO 2 oxidation than the molecular oxidants formed during radiolysis of water or present in water from atmospheric sources. The oxidation of UO 2 in the presence of oxidants produced by the gamma radiolysis of water occurs in two distinct stages: (a) the formation of a thin layer ofUO 2 + x with a stoichiometry close to UO 2.33 and a thickness similar to that obtained (over longer exposure periods) in unirradiated oxygenated solutions; and (b) the subsequent oxidative dissolution of this surface layer to produce soluble U VI species and secondary phases, probably hydrated schoepite (UO 3 · xH 2O), on the UO 2 substrate. The first stage occurs in the potential range- 500 mV < E PCORR≲-100 mV (versus SCE). The second stage starts around ECORR˜- 100 mV and eventually achieves steady state at a value of ECORR determined by the gamma dose.

  18. A standardized method to determine the concentration of extracellular vesicles using tunable resistive pulse sensing

    PubMed Central

    Vogel, Robert; Coumans, Frank A. W.; Maltesen, Raluca G.; Böing, Anita N.; Bonnington, Katherine E.; Broekman, Marike L.; Broom, Murray F.; Buzás, Edit I.; Christiansen, Gunna; Hajji, Najat; Kristensen, Søren R.; Kuehn, Meta J.; Lund, Sigrid M.; Maas, Sybren L. N.; Nieuwland, Rienk; Osteikoetxea, Xabier; Schnoor, Rosalie; Scicluna, Benjamin J.; Shambrook, Mitch; de Vrij, Jeroen; Mann, Stephen I.; Hill, Andrew F.; Pedersen, Shona

    2016-01-01

    Background Understanding the pathogenic role of extracellular vesicles (EVs) in disease and their potential diagnostic and therapeutic utility is extremely reliant on in-depth quantification, measurement and identification of EV sub-populations. Quantification of EVs has presented several challenges, predominantly due to the small size of vesicles such as exosomes and the availability of various technologies to measure nanosized particles, each technology having its own limitations. Materials and Methods A standardized methodology to measure the concentration of extracellular vesicles (EVs) has been developed and tested. The method is based on measuring the EV concentration as a function of a defined size range. Blood plasma EVs are isolated and purified using size exclusion columns (qEV) and consecutively measured with tunable resistive pulse sensing (TRPS). Six independent research groups measured liposome and EV samples with the aim to evaluate the developed methodology. Each group measured identical samples using up to 5 nanopores with 3 repeat measurements per pore. Descriptive statistics and unsupervised multivariate data analysis with principal component analysis (PCA) were used to evaluate reproducibility across the groups and to explore and visualise possible patterns and outliers in EV and liposome data sets. Results PCA revealed good reproducibility within and between laboratories, with few minor outlying samples. Measured mean liposome (not filtered with qEV) and EV (filtered with qEV) concentrations had coefficients of variance of 23.9% and 52.5%, respectively. The increased variance of the EV concentration measurements could be attributed to the use of qEVs and the polydisperse nature of EVs. Conclusion The results of this study demonstrate the feasibility of this standardized methodology to facilitate comparable and reproducible EV concentration measurements. PMID:27680301

  19. Film dosimetry calibration method for pulsed-dose-rate brachytherapy with an 192Ir source.

    PubMed

    Schwob, Nathan; Orion, Itzhak

    2007-05-01

    192Ir sources have been widely used in clinical brachytherapy. An important challenge is to perform dosimetric measurements close to the source despite the steep dose gradient. The common, inexpensive silver halide film is a classic two-dimensional integrator dosimeter and would be an attractive solution for these dose measurements. The main disadvantage of film dosimetry is the film response to the low-energy photon. Since the photon energy spectrum is known to vary with depth, the sensitometric curves are expected to be dependent on depth. The purpose of this study is to suggest a correction method for silver halide film dosimetry that overcomes the response changes at different depths. Sensitometric curves have been obtained at different depths with verification film near a 1 Ci 192Ir pulsed-dose-rate source. The depth dependence of the film response was observed and a correction function was established. The suitability of the method was tested through measurement of the radial dose profile and radial dose function. The results were compared to Monte Carlo-simulated values according to the TG43 formalism. Monte Carlo simulations were performed separately for the beta and gamma source emissions, using the EGS4 code system, including the low-energy photon and electron transport optimization procedures. The beta source emission simulation showed that the beta dose contribution could be neglected and therefore the film-depth dependence could not be attributed to this part of the source radioactivity. The gamma source emission simulations included photon-spectra collection at several depths. The results showed a depth-dependent softening of the photon spectrum that can explain the film-energy dependence.

  20. Method for Thermal Spraying of Coatings Using Resonant-Pulsed Combustion

    NASA Technical Reports Server (NTRS)

    Paxson, Daniel E.

    2008-01-01

    A method has been devised for high-volume, high-velocity surface deposition of protective metallic coatings on otherwise vulnerable surfaces. Thermal spraying is used whereby the material to be deposited is heated to the melting point by passing through a flame. Rather than the usual method of deposition from the jet formed from the combustion products, this innovation uses non-steady combustion (i.e. high-frequency, periodic, confined bursts), which generates not only higher temperatures and heat transfer rates, but exceedingly high impingement velocities an order of magnitude higher than conventional thermal systems. Higher impingement rates make for better adhesion. The high heat transfer rates developed here allow the deposition material to be introduced, not as an expensive powder with high surface-area-to-volume, but in convenient rod form, which is also easier and simpler to feed into the system. The nonsteady, resonant combustion process is self-aspirating and requires no external actuation or control and no high-pressure supply of fuel or air. The innovation has been demonstrated using a commercially available resonant combustor shown in the figure. Fuel is naturally aspirated from the tank through the lower Tygon tube and into the pulsejet. Air for starting is ported through the upper Tygon tube line. Once operation commences, this air is no longer needed as additional air is naturally aspirated through the inlet. A spark plug on the device is needed for starting, but the process carries on automatically as the operational device is resonant and reignites itself with each 220-Hz pulse.